Professional Documents
Culture Documents
in Drinking Water
and Manganese Control
Subject Area:
High-Quality Water
Occurrence of Manganese
in Drinking Water
and Manganese Control
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Prepared by:
Paul M. Kohl
Philadelphia Water Department, Philadelphia, PA 19107
and
Steven J. Medlar
Camp Dresser & McKee Inc. (CDM), Philadelphia, PA 19102
Published by:
This study was jointly funded by the Awwa Research Foundation (AwwaRF) and the U.S. Environmental Protection
Agency (USEPA) under Cooperative Agreement No. R-82940901. AwwaRF and USEPA assume no responsibility
for the content of the research study reported in this publication or for the opinions or statements of fact expressed
in the report. The mention of trade names for commercial products does not represent or imply the approval or
endorsement of AwwaRF or USEPA. This report is presented solely for informational purposes.
Copyright 2006
by Awwa Research Foundation
FIGURES............................................................................................................................... xi
FOREWORD ......................................................................................................................... xv
vi
vii
viii
2.4 Analytical methods for determining manganese in water and environmental samples 27
3.1 Items shipped to each utility participating in the seasonal sampling study ............... 55
4.5 Analysis of source and finished water Mn concentration data from detailed surveys 87
4.6 U.S. region, source water type, and Mn treatment type for utilities
participating in distribution system occurrence sampling for Mn ................. 94
4.8 Results of correlation plots of Mn with other water quality parameters.................... 109
4.9 Number of occurrences of near Mn concentrations being more than entry........ 115
4.10 Condition of flow at sample tap for entry and near sample taps ............................... 116
4.11 Mass capture rate and % removal of Mn for IOCME process once chlorine is
terminated ..................................................................................................... 125
4.13 Avg. percent Mn removal by GAC and dual media filters depending upon
applied chlorine............................................................................................. 136
4.2 Types of source water treated by facilities in initial survey (n = 242) ...................... 69
4.6 Box-and-whiskers plot of average finished water Mn data from initial surveys....... 73
4.8 Facilities grouped by oxidant and oxidant combination within WTP ....................... 76
4.10 Types of source water treated by facilities in detailed survey (n = 52) ..................... 79
4.12 Type of primary coagulant used to treat water in detailed surveys (n = 52) ............. 80
xi
4.21 Seasonal distribution system testing: correlation of total Mn to various water quality
parameters collected at the entry, near, mid, and far points of the distribution
system ............................................................................................................ 107
4.22 Total Mn versus apparent color. The solid regression line is for all data, the
second, dashed regression omits the single data point at 25 color units and
0.131 mg/L Mn. ............................................................................................ 110
4.24 Mn that passes through a 0.22-m filter as a function of Mn that passes through a
30-kDa filter.................................................................................................. 111
4.29 Seasonal distribution system testing: correlation of total and dissolved manganese
at the distribution system near point to the entry poiny, and 1:1 line
reference line................................................................................................. 116
4.30 Seasonal distribution system testing: correlation of total and dissolved manganese
at the distribution system near point to the entry point, and 1:1 line
reference line.................................................................................................. 117
xii
4.37 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss
and pH on Mn control. .................................................................................. 127
4.38 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss
and pH on Mn control. .................................................................................. 128
4.39 Baxter pilot plant; Mn and EH as a function of time. Effect of chlorine loss
and pH on Mn control. .................................................................................. 129
4.40 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss
and pH on Mn control. .................................................................................. 130
4.41 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss
and pH on Mn control. .................................................................................. 131
4.42 Baxter pilot plant; Mn and EH as a function of time. Effect of chlorine loss
and pH on Mn control. .................................................................................. 132
4.43 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss
and pH on Mn control ................................................................................... 133
4.45 November 2004 full-scale Case Study II sample event ............................................. 141
4.46 December 2004 full-scale Case Study II sample event ............................................. 141
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The 242 utilities are not named in this report as part of the participation agreement
established at the initiation of the project. When this project started, security concerns were
prevalent and it was thought that utilities would be reluctant to participate. Therefore, it was
agreed that process information and water quality data would not be associated with water
utilitys name and location, therefore a numbering system was used instead. To all those utilities
that participated, the principle investigators (PIs) hereby acknowledge you, in anonymity, with
heart felt gratitude.
The help and advice provided by AwwaRF project manager Linda Reekie and the Project
Advisory Committee (PAC) including David Chang, Golden State Water Company, Christy
Muhlen, U.S. Environmental Protection Agency, Office of Research and Development, and
Steve Schindler, New York City Department of Environmental Protection are truly
appreciated.
The authors would like to thank our Technical Advisory Committee members, David
Dixon (Univ. of Melbourne), Phillippe Daniel (CDM), Chris Schultz (CDM), and Philip Singer
(Univ. of North Carolina).
The authors would lastly like to thank those who helped conduct interviews, run the pilot
plants, analyze samples, interpret data, write sections of the report, keep us on schedule, and sign
the contracts. Thanks to Amit Sen (CDM) and Steven Pugsley (PWD); John Consolvo, Nicole
Charlton, Matthew Smith, Doug Crawshaw, Shawn Garner, Philip Godorov, Gary Burlingame,
and Juliana Appiah (PWD); Nick Maxin, Larry Smith, Theodore Schlette, Mack Rugg, Miles
Ehrlich, and Christina Davis (CDM); David Hambly (Anthratec Western Inc.), and Fred Pontius
(Pontius Consultants).
xvii
BACKGROUND
We interviewed many drinking water utilities over a wide geographic area to explore the
industrys general understanding of manganese (i.e., issues, treatment, and occurrence). We
found that few utilities fully understand the chemistry, treatment, and problems associated with
manganese. This is not surprising, as Mn chemistry is very complex and the understanding of the
realm of chemical/biological interactions within the distribution system is an emerging issue.
The trends in water treatmentwith greater emphasis on aesthetic issuesare making water
professionals more and more aware of Mn.
Mn was an issue in every area we looked at, but not every utility within each area had Mn
issues. There are many sources of Mn; source water, component of an added chemical or an
impurity in an added chemical, resuspended or solubilized in sediment, recycled in a side stream
process, or leached from oxide-coated filter media. There was also a wide range in the severity of
and response to Mn issues, with some utilities having operational alarms if Mn was greater than
15 g/L while others allowed concentrations of up to 300 g/L (but always within the regulatory
limit for their state).
The survey was executed in such a way as to gain input from at least one utility that uses
each type of Mn treatment technique that we identified. From the survey data we discerned that,
Mn-specific treatment processes work very well. Problems associated with certain treatment
techniques are those that occur when a process was designed primarily for something else and
was forced, by necessity, to handle Mn as well. While utilities told many successful stories of
treatment for Mn, not all have been successful.
We found that even though the addition of potassium permanganate is a frequently used
technique to control manganese, most of the utilities that control manganese do so with chlorine
and a filter media. Of interest is that many places that use ozone for disinfection and/or oxidation
do not control manganese with it; they rely on other processes to control Mn. These findings
allowed the researchers to see that simply oxidizing Mn is not the whole story of Mn treatment
because both KMnO4 and O3 oxidize Mn.
One of the most counter-intuitive survey findings was that the utilities that have the most
problems dealing with manganese are not those with the highest influent Mn concentrations.
Instead, it is those that have a markedly variable amount of Mn in their influent water. Those
utilities that have high influent Mn have specific Mn treatment and it usually works well. The
ones with variable or intermediate Mn loading are often not prepared to handle it and therefore
Mn passes through treatment directly into the distribution system. From the analysis of reported
influent Mn concentrations, the researchers found that a ratio of maximum Mn to average Mn
concentration greater than 10:1 resulted in obvious Mn problems.
We looked at several different drinking water utilities distribution systems to see if the
amount of manganese in the distribution system water was related to how much Mn was in
treated water at the plant effluent. The simple answer is yes they are related, the more manganese
added the more manganese will be found in the distribution system. However, the further the
distance from the water treatment plant the less manganese is found in the water. Manganese is
therefore accumulated within the distribution system. Even if only a small amount of manganese
is added to the system, it will accumulate and under the correct conditions resuspend. This
implies that if a water treatment plant fails to control manganese during an episode of high
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CASE STUDIES
The case study work looked into the limits of the induced oxide-coated media effect
(IOCME). When dissolved manganese in the water is loaded onto a granular media filter in the
presence of chlorine, an oxide coating is established. This oxide coating then becomes an
efficient adsorption site for other dissolved manganese and the adsorbed manganese is then
oxidized to manganese dioxide (MnO2). This process is very effective but we know little about
it. It works so well over such a wide range of conditions that it calls little attention to itself and
sometimes goes unnoticed.
Removal of manganese relies on the combination of two independent mechanisms which
are interrelatedoxidation and adsorption. The parameters that control these processes overlap.
The pH of the filtered water is the most significant water quality parameter these two processes
share. The higher the pH, the more rapid the oxidation process and the greater the adsorption
capacity of the oxide-coated media. Another water quality parameter that affects both processes,
but not so obviously, is temperaturethe warmer the water, the more rapid the oxidation process
and, seemingly, the greater the media adsorptive capacity. A water quality parameter that seems
to be paramount in oxidation with a secondary effect on adsorption is the presence of free
chlorine. Free chlorine oxidizes adsorbed manganese and converts it to MnO2, thus yielding
more sites for future adsorption. This increases the adsorptive capacity. IOCME can occur even
when there is no free chlorine residual leaving the filter. Free chlorine must be present and
available when manganese is adsorbed onto the media surface. This explains why granular
activated carbon (GAC) can be used as a media for IOCME in the presence of chlorine, even
though GAC dechlorinates water.
IOCME is a self-regenerative process and, as such, requires both chlorine and
manganese. If there is no manganese in the filter influent water, there is not likely to be an
available coating of MnO2. If there is no chlorine, then the surface chemistry changes and Mn is
released back into the water. Therefore, intermittent use of IOCME is not recommended. MnO2
xxi
COST MODELS
The main purpose of the cost model was to quantify the approximate economics of
constructing and operating a treatment facility to produce water with a manganese concentration
less than 0.05 milligrams per liter.
Reduction of manganese at the water treatment plant makes sense. The utility will most
likely end up saving money through less flushing and fewer customer service calls. However,
this is hard to quantify. The main societal advantage is that for every dollar spent by the utility,
the overall benefit to the customer is higher. It makes more economic sense for the utility to
control manganese than it does for each customer to deal with the manganese in the drinking
water. In the work we have done to date, all the utilities that we spoke to agree with this. It is
better to control manganese in a cost-effective manner than to simply do nothing until the
customer calls.
The cost associated with improving removal, via operational changes, is small as
compared to the capital cost associated with changing the primary Mn treatment. It cost more to
start to treat for Mn than it does to improve upon existing treatment. Therefore the reluctance to
treat for Mn is often the reluctance to build new treatment, not to optimize existing treatment.
Therefore, the change in a utilitys internal goal from 0.05 mg/L to any other, has less to do with
aesthetics or customer complaints than it has to do with the threshold limit for which they will
have to build new treatment.
The results from this research program indicate that problems associated with manganese
are much more common than previously thought. Geographically, manganese can occur,
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The purpose of the research conducted under this project was to further our
understanding of the occurrence and control of manganese (Mn) in drinking waterfrom source
water to the treatment process to the distribution systems that deliver water directly to
consumers. This overall goal encompassed a number of more specific objectives, including:
This final report presents and interprets existing and new data and offers practical
recommendations that will help utilities make optimum decisions about manganese control.
Moreover, it is a step towards developing more scientific basis upon which future manganese
regulation can rely.
Research Tasks
At the outset of the project, the authors conducted an extensive literature review to more
clearly identify what was known and not known about manganese in drinking water, and to set
the stage for the research. Hundreds of papers, texts, and reports were reviewed. In Chapter 2 we
have attempted to summarize the pertinent existing knowledge in some detail. While papers on
the occurrence, chemistry, and treatment of Mn are most relevant to the current project, we have
also summarized medical literature that has helped shape the developing consensus that Mn is an
aesthetic, rather than health-related, problem.
The chapters of this report follow the sequence of (1) Introduction, (2) Literature Review,
(3) Methods & Materials, (4) Results and Discussion, (5) Summary and Conclusions, and (6)
Recommendations to Utilities.
The Literature Review chapter serves in a sense as an expanded Introduction, presenting
a more in-depth background on current industry concerns, concepts, and solutions regarding
manganese. The References section at the end of this report gives full citations to references
cited in the literature review and throughout this document.
Since each of the research tasks listed above followed its own distinct method and
produced its own uniquely structured set of data, for ease of organization the authors have
divided each of Chapters 3, 4, and 5 into subsections covering these tasks in order. Chapter 6
attempts to distill the most important and clearest findings of the project as a whole into useful
recommendations.
During the conduct of the project so much data was generated that only a selected portion
is presented in the text of this report. Additional detailed data has been compiled into extensive
appendices supplied on CD-ROM. Appendices A and B give more detail on the materials and
methods discussed in Chapter 3. Appendices C through F provide more detailed data from the
surveys, sampling and case studies, and Appendix G supplies detailed cost analysis tables and
charts.
Mn is an essential trace element for both plants and animals. Chemically it occurs in
several species with different valence states (+2, +3, +4, +5, +6, +7), often represented by roman
numerals. For this study we will focus on Mn(II), Mn(IV), and Mn(VII). The key significance of
Mn speciation in relation to drinking water is that both Mn(II) and Mn(VII) are soluble in water
while Mn(IV) is not. Manganese is most stable in its +2 valence state; therefore most naturally
occurring manganese is dissolved Mn(II). The next most common species is the particulate state
of Mn(IV). To remove Mn from water one usually tries to convert it into an insoluble state and
remove it physically; that is, converting Mn(II) or Mn(VII) into Mn(IV). This means either
oxidizing Mn(II) to MnO2(s), or else reducing MnO4 permanganate ions to MnO2(s), where the
(s) notation indicates solid form. It is important to note that stoichiometric manganese dioxide,
MnO2, is extremely rare if it exists at all. Though we will refer to MnO2 or manganese dioxide
frequently, in reality it is a nonstoichiometric oxide solid of Mn. The common property of most
Mn dioxides is that they are black.
Treatment of water to remove Mn may be categorized into four distinct, yet somewhat
interrelated, approaches:
The first two types of processes are by far the most commonly used, although all four are
addressed in this study.
For the second example of the second process given above, a word of elaboration is in
order. A filter media that is covered with a manganese dioxide will adsorb Mn(II) directly onto
its surface. Once there, it can be quickly oxidized to Mn(IV) in the presence of chlorine. The new
Mn dioxide will become a new site for additional Mn(II) adsorption. This process is similar
enough to the process of Mn removal with manganese greensand that some refer to it as the
induced greensand effect (IGE). However, it is more complicated than that and there is no
greensand involved, so the authors have used a more generic term, the induced oxide-coated
media effect (IOCME).
For the most part, manganese chemistry for the purposes of water treatment can be
usefully simplified, as it was in the preceding explanation. Yet problems exist with this
3
Although research data is continually being developed, it appears that Mn has no negative
health effects at the levels commonly found in drinking water. However, the long-recognized
aesthetic problems caused by Mn are a continuing source of concern for customers and for water
utilities. Problems associated with Mn include water discoloration (usually black or dark red),
clothes and fixture staining, turbid water, sediments, and, at very high levels, metallic taste.
Household problems only occur when the manganese is in the particulate or oxidized
form. If the Mn remains soluble it will pass through undetected by the human eye. The problem
is that Mn usually does not stay dissolved in the oxidizing environments of our water distribution
systems. Even if the Mn did remain dissolved until reaching a customers home, the clothes for
which it causes the biggest problem (whites) are often washed with bleach (NaOCl), an oxidizer.
In such a chemical environment, the Mn precipitates directly onto the surface of the clothing,
leaving small black dots. While these dots can often be removed by washing the clothes with a
reducing agent, the idea of bleaching and then reducing each load of white laundry can quickly
become asinine.
There are many sources of manganese. Manganese may enter a water supply from a
surface water or groundwater source, from the treatment chemicals being used, as a contaminant
in treatment chemical or internally from a recycle stream. The occurrence of Mn in a particular
utilitys source water may be episodic, such as during reservoir turnover, or it may be persistent,
as in many systems whose main source is groundwater wells. Manganese may seem ubiquitous
because there are enough sources and enough variability in concentrations to confound simple
explanation.
The current U.S. EPA secondary standard, or SMCL, for Mn is 0.05 milligrams per liter
(mg/L). Most states have adopted this standard, although a few regulate both iron and manganese
with a combined standard of either 0.3 or 0.5 mg/L for these elements. Some states enforce the
secondary standards as a primary standard.
The standard for Mn of 0.05 mg/L was established subjectively over 40 years ago
(1962)and later adopted without change by EPA (1979)as the level at which most
consumers will avoid household problems with discoloration or staining. It first appeared in a
United States Public Health Service (USPHS) publication of 1943 in combination with iron (Fe),
it suggested the combination of Fe and Mn should not exceed 0.3 mg/L. Prior to this the USPHS
(1925) listed "Iron (Fe) should not exceed 0.3 p.p.m." and made no mention of Mn. However,
as consumer expectations for water quality, often based on aesthetics, increase, the public
perception that a particular water is acceptable decreases. Thus the historical standard of 0.05
As mentioned above, before the main investigative work of the project began, a literature
review updated the project team about the state of knowledge on Mn in drinking water, and the
gaps in that knowledge, so as to best focus the new research efforts.
The following overview of the research tasks undertaken during the project discusses the
primary activities and goals of each task and briefly sketches the methods used. It conveys an
understanding of the logical sequence of the work and some of the difficulties involved in
developing not only reliable data but also practical recommendations for handling the real but
sometimes elusive problem of Mn in drinking water. Throughout the project, the research team
acknowledged the importance of both anecdotal reports from participating water utilities and
hard scientific data, and attempted to derive useful analysis and conclusions from both.
Initial Surveys
The participation of water utilities being central to the projects success, the research
team gave considerable thought to how best to elicit useful data from them. The initial surveys
were designed as a telephone interview between a member of the research team and a utility
representative that had a good understanding of Mn concerns. The purpose of the initial surveys
was to develop a geographically diverse database of information about manganese problems, and
to find utilities that were willing to participate further in the project.
The initial survey questionnaires were designed to obtain the most useful information in
the least amount of time. Before actual surveys began, the principal investigators (PIs) of the
project conducted a formal training program with the interviewers and ran through dress
rehearsals. The PIs then participated in a series of trial run interviews with utilities to ensure that
interviewers were including follow-up questions appropriately. The actual conduct of the
surveys varied from 15 minutes to over two hours, depending on the extent of Mn issues at that
particular facility. An interview form was completed for each facility water source or treatment
plant.
The scope of the initial surveys was to determine the extent of Mn occurrence, identify
types of treatment systems for Mn, ask about problems associated with Mn, obtain limited water
Detailed Surveys
Once the initial surveys were completed, 52 detailed interviews were conducted with
utilities that clearly were experiencing Mn treatment or system problems and that were willing to
spend the time for the interview and to send additional analytical data for inclusion in the
research database. Of the 52 detailed surveys, 10 were conducted with utilities outside the United
States. The purpose of the detailed surveys was to obtain more specific information in three
areas: (1) the source of the Mn, (2) the manner in which the problem was resolved, if any, and
(3) the type of treatment process or chemical addition that was used relative to the Mn. The
detailed surveys were also used to identify systems willing to participate in the next phase of the
projecttaking seasonal distribution system samples for Mn speciation analysis.
The detailed surveys collected considerable information about the distribution system,
types of complaints if any, treatment chemicals used, and levels of Mn in the distribution system.
We were particularly interested in those systems that were at or close to the regulatory limit of
0.05 mg/L for Mn, but were still experiencing discoloration or sediment problems. Each utility
was asked to complete a detailed water quality table with historical data for such parameters as
raw, treated, and distribution system Mn; pH; color; TOC; iron; turbidity; alkalinity; hardness;
calcium; and conductivity. For each treatment plant we identified each unit process in the train
along with pertinent design and operating criteria. We also explored target treatment goals and
The purpose of Case Study I was to use the pilot plant facilities at the Philadelphia Water
Department (PWD) to conduct research on alternative methods and operating procedures for
reducing Mn in a surface water supply. More specifically, this case study tested the operational
boundaries of Mn control via oxide-coated media. The setting of a pilot plant allowed for the
type of controlled experimentation that is difficult to perform at a full-scale WTP relied on by
customers for consistently high-quality water.
PWD has two substantial pilot plants available for research, one at the Baxter Water
Treatment Plant and the other at the Belmont WTP. The two pilot plants have similar process
trains but different source waters. The process trains include flash mixing, tapered flocculation,
sedimentation, intermediate ozonation, and filtration. Of the six filters per plant, four contain
dual media coal-over-sand and two contain granular activated carbon (GAC). The pilot plants are
designed to closely parallel full-scale plant operation of a conventional and modified
conventional water treatment plant. No intermediate pumping occurs from flash mixing through
filtration. The plants are equipped with on-line, continuous monitors for turbidity, particle
counts, filter head loss, pH, flow, and ozone concentration. Operating variations can be obtained
by taking units from service, changing flow rate, or bypassing units. The pilot plants are fully
supported by the analytical services of the PWD-BLS.
The operating variables studied in this task were pH, chlorine application point and dose,
ozone, coagulant concentration, and filter media type. The pilot plant was used to determine if
ozone or chlorine alone or in some combination could be used to control Mn without sacrificing
other water quality. Another purpose was to explore the sensitivity of Mn reduction to pH,
taking into account seasonal and temperature variations. The research evaluated a comparison of
filter media with and without pre-chlorine addition. We wanted to determine if there was an
elution effect of Mn from filter media that had been precoated with manganese dioxide, if the
preoxidant ahead of the filters were suddenly terminated.
This particular phase of the research went very well. The limits of the IOCME were
discerned for both pilot plants. IOCME is a robust treatment process but it does have limits,
mostly associated with temperature and pH. Once established the oxide-coated media is stable
as long as the redox-potential does not change significantly.
The purpose of Case Study II was to evaluate the full-scale efficacy of Mn removal using
the induced oxide-coated media effect on GAC at an operating WTP. The oxide-coated media
process is known to work on sand and anthracite filters that have a free chlorine residual in the
effluent. However, a GAC filter will consume the chlorine so there will be no chlorine residual in
the effluent. Yet an induced oxide-coated media was established and Mn was removed.
A water treatment plant in West Virginia agreed to participate in this study. The facility
uses flash mixing, flocculation, sedimentation, and filtration of a surface water supply source that
contains variable and elevated levels of Mn. One of the treatment plants 12 filters is an
anthracite coal filter; the rest are GAC, providing a somewhat unusual opportunity for
comparison. The plant has successfully reduced Mn by controlling the pH going on the filters
along with the addition of chlorine.
Therefore the major part of the research effort was a success. However, as with most
full-scale endeavors the control of certain variables and the retrieval of all pertinent information
was difficult. This has a lot to do with the need to keep the process optimized regardless of the
Cost Analysis
In the cost analysis, a cost model and tables were developed to give utilities an
approximate comparison of the capital and operating costs of various treatment methodologies
for reducing Mn. The bases of this comparison are national average treatment costs and are not
adjusted for geographically specific unit costs. However, the tables should be accurate for cost
comparisons. Cost comparison tables were developed for three sizes of treatment plants: 1 mgd,
10 mgd, and 100 mgd. The tables are based on the cost to reduce Mn from an assumed raw water
level of 0.5 mg/L down to one of four finished water concentrations: the current regulatory
standard of 0.05 mg/L, or alternatively to 0.02 mg/L, 0.015 mg/L, or 0.01 mg/L. In some cases
the capital cost to reduce Mn to levels well below the regulatory standard is the same as the cost
to just meet the standard since the type of process, e.g. membranes, will inherently remove the
Mn to levels below detection. In those cases the operating cost is usually for additional analytical
testing that may be required to ensure that the lower level is being met.
The types of treatment processes included in the cost analysis include conventional
treatment with coagulation, flocculation, sedimentation and dual media filtration, direct filtration,
lime softening, advanced clarification, membrane filtration, manganese greensand filtration,
diatomaceous earth filtration, and ion exchange. The capital costs presented are for the treatment
plant as if it were constructed only for the removal of Mn; that is, a new plant using a particular
technology but constructed specifically for Mn. Obviously, in many cases Mn might be
incidental to other water quality problems and some processes, such as conventional treatment or
even lime softening, would only be used for Mn if some other water issue were also present.
Other processes, such as manganese greensand, might be selected solely on the basis of reducing
Mn. All the operating costs presented in the tables relate to the incremental cost for reducing Mn.
In some cases this incremental cost is for additional monitoring, reporting, or testing and for
additional chemical doses, if necessary. In some cases the filter run time may be reduced and
more frequent backwashing required.
INTRODUCTION
The first reported case of manganese-related water quality problems in the United States
was in 1898, when a well water supply for a New England mill contained so much Mn that the
well had to be abandoned (Weston 1909). The well extended below a peaty layer overlying
water-bearing sand, from which Mn was suspected to have leached into the groundwater.
Manganese is an abundant metallic element that constitutes about 0.1% of the earths
crust. The elemental form of Mn does not occur naturally in the environment, but Mn is a
component of over 100 minerals. Manganese oxide, manganese carbonate, and manganese
silicate are a few of the most common mineral forms.
Manganese occurs naturally in soil, air, water, and food at low levels. Deutsch, Hoffman,
and Ortner (1997) even found Mn concentrations ranging from 0.3 to 11.3 g/L in rain and snow
samples in Darmstadt, Germany. In groundwaters, Mn concentrations depend upon the mineral
composition of the alluvium, the pH, and redox potential (Troester 1998). Manganese in
groundwater wells may initially be low and remain low for many years, but then unexpectedly
increase until the water quality becomes unacceptable (Viraraghavan et al. 1987).
Biologically, Mn is essential for the proper function of several enzymes and is necessary
for normal bone structure and brain function. Although manganese is an essential trace element
in humans, exposure to high levels of it can have adverse neurological effects. The USEPA
(2004) put it this way Adverse health effects can be caused by inadequate intake or over
exposure. Mn deficiency in humans is thought to be rare because Mn is present in many
common foods. Many of the reports of adverse effect from Mn exposure in humans are from
inhalation exposure in occupational settings.
Manganese concentrations at or even below the current USEPA Secondary Maximum
Contaminant Level (SMCL) of 0.05 mg/L can create problems for drinking water providers by
11
12
REGULATORY BACKGROUND
The 1962 U.S. Public Health Service (USPHS 1962) standards included a drinking water
guideline for manganese; it was 0.05 mg/L, based solely on controlling aesthetic water quality
problems caused by Mn. In 1977, the USEPA issued a proposed rule for manganese under the
Safe Drinking Water Act (SDWA) for a non-enforceable Secondary Maximum Contaminant
Level (SMCL) of 0.05 mg/L (USEPA 1977a). The following justification was provided by the
agency for this proposed level:
Manganese, like iron, produces discoloration in laundered goods and impairs the
taste in drinking water and beverages, including tea and coffee. At concentrations
in excess of 0.05 mg/L, manganese can occasionally cause buildup of coatings in
distribution piping which can slough off and cause brown spots in laundry items
and unaesthetic black precipitates. Manganese can usually be removed from water
by the same process used for iron removal.
It should be noted that at approximately the same time, Stiles (1978) estimated that 20
percent of U.S. municipal water sources contained Mn above 0.05 mg/L, with small systems
being the most vulnerable to these problems. No public comments were submitted on USEPAs
1977 proposed SMCL for manganese. From the time the SMCL was finalized by USEPA in
1979 at 0.05 mg/L (USEPA 1979) until the writing of this report in 2005, the regulatory
guideline has remained unchanged.
Between 1979 and 1998, manganese in drinking water received very little regulatory
attention because it was not thought to pose a major risk to human health. However, in 1998, Mn
was included on USEPAs Drinking Water Contaminant Candidate List (DWCCL) as a
regulatory determination priority contaminant (USEPA 1998a). SDWA Section 1412(b)(1)(A)
specifies that the determination to regulate a contaminant on the DWCCL must be based on a
finding that each of the following criteria are met:
13
USEPA evaluated available data regarding the occurrence, health effects, and control of
Mn in drinking water for a regulatory determination to address the above three statutory criteria
(USEPA 2001a, 2001b). However, because Mn is generally not considered to be very toxic when
ingested with the diet, and because drinking water accounts for a relatively small proportion of
Mn intake, USEPA concluded that setting an enforceable National Primary Drinking Water
Regulation (NPDWR) for Mn was unwarranted at this time because it would not likely present a
meaningful opportunity for health risk reduction for persons served by public water systems. A
preliminary determination from USEPA to this effect was published June 3, 2002 (USEPA 2002)
and a final determination was published July 18, 2003 (USEPA 2003). USEPA has, though,
decided to develop a Drinking Water Advisory for Manganese (Pontius 2004).
Besides the U.S. federal government, numerous other governmental and inter-
governmental agencies have issued regulatory guidelines or limits for Mn in drinking water. For
instance, the World Health Organization (WHO) also recommends a manganese concentration of
not greater than 0.05 mg/L. Comparable recommended limits for Mn have been established by
various international and state drinking water agencies (see examples in Table 2.1). In general,
these guidelines are based on ensuring the aesthetic quality of drinking water, and are not health-
based limits. A few states, however, have adopted enforceable limits for Mn.
Non-Drinking-Water Regulation of Mn
Manganese and manganese compounds are regulated under several U.S. federal programs
in addition to the SDWA (USEPA 2000). Discharge of Mn to surface waters is regulated as total
Mn under the National Pollutant Discharge Elimination System (NPDES). Both Mn and Mn
compounds are listed as Hazardous Air Pollutants under section 112(b) of the Clean Air Act and
are subject to Best Available Control Technology limits (USEPA 2000). The Comprehensive
Environmental Response, Compensation, and Liability Act (CERCLA or Superfund) includes
Mn compounds as hazardous substances, although no reporting thresholds are assigned to this
broad class (USEPA 1998b).
Manganese is also a Toxic Release Inventory (TRI) chemical. The TRI was established
by the Emergency Planning and Community Right-to-Know Act (EPCRA), which requires
certain industrial sectors to publicly report the environmental release or transfer of chemicals
included in this inventory (USEPA 1998b). Mn and some of its compounds are also listed as air
contaminants by the Occupational Safety and Health Administration (OSHA). This listing
establishes permissible exposure limits (PELs) for various Mn compounds to regulate workplace
exposure (ATSDR 2000).
14
15
HEALTH EFFECTS
Manganese is absorbed via oral or inhalation routes. The adrenal glands regulate the
concentration of Mn in the blood. Aschner (2000) reviews Mn speciation in the blood and the
transport kinetics of Mn into the central nervous system. Although Mn may be distributed to the
tissues, most of the excess is discharged via the bile or by other gastrointestinal routes. Mn
concentrates in mitochondria and organs with high mitochondrial density, such as the liver,
pancreas, kidney, adrenal glands, and intestines (Hudnell and Mergler 1999). Inorganic
manganese excretion is almost exclusively fecal; whereas organic forms are excreted in both
feces and urine (USEPA 1975). Diets associated with higher Mn intake include food such as
whole-grain cereals, nuts, green leafy vegetables, and tea.
The biochemical role of Mn is to serve as an activator of several enzymes including
hydrolase, kinases, decarboxylases, and transferases. Mn is also required for the activity of three
metalloenzymes: arginase, pyruvate carboxylase, and mitochondrial superoxide dismutase
(Welder 1994). It has also been determined that Mn uptake into the central nervous system is
16
The representative oral LD50 values for rats are 410 to 475 mg Mn/kg for manganese
chloride, 379 to 750 mg Mn/kg for potassium permanganate, and 2,197 mg Mn/kg for
manganese dioxide (Holbrook et al. 1975, Kostial et al. 1978, Smyth et al. 1969, Shigan and
Vitvitskaia 1971). USEPAs Integrated Risk Information System (IRIS) database lists a total oral
reference dose (RfD) for Mn of 0.14 mg/kg/day (USEPA 1996). The RfD is an estimate of daily
exposure that is likely to be without appreciable risk of deleterious health effects during a
lifetime. This RfD of 0.14 mg/kg/day translates to a drinking water lifetime health advisory of
300 g/L (USEPA 2004). This limit was derived using a 70 Kg adult, 20% intake from drinking
water, 2L per day of water consumed and a modifying value of 3. It is important to note that
health advisory is not a regulatory limit and is to be used as guidance by public health officials
during emergencies or episodic events. Concentrations below the health advisory are expected to
be with out adverse effects on both health and aesthetics.
However, in a chapter of a book on occupational medicine Hudnell and Mergler (1999),
using the USEPAs IRIS database as the source, published an RfD of 200 g/L (which we
suppose to be a health advisory and not an RfD). In the field of public health physicians are
greatly trusted (as well they should be) so a physician in your community may present the 200
g/L as the appropriate value to guard public health based on a medical text as opposed to the
current USEPA lifetime health advisory of 300 g/L. A communitys health department is often
a good source of clarity on such matters and they will have access to the current health advisory
levels.
To continue with the theme of changing standards for Mn, the World Health Organization
(WHO) listed a limit of 0.5 mg/L (WHO 1993) is adequate to guard public health. However
within that publication they calculated a 0.4 mg/L drinking water limit based on 12 mg/day safe
exposure, 60 Kg adult, 20% intake through drinking water and an uncertainty factor of 3. They
also said that no single study is suitable for calculating a guideline value. In 2004 the WHO
(2004a, 2004b) revised their limit from 0.5 to 0.4 mg/L.
Several oral studies conducted in rodents identified biochemical changes in the brain
following administration of manganese chloride tetrahydrate in drinking water (Chandra and
Shukla 1981; Lai, Leung, and Lim 1981; Lai et al. 1982; Leung, Lai, and Lim 1981). The
relevance of these biochemical changes to humans has been challenged since rodents do not
exhibit the same neurological deficits following exposure to Mn. Marsden and Jenner (1987)
hypothesized that the ability of certain drugs to induce Parkinsonism in primates, but not in
rodents, is due to the relative lack of neuromelanin in rodents. Because Mn selectively
accumulates in pigmented regions of the brain, this species difference is fundamentally
important. A study performed in a group of four Rhesus monkeys showed muscular weakness
and rigidity of the lower limbs after 18-month exposure to 6.9 mg Mn/Kg-day (Gupta, Murphy,
and Chandra 1980). Histological analysis showed degenerated neurons in the substantia nigra
and scanty neuromelanin granules in other pigmented cells. While this study demonstrated
neurotoxicity resulting from excessive exposure to Mn, the exact mechanism is not clear.
Oral exposure studies conducted in animals have demonstrated subchronic toxicity
including hematological changes, alteration of liver enzyme activities, decreased rate of body
weight gain, decreased absolute and relative liver weights, and histopathological changes in liver
tissue following exposure to inorganic manganese compounds (Shukla, Sigh, and Chandra 1978;
17
Couper (1837) first recognized the toxic capacity of manganese. Since then, numerous
descriptions of manganese poisoning (manganism) have been detailed (Rodier 1955; Schuler et
al. 1957; Tanaka and Lieben 1969; Smyth et al. 1973; Cook, Fahn, and Brait 1974; Chandra,
Shukla, and Srivastava 1981; Roels et al. 1999; Ferraz et al. 1988; Iregren 1990; Wennberg et al.
1991; Chia et al. 1993; Mergler et al. 1994; Chu et al. 1995; Lucchini et al. 1995, 1997, 1999).
The signs and symptoms of manganism present a variety of neurological and behavior symptoms
that are related to the three functional areas of the nervous system (cerebellum, cerebral cortex,
and corpus striatum).
18
Essentiality
19
CHEMISTRY
To begin this topic, it is prudent to start with the basics before exploring the more
complex world of Mn chemistry. The authors want the reader to start this journey knowing that
we do not yet know all there is to know about Mn. There are mysterious things about
Table 2.2
Dietary reference intakes: intakes recommended for individuals
AI UL
Life stage group
(mg/day) (mg/day)
Infant
0-6 months 0.003 ND
7-12 months 0.6 ND
Children
1-3 years 1.2 2
4-8 years 1.5 3
Males
9-13 1.9 6
14-18 2.2 9
19-70 2.3 11
Females
9-13 1.6 6
14-18 1.6 9
19-70 1.8 11
Pregnancy
14-18 2.0 9
19-50 2.0 11
Lactation
14-18 2.6 9
19-50 2.6 11
Source: Data from Institute of Medicine, National Academy of Science (2004)
20
Of particular interest in this long reference is that Mn is not a simple element that makes
up simple compounds. It can change oxidation states and therefore chemical properties. The
solid form of Mn oxide is also an oxidizing agent and a cation exchange agent, not an inert solid.
Then if one puts this complex element into real settings the chemistry gets even more complex.
For example, Bratina says that although Mn is a minor chemical constituent of marine water and
freshwater, the oxides of manganese may play a pivotal role in aquatic geochemical cycles. The
central role for manganese oxides is due to their remarkable surface area and charge distribution,
which make them a potentially rich reservoir of adsorbed metals. Hydrous manganese oxides are
often present in amorphous or microcrystalline forms which have surface areas as high as 300
m2/g. (Bratina et al. 1998). Post (1999) writes that because Mn oxide minerals commonly occur
as coatings and fine-grained aggregates with large surfaces areas, they exert chemical influence
far out of proportion to their concentration. He adds because of the large tunnels in todorokite
(common mineral of Mn) it is of interest for use as a catalyst and as a cation exchange agent.
Also for another one of the common minerals, birnessite; the birnessite-group minerals have
layer structures and readily undergo oxidation reduction and cation-exchange reactions and play
a major role in controlling groundwater chemistry.
1
Stoichiometry is the branch of chemistry that deals with the proportions of chemical analysis. A
stoichiometric molecule of MnO2 means that there are two atoms of oxygen for each atom of Mn. Nonstoichiometric
means that the molecule is not actually in those exact proportions.
21
Table 2.3
Manganese compounds of common valence states
Valence
Chemical formula Physical form and description
state
0 Mn(s) Manganese metal, silvery metal with slight pink
appearance
2 Mn(OH)2 Manganese(II) hydroxide, flesh colored
2 MnS Manganese(II) sulfide, salmon colored
2 MnSO4 Manganese(II) sulfate, reddish
2 MnCl2 Manganese(II) chloride, pink
MnCl2 4H2O Manganese(II) chloride tetrahydrate, rose colored
4 MnO2(s) Manganese in solid pyrolusite, dark brown or black
(nonstoichiometric)
6 K2MnO4 Potassium manganate(VI), dark bottle-green
7 KMnO4 Potassium permanganate(VII), intense purple
Source: Data from Bailar et al. (1978)
22
Biochemical Phenomena
23
Speciation
24
25
26
Table 2.4
Analytical methods for determining manganese in water and environmental samples
Generalized Sample
Matrix & method Technique
detection limit preparation
Air
Collection on
NIOSH 1984a XRF 2 g/sample filter, direct
analysis
Collection on
1 g/sample
NIOSH 1984b ICP/AES filter, acid
(5 g/m3)
digestion
Sediments, sludges, soils
Acid digestion,
EPA Methods Variable,
oxidation,
3050 and 6010 AAS, ICP/AES depending on
filtration /
(USEPA 1986a, b) matrix
centrifugation
Water
ASTM D858-02A Acidify with nitric
AAS (direct) 100 g/L
(ASTM 2002) acid
ASTM D858-02B AAS, chelation- 10 g/L Acidify with nitric
(ASTM 2002) extraction acid
ASTM D858-02C AAS (furnace) 5 g/L Acidify with nitric
(ASTM 2002) acid
Beklemishev et al. Catalytic kinetic 0.005 g/L Preconcentration
1997 method
Deutsch et al. 1997 IC 1 g/L Oxidize with NaIO4
in an acetate buffer
EPA Method 243.1 AAS (direct 10 g/L Acidify with nitric
(USEPA 1983a) aspiration) acid
EPA Method 243.2 AAS (furnace) 0.2 g/L Acidify with nitric
(USEPA 1983b) acid
SM 3111 B AAS (direct 10 g/L Acidify with nitric
(APHA 1998) aspiration) acid
(continued)
27
In situ treatment
Biological treatment
Chemical oxidation
Oxide-coated media
Physical separation
Ion exchange
Incidental precipitation
Sequestration
28
Aeration
29
Hypolimnetic Systems
Conventional diffused aeration systems use rising air bubbles to pump low-oxygen
bottom water to the surface so that natural re-aeration processes can occur. Hypolimnetic
aeration systems allow aeration of the low dissolved oxygen layer without disturbing the natural
stratification of the reservoir. Hypolimnetic systems may be used to aerate water within the same
temperature gradient, thereby preventing mixing of the thermal layers. Alternatively, lake
aeration systems such as the SolarBee may be used to provide aeration as well as mixing of the
water body, thereby maintaining dissolved oxygen levels throughout the water column. Utilities
that correctly size and operate these aeration systems can benefit from improved Mn control,
frequently realize benefits in control of taste and odor problems as well, and can dramatically
reduce treatment chemical costs. Van der Tak, Snyder, and Martens (1992) suggested that lake
aeration can be an effective control measure for Mn, but all areas of the sediment/water interface
near the drinking water supply intake must be adequately aerated.
While successful in some instances, reservoir aeration should not be viewed as a panacea
for manganese problems. Chiswell and Mokhtar (1990) reported that installation of a reservoir
aeration system in the Hinze Reservoir near Brisbane, Australia, destratified the reservoir and
indeed changed the nature and concentration of Mn in the water column. However, based on two
years of testing, reservoir destratification with air was found to increase the concentration of Mn
in the water column and was more of a detriment than a benefit. Jung (2004) of the East Bay
MUD in California has also been tracking the use of a hypolimnetic oxygenation system (HOS)
in that agencys Upper San Leandro and Sobrante reservoirs for three years. The HOS delivers a
small flow of oxygen (not air) under pressure, at the bottom of the reservoir. The system was
installed to control algae that were causing taste and odor (T&O) problems, with Mn control
being incidental to that. The system is successful in creating saturated and supersaturated DO
levels within the reservoir, and the amount Mn entering the water treatment plants is lower than
in the two years prior to installation. It effectively reduced the T&O (blue-green) algae, but in the
second year of operation, it seems to have created an environment that favored filter-clogging
algae (Cratium). East Bay MUD recently reduced the amount of oxygen transferred, so that only
the lower stratum of the lake is saturated with DO. Clearly, the effectiveness of reservoir aeration
for Mn control will be site specific.
Groundwater in situ
Water systems with wells drawing groundwater containing soluble Mn can have
production capacity losses. Zienkiewicz (1985) reported on the Vyredox method for removing
Mn from groundwater at the source, in the ground, before the water is drawn to the well. This is
an in situ method that works by raising the redox potential in the ground around a well with
periodic recharges of aerated water using specially engineered conditioning equipment and
recharge wells. Oxygen in the recharge water acts as a catalyst to begin a biochemical reaction
that transforms Mn from its soluble form to insoluble compounds that are kept in the ground
away from the well. Braester and Martinell (1988) described and formulated mathematically the
phenomena involved in the Vyredox process, including flow, transport, chemical reactions, and
bacteriological processes.
30
Biological treatment for Mn is essentially a filtration process that takes advantage of the
oxidizing ability of certain bacteria and their ability to assimilate Mn. Usually applied as a
pretreatment for wells, this process attempts to promote the selective growth of beneficial
bacteria. Since the bacteria are aerobic the technology employed is simply a surface to grow on
and air to make sure there is oxygen in the water. The oxidized metal must be later removed by
physical separation or by removal of bacteria that have accumulated the metal.
Biological filtration processes are not typical in the United States, but they are common
in Europe. The first facilities for the biological removal of iron and manganese were built in
Germany more than 100 years ago (Charlottengurg, in 1874) and in the United States (Atlantic
Highland, NJ, in 1893) (OConnor 1971).
Large bacterial populations can be established in filters that oxidize iron and manganese
and precipitate the metals in the surrounding filter medium. These processes are generally rapid,
occurring more quickly than physical/chemical treatment processes. The cost of a biological
oxidation plant may be considerably less than the cost of a conventional chemical
oxidation/filtration system, and pilot studies are typically conducted to demonstrate the
effectiveness of the process for a particular water (Larson 1995; Yannoni, Kinsley, and Marston
1999).
Bacteria capable of removing Mn include Sphaerotilus, Leptothrix, Crenothrix,
Siderocapsa, Siderocystis, Hyphomicrobium, and Metallogenium (Mouchet 1992). These
organisms remove Mn through the following processes: (1) intercellular oxidation by enzymatic
action, (2) adsorption of dissolved Mn at the surface of the cell membranes, and (3) extracellular
oxidation by catalytic action of excreted polymers (Czekalla, Mevius, and Hanert 1985;
Schweisfurth 1972; Ghiorse 1984; Gounot, Di Ruggiero, and Haroux, C. 1988; Rittmann and
Snoeyink 1984; Sokolova-Dubinina 1979; Vandenabeele et al. 1992). Sphaerotilus and
Leptothrix transform Mn(II) to Mn(IV) (Mulder and van Veen 1983). Generally, these
manganese dioxide precipitates have better structures than those produced by physical-chemical
processes and are more likely to be removed in the filter (Czekalla, Mevius, and Hanert 1985;
Tuschewitzki and Dott 1983; Hatva et al. 1985).
Specific operating conditions are required to establish the necessary microbial
populations to successfully remove Mn as follows: (1) full aerobic conditions must prevail
within the biofilter, (2) dissolved oxygen levels must be greater than 5 mg/L, (3) the pH must be
7.5 or greater, and (4) a redox potential of 300 to 400 mV must be achieved (Mouchet 1992). If
necessary, the water should be aerated in pretreatment to produce appropriate dissolved oxygen
levels. In addition, the source water must not contain substances toxic to the bacteria, including
chlorine (from pretreatment of backwash water), hydrogen sulfide (levels must be less than 0.01
mg/L), heavy metals, ammonia nitrogen, phosphates, organics, or hydrocarbons (Sommerfeld
1999).
Iron can also be removed through biological processes, although the operating conditions
differ from those for Mn removal (Cameron 1996, Sommerfeld 1999). Bacteria commonly used
for iron removal are Gallionella, Leptothrix, Crenothrix, and Siderocapsa. Operating conditions
require (1) pH between 6.5 and 7.22 (2) dissolved oxygen levels of 5 to 25 mg/L, and (3)
temperatures of 10 to 25oC. The same toxicity restrictions apply for the iron- and manganese-
removal bacteria. Generally, if both iron and manganese bio-removal processes are used, they are
2
Seemingly contradictory, pH above 7.2 generally does not adversely affect removal, the mechanism of
removal may change from biological to chemical.
31
32
This is the most common practice employed for the removal of Mn in drinking water. In
the simplest of descriptions, it is the oxidation of soluble Mn(II) to solid Mn(IV) via an oxidizing
compound, producing a precipitate that can be physically separated (Carlson, Knocke, and Gertig
1994). The process description is simple but the application of the oxidant and the later physical
removal of the solid can be very complicated.
Various oxidizing agents can be used to change the oxidation state of Mn so that it can be
removed from a drinking water supply. Table 2.5 describes the Mn oxidation reactions for
oxidants typically used in drinking water, listing the ideal or theoretical stoichiometric ratio of
oxidant to metal for each reaction.
The ability of an oxidant to effectively convert manganese from its dissolved state (Mn+2)
to solid MnO4 depends on a variety of factors: total oxidant demand in the water, temperature,
pH, alkalinity, and the presence of competitive oxidizing species (iron, sulfide, nitrate, ammonia,
and organic compounds) (Posselt, Reidies, and Weber 1968; Posselt, Anderson, and Weber
1968; Hammer 1975). Generally, oxidant doses greater than the stoichiometric ratios are
necessary in actual drinking water applications. Additionally, the kinetics of the specific reaction
under the existing treatment process condition must be considered to determine if adequate
oxidation will occur within the available process detention times.
Table 2.5
Theoretical reaction stoichiometry for manganese (II)
Stoichiometric ratio,
Oxidant Reaction
mg oxidant : mg Mn metal
2+ +
O2(aq.) Mn + 1/2O2 + H2O MnO2(s) + 2H 0.29 : 1
HOCl Mn2+ + HOCl + H2O MnO2(s) + Cl + 3H+ 1.30 : 1
MnO4 3Mn2+ + 2KMnO4 + 2H2O 5MnO2(s) + 2K+ + 4H+ 1.92 : 1
O3(aq.) Mn2+ + O3 + H2O MnO2(s) + O2 + 2H+ 0.88 : 1
ClO2 Mn2+ + 2ClO2 + 2H2O MnO2(s) + 2ClO2 + 4H+ 2.45 : 1
Source: Adapted from Sommerfeld 1999
33
The kinetics of oxidation are very important. Knocke et al. (1990) did seminal work in
this area and presented information about the kinetics of oxidation, mostly in the bulk water
phase. However, the concentrations of Mn used to do this research were higher than one might
find typically, so Gregory and Carlson (2003) conducted research using lower concentrations of
Mn. They found that the reaction kinetics were even slower than Knocke predicted. They also
found that for ozone, when the initial Mn concentration was low (60 and 200 g/L) a final
residual of <10 g/L was not achievable and in many cases permanganate was formed.
Because of its adsorptive properties, manganese dioxide accelerates the removal of
Mn(II) from solution and causes the mixed oxide to form. It is the presence of this manganese
dioxide on filter media that makes the removal of Mn(II) during oxide-coated media filtration so
effective. Later in this chapter there will be a more detailed discussion of this process.
The presence of organic material can complicate the oxidation and removal of Mn. The
organic matter influences Mn oxidation through one or more of the following three strategies:
Aeration can be an effective oxidation process for iron removal, but it is generally not
effective for oxidation of Mn (Griffin 1960, Stumm and Lee 1961). It is possible to oxidize Mn
by air, but that is a slow process and requires alkaline pH conditions above 9.5 (Morgan and
Stumm 1964, Weber 1972). Highly alkaline conditions are not prevalent in most drinking water
treatment processes, except in water-softening operations, which require highly alkaline pH
conditions.
Raveendran, Ashworth, and Chatelier (2001) evaluated alternative methods for oxidizing
and removing Mn from the South Gippsland Region Water Authority (SQRWA) in Australia,
which owns and operates 10 water treatment plants that experience reoccurring Mn problems.
Methods examined included aeration, chlorine, sodium hypochlorite, and potassium
permanganate. The researchers concluded that reservoir aeration might be considered as primary
treatment, but would likely not oxidize all of the reservoir Mn and that oxidizing agents would
still be required at the treatment plants. Potassium permanganate as an oxidizing agent was found
to be very effective for converting soluble Mn to the insoluble form, but if the source-water Mn
concentration fluctuated significantly, adjusting the permanganate dose was operationally
difficult. High pH, above 8, resulted in improved Mn removal by subsequent filtration, but alum
coagulation at the higher pH would be difficult. SGRWA found adequate Mn removal when they
raised the pH up to 7.5 to 8.0 with a detention time of 10 minutes before alum addition.
Once adequately oxidized from a soluble form to an insoluble form, Mn can be removed
from water by physical separation. In cases where there is a large enough quantity of Mn, a
significant percentage of it is removed by settling. That which is not removed by settling (or
clarification in general) is removed by filtration. Complications occur in these unit processes
34
Chlorine oxidizes Mn much less efficiently than it oxidizes iron. Alkaline pH conditions
and dosages well above the stoichiometric requirements are needed to produce effective rates of
Mn oxidation (Griffin 1960; Knocke, Hoehn, and Sinsabaugh 1987; Knocke et al. 1990). Mn(II)
oxidation is extremely slow under neutral or acidic pH conditions.
Hao, Davis, and Chang (1991) reported on the mechanism of soluble Mn oxidation to the
insoluble Mn(IV) form with chlorine. Experimentally, ratios of chlorine to Mn(II) of 0.8 to 3.8
were investigated. At an experimental pH of 8, the time for Mn(II) to convert to MnO2 was
significantly reduced as the ratio of chlorine to manganese increased. However, even at a
chlorine to manganese ratio of 3.8, over 100 minutes was required for 1.0 mg/L of Mn(II) to be
fully oxidized. The rate of Mn oxidation greatly depends on the pH of the solution, and most
importantly on the dose of chlorine. A model was developed based on homogenous Mn(II)
oxidation and heterogeneous Mn(II) adsorption/ oxidation onto MnO2. The addition of MnO2
accelerated the oxidation of Mn(II), as did excess chlorine.
Knocke et al. (1990) found that even at dosages 4 times greater than stoichiometric
requirements for free chlorine, a minimum of a 3-hour contact time was necessary to achieve the
reduction in the soluble Mn concentration from 1.0 mg/L to 0.7 mg/L at pH 7.0. When pH was
increased to 9.0, Mn(II) was effectively oxidized within 1 hour to below the SMCL of 0.05
mg/L. Temperature also influences Mn(II) oxidation. When temperature was reduced from 25C
to 14C, comparable Mn(II) oxidation was not possible even if reaction time was increased by a
factor of three or four.
Knocke, Hamon, and Thompson (1988) also observed that the presence of fulvic acids
inhibited the rate of Mn(II) oxidation by free chlorine. However, effective removal was still
observed at a pH of 9.0 and dissolved organic carbon (DOC) concentrations up to 5.0 mg/L.
Manganese removal is significantly enhanced when free chlorine is used in combination with
oxide-coated filter media (Weng, Hoven, and Schwartz 1986; Knocke, Hamon, and Thompson
1988).
For facilities that do not practice breakpoint chlorination and maintain a chloramine
residual as the preoxidant, Mn removal is generally not effective. The oxidation rate of
chloramines is too slow to be useful in water treatment processes for the removal of Mn
(Kawamura 2000).
35
Ozone used in preoxidation for water treatment processes allows the removal of inorganic
compounds such as iron and manganese (Seby et al. 1995). The extremely fast kinetics of iron
oxidation result in the preferential oxidation of uncomplexed Fe(II) over Mn(II) (Stoebner and
Rollag 1981, Knocke et al. 1990). Although ozone may be utilized for iron and manganese
oxidation, ozonation is not frequently practiced due to greater capital costs than other available
methods, as well as the risk of completely oxidizing the manganese to permanganate with a
result of pink effluent water.
Netzer and Bowers (1975) discussed the potential for excessive ozone doses to cause the
formation of permanganate. Long, Hulsey, and Hoehn (1999) reviewed water quality problems
that can occur when pre-ozonation is used to oxidize Mn. Most likely, if either oxidized or
reduced Mn concentrations in the raw or settled water exceed 0.1 mg/L, permanganate would
form at concentrations sufficiently high to create problems, especially if the ozone dosages are
high enough to achieve pathogen inactivation.
Knocke et al. (1990) found that ozone oxidized uncomplexed Mn(II) more effectively
than organically complexed Mn(II). Additionally, ozone oxidation occurred more effectively
under acidic conditions than basic. They found that although alkalinity conditions did not
significantly influence the rate of Mn(II) oxidation, pH was a factor in the decomposition of
ozone. They found that the concentration of soluble Mn decreased at pH 5.13 for the first 60
seconds, but at pH 6.35, there was no additional decrease in soluble Mn after 30 seconds. Nowell
and Hoigne (1987) also found that Mn reacts directly with ozone and is not an initiator of
hydroxyl radicals. The decomposition of ozone is initiated by hydroxide ions (Hoigne and Bader
1977, Staehelin and Hoigne 1983). An increase in pH increases the rate of ozone decay, thereby
reducing the effective ozone dose.
Seby et al. (1995) studies the reactivity of ozone and Mn over a wide pH range. They
characterized oxidized Mn species as permanganate ion at pH = 2, and manganese dioxide at pH
= 4 to 8. They also said that it was difficult to determine species because of secondary reactions,
the main one being the interaction between indigo (used to determine ozone concentration) and
MnO2, which will oxidize the indigo and return to Mn(II).
37
Chlorine dioxide can be used in drinking water treatment for disinfection, DBP reduction,
and taste and odor control as well as oxidation of Mn(II) and subsequent removal of manganese
dioxide (Griffin 1960). The mechanism of oxidation of Mn by chlorine dioxide is similar to its
oxidation by potassium permanganate (Knocke et al. 1990). Reaction rates for oxidation with
chlorine dioxide are similar to permanganate. Rates increase when pH increases and decrease in
the presence of organic carbon. When humic carbon is present, improved Mn(II) oxidation is
observed when the pH is increased. Temperature <10C is a limiting factor to Mn oxidation
(Knocke, Hoehn, and Sinsabaugh 1987).
In the presence of reduced Mn, chlorine dioxide is not completely reduced to chloride ion
(Cl); rather, it is only reduced to chlorite (ClO2). When the oxidative capacity is limited in this
manner, a transfer of only one electron rather than five occurs. The Stage 1 D/DBP Rule
(USEPA 1998c) sets an MCL for chlorite at 1.0 mg/L. Because only a small portion of the
oxidizing capacity of chlorine dioxide is utilized in this reaction, the stoichiometric dosage for
Mn(II) oxidation is very high (Table 2.4) and the application of chlorine dioxide for Mn(II)
oxidation is limited (Knocke et al. 1990).
Knocke et al. (1987, 1990) found that no reaction occurred between Mn(II) and hydrogen
peroxide over the pH range of 5.5 to 8.5.
Oxide-Coated Media
Manganese Greensand
Pyrolusite
Manganese and iron can also be removed from solution by adsorption on a packed bed of
granular pyrolusite (McGhee 1991). Pyrolusite is the mineral form of MnO2(s). It is mined in the
United States, Australia, Brazil, and South Africa. The ore is crushed into specific sizes needed
for filters used in potable water treatment. Since the individual pieces of pyrolusite media are
actually MnO2, it is not necessary to develop a manganese dioxide coating on the media particles
as is required with greensand-type filters.
Pyrolusite filters are typically a blend of pyrolusite and sand. The range of this blend is
from 10% pyrolusite / 90% sand to 50% pyrolusite / 50% sand (percent by volume (Sommerfeld
1999). The necessary ratio of pyrolusite to sand will depend on the levels of iron and manganese
that need to be removed from the raw water. Depending upon source water quality, aeration can
be used to remove unwanted gases (hydrogen sulfide) and to oxidize iron. Typically, chlorine is
fed at a sufficient level to keep the pyrolusite continuously regenerated. If preoxidation with
chlorine is not desired due to minimizing disinfection byproduct formation, intermediate
regeneration practices are used and regeneration occurs when chlorinated water is used for filter
backwash.
Since pyrolusite has a high specific gravity (approximately 4.0), pyrolusite filters require
higher backwash flow to fluidize the bed and provide necessary cleaning. Generally, air scour is
also used in the backwash to adequately clean these filters. Since this media does not have a
41
42
Physical Separation
Filtration Processes
43
Although not specifically an iron or manganese removal technique, dissolved air flotation
can remove the precipitates formed following the oxidation of soluble iron and manganese
(Sommerfeld 1999). Dissolved air flotation is generally more effective on waters with low rather
than high Mn concentrations.
Roscoe (2002) reported on Mn problems at the North East Water (NEW), Australia towns
of Benalla, Tungamah, and St. James. Black-water events from Mn were periodically a major
problem. At times the Mn concentration in the finished water exceeded the Australian guideline
of 0.1 mg/L. Consumer confidence was diminished as a consequence of the black-water
problems.
Until 1998 the town of Benalla was supplied from a surface water reservoir with water
that only received chlorination. In December 1998 a new treatment plant was commissioned with
a capacity of 19 ML per day using dissolved air flotation. The plant used liquid alum as the
primary coagulant, LT20 polymer as the flocculation aid, and soda ash for pH correction. The
filtered water was disinfected with chlorine at a residual of 0.2 to 0.5 mg/L. The plant was also
capable of adding powdered activated carbon, potassium permanganate, and aqueous ammonia.
In October 1999 after 10 months of operation the daily demand on the plant significantly
increased, causing oxidized deposits of Mn on the supply pipelines to be scoured into the
distribution system, resulting in serious consumer complaints about black water from the
manganese. Potential solutions considered by the utility included optimizing the current
coagulant and aids, pretreatment with potassium permanganate, alternative coagulants, and
implementing different detention times and alternative disinfection treatment and processes. The
average raw water Mn concentration at the Benalla plant was 0.08 mg/L with virtually all of the
Mn passing into the distribution system. After conducting a series of jar tests, potassium
permanganate was introduced into the raw water to oxidize the soluble manganese. First the
permanganate was added to the raw water, and then the pH was raised to 8.0 with soda ash,
followed by a retention time of 5 to 20 minutes. Subsequently alum was added at a pH of 5.5 to
7.5 followed by flocculation and dissolved air flotation. The full-scale plant results were poor. It
was concluded that a longer oxidation contact tank would be needed which would require major
capital works improvement.
Additional jar testing on PACl (polyaluminum chlorohydrate) suggested that changing
the coagulant might significantly improve the removal of Mn in the DAF process. Once the full-
scale plant change had been implemented, the total soluble Mn was reduced from over 0.08
mg/L to less than 0.02 mg/L. Based on both jar tests and full-scale testing, PACl was an effective
coagulant for removing Mn as compared to aluminum sulfate. The PACl performed 95 percent
better than the alum alone even with a preoxidant. The change to PACl produced a treated water
quality well below the Australian guideline of 0.1 mg/L of manganese, and significantly reduced
black-water complaints. Additional research is needed to determine exactly how PACl removes
Mn.
Membrane Processes
Schneider, Johns, and Huehmer (2001) studied the application of oxidation followed by
microfiltration on three types of surface water: the Eagle River in Colorado, the Tygart River
44
The free cations of iron and manganese can be removed using zeolite processes. As water
flows through the zeolite medium, cationic exchange occurs. Backwashing the zeolite, typically
with a brine solution prepared from sodium chloride (NaCl), removes the iron, manganese, and
hardness cations that have accumulated. After regeneration, the zeolite medium is rinsed with
clean water to remove residual brine prior to returning the process to service.
The use of oxidation practices prior to zeolite softening is not recommended for iron and
manganese removal because the zeolite process requires the iron and manganese to be in a
cationic form and not in an oxidized, insoluble form. Additionally, the accumulation of solid iron
and manganese oxides can clog and plug the zeolite medium (Sommerfeld 1999).
Incidental Precipitation
Lime (CaO) or soda ash (Na2CO3) treatment is effective for removing both iron and
manganese because it raises the pH to a level at which iron and manganese are insoluble
(Ferguson and Given 1976). Softening processes are especially effective for pre-aerated waters
with pH above 9.5 and an alkalinity above 20 mg/L. Manganese will not precipitate at pH less
8.8, but at pH 9.4 to 9.8 manganese was removed at 98% to 100% (Kawamura 1991). Since
lime softening is more expensive than other iron and manganese removal processes, lime
softening would typically only be used if significant softening of the water is required in addition
to iron and manganese removal (Wormald and Clark 1994, Benefield and Morgan 1990,
Sommerfeld 1999).
Aziz and Smith (1992) conducted batch experiments using dolomitic limestone, gravel,
and crushed red brick to remove Mn. At a final pH value of 8.5, limestone gave 95% removal of
Mn, crushed brick gave 82% removal, and gravel gave about 60% removal. Mn removal using
aeration and settling with no solid media was <15%. The results indicated that rough solid media
and the presence of carbonate are beneficial in the precipitation of Mn from water. These media
are low cost and may be suitable for rural water treatment in developing countries. Subsequent
laboratory-scale filtration studies found good Mn removal using limestone media at an input pH
of 7 and a manganese concentration of 1 mg/L (Aziz and Smith 1996).
Sequestering Agents
Sequestering can be used to control aesthetic water quality problems associated with Mn.
However, sequestering is not a removal technique (Knocke, Hoehn, and Sinsabaugh 1987;
Knocke et al. 1990; Carlson, Knocke, and Gertig 1997). Sequestering agents will keep
manganese in a form that generally will not cause consumer problems. Sequestering agents
essentially keep manganese in solution by preventing soluble manganese from oxidizing to an
insoluble form, or by inhibiting colloidal manganese from forming larger colloids.
Use of sequestering agents to control negative aesthetic effects is generally applicable to
water containing less than 2 mg/L of iron and manganese (Kawamura 2000). To be effective,
iron and manganese must be in the bicarbonate form. Sequestering agents include compounds
such as sodium silicate, trisodium phosphate, hexametaphosphate, and zinc orthophosphate. The
proper dosage of sequestering chemicals must be determined based on water quality
characteristics and the manufacturers recommendations. A typical hexametaphosphate dose
required to control 1 mg/L of iron would be approximately 2 mg/L. However, the industry
approach is to limit hexametaphosphate doses to 4 mg/L, since it can promote biological growth
46
Changing Process pH
Changing process pH and oxidation practices can have a direct, negative impact on Mn
removal strategies. If Mn is oxidized completely before the coagulation process, effective
removal is possible, especially if the MnO2(s) remains stable. However, if Mn is oxidized after
the coagulation process, the pH depression associated with enhanced coagulation can affect the
efficiency of the removal process. The extent that Mn removal is affected is dependent on
solution pH, temperature, oxidant type and concentration, and contact time. If potassium
permanganate, chlorine dioxide, or ozone is applied before coagulation, the oxidation rate is fast
enough that complete reaction can occur in the contact time available before coagulation
(typically less than 5 minutes) even at pH values as low as 4.5 (Knocke et al. 1990). The impact
of the low oxidizing power of chlorine and the short contact time associated with most enhanced
coagulation practices makes Mn removal in the bulk water by chlorine ineffective. Most
conventional water treatment plants have less than 2 hours of chlorine contact time between the
coagulation and filtration processes.
USEPA (1999) provides guidance for the development of a Mn removal strategy with
enhanced coagulation. A utility should (1) document Mn concentration and fractionation
(particulate, colloidal, and dissolved); (2) identify unambiguous finished water Mn goals; and (3)
optimize processes with respect to oxidation, adsorption, and coagulant purity.
Manganese contained in many ferric salts that are used in water treatment is also a
potential problem in that it can introduce additional Mn beyond what is found in the source
water. If a utility switches from low doses of ferric or alum to high doses of ferric, the coagulant
itself may significantly increase the amount of dissolved Mn added to the water stream. In an
enhanced coagulation study, Mn contamination of liquid ferric chloride resulted in soluble Mn
concentrations up to 0.5 mg/L (Crozes et al. 1996). The greater the amount of Mn in the water
47
Residual Management
48
LITERATURE REVIEW
The literature review was conducted to update the PIs on current understanding and
developments in Mn treatment, occurrence, chemistry, problems, and related areas. The literature
review also served as a source of utility contacts for the initial survey part of this project.
The techniques used to identify references were primarily database searches, library
reviews, association inquiries, university sources, personal contacts, and known thesis
publications. The searches revealed hundreds of relevant references. The investigators collected
as many as possible (although some were unobtainable) and considered the literature review
sufficiently complete and current to meaningfully advance the project goals. The lengthy list of
initial references was narrowed down to identify those articles and documents that provided the
most pertinent information. This smaller list of detailed references was read by the PIs,
summarized, and subsequently used as part of the literature review presented in Chapter 2,
augmenting previous review efforts.
INITIAL SURVEYS
The initial surveys were conducted to help the researchers determine the depth and
breadth of utility experience with manganese issues, problems, and experiences. A manganese
issue is defined as any problem associated with the treatment, sequestration, or occurrence of Mn
that could or does result in a distribution system problem. Distribution problems could be in the
consumers homes or associated with the operation of the distribution system, such as flushing.
The collection of this information was focused on utilities that had reported Mn problems in the
literature, had constructed a treatment plant to remove Mn, or were known to the PIs as locations
where Mn was a potential problem.
A list of potential survey utilities was assembled to ensure that we contacted utilities that
were representative of surface waters and groundwaters; diverse geographical regions; small,
medium, and large utilities; and at least one of each of the commonly used Mn control
49
50
Miscellaneous Considerations
Each survey was facility specific. A facility was defined as a treatment plant, chemical
feed system, or source of supply if no treatment was provided, that had a discrete connection to
the distributions system. For example if a water treatment plant had vastly different treatment
trains but the combined effluent connected to the distribution system in one place it was
considered one facility. If a utility had three separate water treatment plants that connected to an
independent (or somewhat independent) distribution system, then each facility was eligible for
the survey.
51
After entry into a database, the information gathered from the initial survey was
examined to determine the typical ranges of source water Mn seen by the utilities and correlate
this with source water type and certain water quality parameters. It was used as the basis for
selection of detailed survey participation. The PIs used it as the initial source to discern the
industrys general awareness of Mn and the implications of Mn control.
DETAILED SURVEYS
The project PIs and core working group met at least monthly to review completed initial
surveys, and from these surveys, select utilities for further in-depth study. The investigators
looked for facilities with substantial challenges related to Mn removal problems or occurrence.
As with the initial survey, criteria for detailed survey facilities included fair
representation of surface and groundwaters, a breadth of Mn removal technologies, utility size,
and geographic distribution throughout the United States.
The detailed survey focused on four specific areas of interest: source water, treatment,
distribution system, and customer satisfaction. The source water questions probed specific issues
such as reservoir turnover or seasonal changes. The treatment questions were designed to probe
utility water quality goals, recycle streams, and fate of solids. The distribution system section of
the survey investigated size, detention time, materials, oxidant residuals, and flushing programs.
The customer satisfaction section reviewed the tracking and follow-up of customer complaints.
A utilitys ability to offer differentiable customer complaint information was one of our criteria
for further investigation. In addition to the survey questionnaire, the utilities were asked to
provide annual water quality data for 20 specific water quality parameters, collected in the raw
water, finished water, and distribution system. A separate spreadsheet was sent electronically to
each participating utility for the respondent to return when completed. The detailed survey
instrument and water quality data spreadsheet are included in Appendix A. NOTE: In Appendix
A, only the raw water quality data (WQ) sheet is shown as the finished and distribution WQ data
sheets are simply duplicates of it.
The detailed survey was also conducted by telephone, usually by the same individual who
completed the initial facility survey. Advance contacts were made to determine utility
willingness to participate, and to give the utility personnel time to gather relevant information
prior to the survey interview and ascertain the most appropriate contact person for specific
survey questions. The survey interviews typically took about one hour to conduct, but the
utilitys overall participation required about two additional hours to compile information and
water quality data and forward it to the research team.
52
Purpose of Sampling
One of the main research efforts associated with this project was the determination of
how much Mn was present in the distribution systems in those utilities that had reported Mn
issues. We knew that some utilities that have source water Mn, and treat for it, still have Mn
issues in the distribution system. We also knew that Mn can become a problem with consumers
even if the Mn leaving a treatment plant is below the secondary standard, and that Mn can
precipitate within system piping over time and then be resuspended during hydraulic transients.
Consequently, our interest was related to systems that were producing water from the source or
treatment plant that contained an identifiable concentration of Mn, even if it was below the
present secondary standard. However, we did not know how much Mn would be found in a
distribution system at any given time compared to the concentration of Mn entering the system.
In addition we did not know how the speciation of the Mn between the particulate and soluble
forms would change as the water flowed through the piping network. We did suspect that there
were various influences on the speciation of Mn, including residence time, pH, temperature,
cation and anion matrix, organic concentration, and biological activity. We asked utilities to
sample their distribution system water once a quarter for a full year, in order to capture seasonal
variations.
Samples were taken seasonally starting in the winter of 2004 ending in the winter of
2005, representing five seasonal sample sets. Samples were sent to the Philadelphia Water
Department Bureau of Laboratory Services (PWD-BLS) for metals analysis, alkalinity, arsenic,
calcium, hardness, total iron/manganese, colloidal iron/manganese, dissolved iron/manganese,
and sodium. The utilities themselves were to analyze the water for general WQ parameters and
when they were not capable of doing certain analysis in-house they sent sample water to a
contract laboratory.
Selection of Utilities
The basis of utility selection for this task had much to do with willingness and
enthusiasm. The demands placed on the utility to conduct this sampling were substantial. From
the pool of willing utilities, 12 were chosen for system sampling and analysis. The utilities
53
Sampling Methodology
Sampling Materials
Prior to initiation of the seasonal testing at each of the 12 utilities, staff in the metals
laboratory of the PWD-BLS water quality laboratory packed and shipped all supplies necessary
for the collection of samples for general water quality parameters and metals. The contents of
each package are listed in Table 3.1. An instructional DVD, explaining the sampling process for
collection of the metals samples, was filmed at PWD and included in the shipment of sampling
supplies.
Grab samples for turbidity, alkalinity, UV254, color, ORP, and conductivity were
collected in 1-L Nalgene (Nalge Nunc International, Rochester, N.Y.) high-density polyethylene
(HDPE) bottles. Metals samples were collected in 250-mL Nalgene HDPE bottles. The metals
samples were sub-sampled into 60-mL polyethylene (PE) bottles from SCP Science (Baie
DUrf, P.Q.). Filtered metals samples were filtered through Millipore Millex-GS 0.22-m filters
(Millipore Corp., Billerica, Mass.), with mixed cellulose ester (MCE) membranes. The filters
were attached to 60-mL plastic Becton-Dickson (Franklin Lakes, N.J.) syringes. A Millipore
Amicon stirred-cell ultrafiltration kit was used to further fractionate an aliquot of each sub-
sample. Millipore YM30 UF regenerated cellulose filters were used for filtration in the
ultrafiltration cell. These filters have a size exclusion fraction of 30 kDa. High purity nitrogen
(N2) gas supplied pressure within the ultrafiltration chamber for filtration.
Presently, many utilities use 0.45-m filters for separating particulate and non-particulate
Mn. However, separation of truly dissolved from particulate Mn may likely require a finer
porosity. Therefore, we selected 0.22 m and 30 kDa as research sizes for this study. The 0.22-
m filter is a size that most utilities treating for Mn could easily incorporate into an analytical
program. On the other hand the 30-kDa requires special equipment and considerably more time.
For this research it was felt that the 30 kDa was a reasonable size that would give good assurance
that the filtered water sample only contained dissolved Mn
Samples for metals analysis were preserved with 0.25 mL of trace metal grade nitric acid
(HNO3) at PWD-BLS, not in the field. This made sample collection and shipping easier.
54
Table 3.1
Items shipped to each utility participating in the seasonal sampling study
Item Manufacturer or source Purpose
1-L HDPE bottles Nalgene General WQ parameter samples
250-mL HDPE bottles Nalgene Metals grab samples
60-mL PE bottles SCP Science Metals sub-samples
Plastic 60-mL syringe Becton-Dickson 0.22-m filtration
0.22-m filters Millipore Filtration
Ultrafiltration kit Millipore Ultrafiltration
30-kDa filters Millipore Ultrafiltration
DVD PWD Sample collection demo
Chain of custody sheets PWD Sample tracking
Field data sheets PWD Field WQ data
Sampling and analysis of general water quality parameters was performed by each
respective utility. For the parameters measured in the field (free and total chlorine, pH,
temperature, and dissolved oxygen), PWD supplied a field data sheet for recording all data and
QC measures. These sheets were returned to PWD and reviewed by project staff.
Sampling for metals analysis was also conducted by the individual utilities. However,
following collection of the samples for metals, utilities returned the samples to the PWD-BLS for
processing and analysis. Details on the sampling and sample preparation protocol followed by
utilities are included in Appendix B, and summarized in the following.
A diagram depicting the sample collection scheme for metals samples is shown in
Appendix B, Figure B.1. In addition to the distribution water samples, each utility collected
55
56
Samples were analyzed for As, Na, Mn, and hardness (Ca and Mg) using inductively
coupled plasmamass spectrometry (ICP-MS), based on EPA Method 200.8. A brief description
of the analytical process, as described in the Standard Operating Procedure for Method 200.8,
Revision 5.4, follows.
Sample material in solution is introduced by pneumatic nebulization into a radio-
frequency plasma where energy transfer processes cause desolvation, atomization, and
ionization. The ions are extracted from the plasma through a differentially pumped vacuum
interface and separated on the basis of their mass-to-charge ratio by a quadrupole mass
spectrometer having a minimum resolution capability of 1 amu peak width at 5% peak height.
The ions transmitted through the quadrupole are detected by an electron multiplier and the ion
information is processed by a data handling system. Interferences relating to the technique are
recognized and corrected. Such corrections include compensation for isobaric elemental
interferences and from polyatomic ion interferences derived from the plasma gas, reagents, or
sample matrix. Instrumental drift as well as suppressions or enhancements of instrument
response caused by the sample matrix are corrected for by the use of internal standards.
The samples were analyzed for Fe levels using inductively coupled plasmaatomic
emission spectrometry (ICP-AES), based on EPA Method 200.7. Iron measurements were
initially made using ICP-MS, but it was discovered that the interference equation that corrects
for the common calcium oxide interference (Ca40O16) at the iron mass (56) was not adequate for
the low levels of Fe in most of these samples. A brief description of the analytical process, as
described in the Standard Operating Procedure for Method 200.7, Revision 4.4, follows.
The Leeman Labs Profile ICP-AES is a sequential instrument. The instrument measures
characteristic atomic-line emission spectra by optical spectrometry. Samples are nebulized and
the resulting aerosols are transported to the plasma torch. Element-specific emission spectra are
produced by a radio-frequency inductively coupled plasma. The spectra are dispersed by a
grating spectrometer, and the intensities of the line spectra are monitored at specific wavelengths
by a photosensitive device. Photocurrents from the photosensitive device are processed and
controlled by a computer system. A background correction technique compensates for variable
background contribution to the determination of analytes. The background is measured adjacent
to an analyte wavelength during analysis.
With both methods, quality control was monitored throughout the analysis. Following
calibration, the calibration standards were analyzed as samples and required to be accurate within
10% of the expected concentration. Following these checks, a second source standard was
analyzed to verify that the calibration standards were accurate. The second source standards were
required to be accurate within 10% of the expected concentration. Throughout each analysis,
one sample in every 10 was analyzed in duplicate. The relative percent difference between
duplicate measurements was required to be <20%. Additionally, one sample in every 10 was
spiked with known amounts of the method analytes, and recoveries of the spiked amounts were
required to be within 30% of the expected concentration. Internal standards were monitored
throughout analysis by ICP-MS, and used to correct analyte measurements for instrumental drift.
Each internal standard response was required to be within 60% to 125% of the response at the
beginning of the analysis. If a sample measurement was outside of the calibration range, an
additional standard outside of the calibration range was run to ensure that the instrument
response was linear and accurate at the sample level. Alternatively, if a sample contained an
analyte at a level significantly greater than the highest calibration standard, the sample was
57
Mathematical Manipulation
When performing statistical evaluation of data, such as averaging, we used the MDL for
all ND data. We prefer this conservative method; however, it may overestimate a sample
concentration.
The analytical data generated by PWD-BLS has MDL values of <0.001 mg/L for Mn,
and <0.005 mg/L for Fe. Therefore, for all [Mn] <0.001 mg/L we used the value of 0.001 mg/L,
and for all [Fe] <0.005 we use 0.005 mg/L, for ND data values. However, not all data used in this
report were generated by BLS. The MDL or RL presented by the source of the data was used.
The handling of triplicate analysis using this method was done using the above described
procedure. For example, if a triplicate sample was analyzed for Mn using a method with an MDL
= 0.001 mg/L for which results were ND, ND, and 0.004 mg/L, then the average result of our
calculation would be (0.001 + 0.001 + 0.004) / 3 = 0.002 mg/L. If the results from the triplicate
samples were all ND then the average would be 0.001 mg/L; yet if this set of data is referred to
in the text the average would be presented as below the detection limit or at <0.001 mg/L.
Some special cases of water quality data analyzed by outside laboratories, and submitted
for use in this project, have much higher reporting limits than the in-house analysis. In some
cases we were forced to discard the data, such as that from a utility which listed an iron MDL of
<0.100 mg/L. Using this MDL would greatly skew the data set. In another case, a utility listed
<0.040 mg/L as the detection limit, and in this case we chose to include the data, using the value
0.040 mg/L (Fe) in our calculations.
Data Presentation
When we present the data in the text or in a table, we list the actual analytical result. For
example, an ND Mn sample will be written as <0.001 mg/L.
For statistical values derived from multiple analyses, data presentation is handled in the
following way: if all values are ND, then the average is presented as below the detection limit,
and if any one of the analytical values is detectable, then the MDL is used for calculation and
presentation of all the ND data points. The average will therefore always be greater than the
detection limit. A zero is not used in a tabular data presentation.
58
When possible the ND data is presented as the MDL with a note on the chart or graph and
a legend entry of hash marks to call it out. Sometimes the MDL may be so low that the value
may appear to be zero on a chart or graph.
For cases where the average value is used in a graphic, the above listed graphing rule
applies. If all the analytical values are ND, then the MDL value appears on that graph.
For example, if a triplicate sample is analyzed for Mn (MDL = 0.001 mg/L) and results in
values of ND, ND, and 0.004 mg/L, it will appear on a figure as a 0.002 mg/L data point or bar,
while values of ND, ND, ND would appear on the figure as a 0.001 mg/L point or bar with hash
marks and a note in the graph or chart legend. There should be no data point represented as a
zero.
Case Study I had four major investigational objectives, plus two minor objectives, only
the first two were used to write the report:
59
The PWD has two pilot plants, each located at a full-scale water treatment plant. These
plants draw water from two different river sources, the Schuylkill River and the Delaware River.
A schematic of the Belmont WTP pilot plant is presented in Appendix B, Figure B.2.
The pilot plants draw water from the river source without any pretreatment. About 20
gpm of river water enters a 600-gallon raw water basin that provides about 30 minutes of contact
time to model pretreatment chemical addition.
The water is pumped and split into two parallel 8-gpm process trains. First the flow enters
two small rapid-mix basins, followed by two (Belmont pilot) or five (Baxter pilot) flocculation
basins, with a tapered floc mixing scheme. The water then flows through a lamella plate,
upflow clarifier for settling; the full-scale plants have gravity settling basins.
Depending on the investigation protocol, the settled water from one of the two process
trains may enter an 8-column, counter current, intermediate ozone contactor. Ozone is typically
added in the first column only, and then quenched, if necessary, in the last column.
The settled water, or post ozone contact water if required in the investigation, is then
filtered by gravity. Each train has two dual media filters (21 in. anthracite and 9 in. sand) and one
biologically active GAC filter (29-in. depth).
Online monitors measure raw water turbidity and flow; flocculation pH; sedimentation
pH, turbidity, and particle counts; filter head loss, turbidity, and particle counts; intermediate
ozone residual in various locations throughout the columns; plus ozone feed gas and off-gas
concentrations. All online data is recorded at 2-minute intervals in a PC-based data logger.
The Case Study I schedule ran from March 2004 to February 2005. At least two of the
investigations were repeated twice to obtain seasonal data.
Chemical doses will be established based on previous testing experience, full scale
plant operations, and jar testing in accordance with the judgment of the pilot plant
staff.
Both Train A and Train B will be in service with equal influent flow of 8 gpm to each
train. Both pilot plants will run at 8 gpm through flocculation and waste 2 gpm before
sedimentation.
Rapid mixing and flocculation will be set to optimized G-values as determined from
previous investigations. The flocculation basins have tapered mixing intensities.
The coagulation and filtration pH will be varied as described above.
For Investigations 1 and 3, intermediate ozone will be used with eight contact
columns, providing a total hydraulic residence time (HRT) of 17 minutes at 6 gpm.
- Apply an ozone dose of 2 mg/L or more as needed to yield a measurable ozone
residual at the outlet of the final contact column in an attempt to oxidize all the
Mn.
- Apply sodium hydroxide for pH adjustment, if necessary, at the influent to the 7th
column to achieve the targeted filtration pH.
- Quench the ozone residual with sodium bisulfite, applied at the inlet to the 8th
column such that an ozone residual of >0.0 but <0.1 mg/L remains at the outlet
bottom tap of the 8th column. This trace ozone residual will verify that there is no
carry over of reducing agent (sodium metabisulfite) into the filters.
Train A will provide settled/ozonated water to dual media Filters A-1 and A-2 and
GAC Filter A.
60
Further details of the pilot testing protocol, operating procedures, and sample collection
schedules are located in Appendix B.
The half cell potential is measured with an inert (platinum) indicator electrode at a given
temperature, and Ereference is the reference potential measured with a reference (Ag-AgCl)
electrode at that same temperature.
The Ereference table provided by the manufacturer to convert ORP read on the meter to EH
is listed in Table 3.2.
61
The Huntington Water Treatment Plant treats water for drinking-water compliance using
traditional treatment techniques. Prior to the D/DBP Rule they coagulated at an elevated pH and
relied on GAC filtration to reduce taste and odor compounds. They have changed their
operational practices to remove more TOC via coagulation and moved the initial point of
chlorination further back into their water treatment process.
Water from the Ohio River is pumped into a holding reservoir where solids are allowed
to settle. Following the initial settling of solids, sulfuric acid (to enhance removal of TOC in
coagulation), ferric sulfate (coagulant) and a polymer coagulant aid are added at the mixing tank,
Table 3.2
Reference half-cell potential
Temperature Ereference half-cell potential
(C) (mV)
10 214
20 204
25 199
30 194
Source: Thermo Electron Corporation (2003)
before the water splits into two settling basins. In each of the settling basins, there are four
flocculation chambers consisting of baffling, settling, and plate settlers. As the water leaves the
sedimentation basin, sodium hydroxide is added to increase the pH to around 7.0, followed by
addition of a filter aid and chlorine. The addition of 2 mg/L chlorine prior to filtration aids in Mn
oxidation and subsequent removal through filtration. To remove taste and odor causing organics,
the plant has historically used GAC media in all twelve of the filter basins. Recently, one of the
GAC filters was replaced with anthracite. Depending on other water quality parameters,
occasionally some Mn (which may remain dissolved) passes through the filter even with the
raising of pH and addition of chlorine. The Mn that passes through the filters manifests itself in
increased turbidity in the clearwell. There is no chlorine residual leaving the GAC filters.
Comparing the levels of Mn in the sedimentation effluent to the effluents of the anthracite
filter and an adjacent GAC filter will directly evaluate the performance of the two media types
on Mn removal ability. The experiment will limit media type as the only variable.
A detailed description of the Case Study II protocol and schematics of the Huntington
WTP unit operations and sampling locations are presented in Appendix B.
The case study protocol calls for continuous measurement of Mn at the filter influent, the
effluent of one anthracite filter, the effluent of one GAC filter, and the combined effluent of all
12 of the plants filters. Online Mn measurements were obtained with a Tytronics Sentinel online
analyzer (Galvanic Applied Sciences USA Inc., Lowell, Mass.).
Grab samples collected throughout the plant process will be analyzed on site for Mn with
the Hach DR/2400 spectrophotometer (Hach Co., Loveland, Colo.) using the 1-2-(Pyridylazo)-2-
Naphthol PAN method (low range). These grab samples will also be analyzed on site for pH,
alkalinity, free and total chlorine, and conductivity.
Additional samples will be collect at points through out the plant process, with portions
filtered, and shipped to Philadelphia Water Department, Bureau of Laboratory Services (PWD-
BLS) for metals analysis. These unfiltered (total) metals samples were analyzed for Mn, Fe, Na,
62
COST MODEL
The purpose of the cost model is to provide utilities a guideline for comparing the capital
and operating costs for various treatment technologies for Mn. The tables are not designed as an
estimating tool for new facilities but rather as a cost comparison. Out of necessity, the tables,
located in Chapter 4, present overall national costs rather than geographical specific estimates.
This section describes how the tables were calculated and the basic assumptions that went into
the tables.
Consumer Benefit
The consumer benefit with any of the secondary standards is very difficult to quantify,
since the acceptable level of a particular contaminant will vary with the individual. Therefore,
the research team developed a set of assumptions that judgmentally seemed reasonable as both
typical and representative of many water utilities in the United States. The assumptions that
formed the basis of the tables are as follows:
The influent Mn concentration is about 0.5 mg/L. Naturally, this concentration will
vary with source and utility location. However, the costs associated with a plant
constructed for raw water Mn between approximately 0.2 mg/L and 2.0 mg/L will be
about the same. Once raw water Mn exceeds 2 to 5 mg/L, some direct filtration
processes would be stressed and, probably not applicable.
Treated water target concentrations were selected as 0.05 mg/L, the present USEPA
secondary standard, 0.02 mg/L, 0.015 mg/L, and 0.01 mg/L. The value of 0.02 mg/L
was selected as a level that would significantly reduce Mn problems compared to the
present standard but would not necessarily completely eliminate some household
difficulties. The value of 0.01 mg/L represents a very low target level of Mn that
might be set by utilities that wished to achieve the very highest water quality relative
to Mn. The value of 0.015 mg/L is quite simply the value between 0.02 mg/L and
0.010 mg/L.
All costs are presented in US dollars based on 2005 estimates
The per capita consumption used for the tables (and consequently population served)
is 378 liters per day (L/d) or 100 gallons per capita per day (gpcd). Per capita
consumption will vary geographically and with type of community. Although the
industry consensus seems to be that the per capita consumption may be less than 100
gpcd, overall national figures suggest that this estimate is reasonable when one
decides plant production by population served. We do recognize that per capita
consumption will vary from over 400 gpcd in the arid southwest to less that 40 gpcd
in the cooler northeast.
Unaccounted water is taken as 15 percent of plant production. Unaccounted water for
this study was taken as the difference between water produced by a plant and the
63
64
Utility Costs
The utility cost assumptions are also presented in the Chapter 4 tables. These cost tables
are based on either constructing a new plant or upgrading an existing facility to produce water at
a lower Mn level. The costs include construction of a new plant or, in the case of upgrading, the
costs associated with adding a chlorine or potassium permanganate feed system. The specific
chemicals would be sodium hypochlorite or dry potassium permanganate solubilized. Capital
costs do not include raw and finished water pumps, equipment superstructure, standby power,
land, legal, engineering or contingencies. Equipment life was taken as 20 years. Costs include
equipment and piping, process tanks, chemical feed storage and equipment, operating labor and
maintenance, plant power, reporting, and costs for chemicals. In many cases, only a nominal
operating cost is associated with a lower Mn target because the process inherently will achieve
very low treated water concentration anyway. An example would be lime or ion exchange
softening, which usually reduces Mn as the process softens the water. Therefore, the additional
cost for a lower Mn target may primarily be for increased sampling and monitoring and
reporting.
Basic Assumptions
All the basic assumptions are tabulated above. These assumptions should be reasonable
for comparing relative impacts of treating water to Mn levels below the regulatory level of 0.05
mg/L. Since many of the impacts from Mn are very difficult to quantify, each utility should
conduct an assessment relative to the benefits that may be achieved from dealing with this
secondary issue. The concept that water with a manganese concentration of 0.05 mg/L will likely
65
The references used for the cost model are included in the References section. However,
it should be indicated that published references of Mn removal costs are at best, sparse. Reliance
was made on in-house cost information available to the project team and individual experience at
particular utilities.
66
INITIAL SURVEYS
The initial surveys were conducted to help the researchers determine the depth, breadth,
and trends of water utilities experience in manganese control. The collection of this information
was focused on known places with Mn issues. In order to understand this analysis it is important
to know that the initial surveys were not a scientifically random sampling of water utilities that
can be used to generate statistically significant projections about the water industry as a whole. It
was, rather, a focused survey to look into the specific experiences of a number of utilities that we
suspected would have Mn issues.
Our goal was to complete at least 100 surveys. Knowing this we had a goal of getting
contact information for over 200; we assumed that only about 50% of the utilities contacted
would respond favorably to our request for information. It turned out that we were wrong, the
industry response was overwhelmingly favorable and our success rate was over 90%. The
industry felt comfortable talking about Mn issues. Therefore, we did not need all 200 potential
candidates based on response rate. However, we had certain demographic criteria (geographic,
Mn technology, source water, population, etc.) and we ended up increasing our pool of potential
candidates to 348. From this pool, we connected with 158 utilities and from these participating
utilities we conducted 242 initial surveys. Each survey is facility-specific, and in some cases a
utility that has several discrete facilities gave information for more than one facility. Since the
research was distribution systemcentric, we defined a discrete facility as one that had its own
connection to the distribution system. Initial surveys were done only for facilities that had
possible Mn issues. That is to say, we did not complete a separate initial survey for each possible
facility, but only for those that helped tell some aspect of the story of Mn in drinking water.
67
Geographic Distribution
Of the 242 initial surveys conducted there were 217 domestic facilities and 25
international facilities, of which 15 were Canadian. The other international participants were
from the UK and Australia.
The map of the U.S. in Figure 4.1 shows the number of facilities that participated from
each state. For the domestic surveys, we attempted to contact at least one utility in each state. We
succeeded for all but four statesHawaii, Tennessee, Kentucky, and Vermontresulting in
robust geographic distribution. The states that received the most attention were Massachusetts,
California, and New Jersey. Massachusetts has the most surveys because of its historical Mn
issues. California was the second largest because of its large population and many wells. New
Jersey is the third largest contributor to the data set as it is the most densely populated state in the
union.
4
4
5 2
7
4 4
3 3 1 3
1 5 NH-3
4 4
2 8 VT-0
3 2 1 4
1 MA-37
3 4 4 0
4 RI-3
28
0 CT-5
2 2 2
8 1 NJ-13
2 1 3
DE-2
3
6 MD-2
3
DC-0
1
Figure 4.1 Geographic distribution of U.S. utilities participating in initial survey (n = 217)
The database created from all of the completed initial surveys has several interesting
characteristics. Figure 4.2 shows the breakdown of source water types. As one might expect,
68
Treatment Type
We wanted to survey a wide variety of facilities using different treatment types and were
successful at getting a good distribution of types. However, to analyze the data and express them
in graphical format conveniently, Figure 4.3, we grouped some techniques into larger categories.
We recognize that since each facility is a unique and a discrete reality, such grouping is, though
useful, in a small way artificial. For example, a plant that uses GAC for taste and odor control
but has a conventional pretreatment process is grouped under conventional gravity settling
(CGS), while if it used the GAC for taste and odor but without pretreatment, it would be a GAC
plant.
The largest treatment type surveyed is conventional gravity settling. Specifically, CGS is
defined as rapid mix, flocculation, settling, and granular media filtration. The next largest group
is pressure filtration for Fe and Mn removal. This group includes mostly proprietary systems that
all utilize pressure filters and specific media. Since we went looking for facilities that have Mn
40%
Ground Water
5%
Surface Water
2%
Blend of GW and SW
GWUDI
53%
Figure 4.2 Types of source water treated by facilities in initial survey (n = 242)
issues it is to be expected that a large portion of them are built specifically for Mn treatment. The
direct filtration and inline filtration plants were grouped together as they were similar, with
inline plants not having flocculation. Disinfection only makes up a considerable proportion of
our database (14%); these are mostly groundwater systems but all have high-quality sources. The
69
The distribution of coagulants used in presented in Figure 4.4. Over half (51%) of the
facilities do not use a coagulant of any kind. Although some GW systems use coagulants, by far
the majority do not, so the 53% of facilities surveyed having GW as a source explains the 51%
without coagulant use. The most prevalent coagulant, of those that do use one, is alum (26%)
with ferric salts making up only 9%. Ferric salts themselves can be a source of Mn. Of the
remaining types most are aluminum-based. Another 5% of the facilities use polymers as the
primary coagulant.
14% 5%
CGS
Disinfection Only 5%
Advanced Clarification
Lime Softening 19%
Sequestration Only
Others 34%
Other treatment types include: Aeration, Air Stripping, Ion Exchange, Membrane Filtration,
Reverse Osmosis, and GAC filters for organics removal.
70
Not Given
51%
Figure 4.4 Type of primary coagulant used to treat water (n = 242)
Self-Reported Mn Concentrations
The initial survey included questions about the concentration of Mn in source water,
finished water, and distribution system water; the response is shown in Table 4.1. Of the 242
participating facilities, 185 provided some form of source water Mn data, be it average,
minimum, or maximum. All told, 204 said that they did measure their source water for Mn. For
finished water, 190 facilities provided some form of Mn data, and 202 said that they measured
finished water Mn. Only 46 facilities provided distribution system Mn data, while 55 said they
measured it.
Thus over 80% of the utilities contacted measure Mn in both source and finished water,
while only 23% look for it in their distribution system. This may appear logical, as most
operational measurements are made at locations that allow for operational adjustment. It may
also reflect the prevailing thought process that the distribution system is a black box in which
nothing changes. However, this assumption is not correct and we as an industry should change
our testing habits.
Table 4.1
Facilities providing Mn concentration data in initial surveys
Number of facilities (out Number of facilities that say
Water of 242) providing data Percent they make the measurement Percent
Source 185 76% 204 84%
Finished 190 78% 202 83%
Distribution 46 19% 55 23%
For source water Mn, 179 of the 242 facilities (74%) provided average Mn concentration
data, 59 gave a minimum, and 77 gave a maximum. Figure 4.5 is a plot of a statistical analysis of
average source water Mn data.
71
1.00
Total Manganese (mg/L)
0.60
75th Percentile
0.40
Mean
0.20 Median
25th Percentile
10th and 5th Percentile
0.00
Ground Water Surface Water Blending GWUDI
n = 92 n = 73 n = 10 n=4
Figure 4.5 Box-and-whiskers plot of average source water Mn concentration data from
initial surveys, showing mean, median, and percentile ranges
of maximum reported values was also done. Table 4.2 presents maximum data. The maximum
GW and maximum SW are similar. This means that SW can, at times, be as great a source of Mn
as GW. This observation must be understood in relation to the average, as SW has a narrower
range of values and a lower mean value, meaning these high points are unusual and occur
infrequently. Yet they do exist, which can significantly influence treatment.
72
For finished water, 189 of the 242 facilities (78%) provided average Mn concentration
data, 47 gave a minimum, and 52 gave a maximum. Average concentrations are plotted in Figure
4.6, in a graphical representation similar to that in Figure 4.5.
Table 4.2
Maximum source water Mn concentrations reported in initial survey
Source water type n value Maximum Mn concentration
(mg/L)
Groundwater (GW) 32 4.5
Surface water (SW) 36 4.0
Blending 6 2.0
GWUDI 3 2.3
0.080
0.070
0.060
Total Manganese (mg/L)
95th Percentile
0.040
0.030
75th Percentile
0.020 Mean
Median
0.010 25th Percentile
10th Percentile
5th Percentile
0.000
Ground Water Surface Water Blending GWUDI
n = 98 n = 75 n = 11 n=5
Figure 4.6 Box-and-whiskers plot of average finished water Mn data from initial surveys
Though hard to see on the figure, for groundwater the median, 25th, and 10th percentiles
were all the same value (0.005 mg/L), and for SW the 10th and the 25th percentiles were the
same at 0.005 mg/L. The preponderance of 0.005 mg/L data resulted from a detail of our data-
handling protocol. As explained in Chapter 3, the non-detect (ND) data values were assigned the
value of the MDL or RL of that analysis. We did this to be able to conduct statistical
calculations. This protocol was spelled out in a document called the playbook, generated by
the project team, that outlined how we handled ND data. Its main points are included in the
Chapter 3 discussion.
73
For distribution system water, 44 of the 242 facilities (18%) provided average Mn
concentration data, 13 gave a minimum, and 14 gave a maximum. This is not a large data set;
however, we did perform a statistical analysis on it, sorted by source water type and presented in
Table 4.3. The GW and SW seem to have about the same amount of Mn in the distribution
system samples, and all but the highest average values are at or below the SMCL of 0.050 mg/L.
Table 4.3
Mn concentrations in distribution system water, from initial surveys
Average reported Mn concentrations in distribution system (mg/L)
10th Geometric Arithmetic 90th
Source type n Lowest %-ile mean mean %-ile Highest
Groundwater 18 0.003 0.005 0.010 0.017 0.050 0.050
Surface water 20 0.001 0.005 0.013 0.021 0.045 0.090
Blending 4 ND 0.005 0.005 0.005 0.005 0.005
GWUDI 2 0.005 0.005 0.005 0.005 0.005 0.005
Notes: ND = non-detect; all values in this cell were ND; refer to playbook.
All utility data reported as non-detect was assigned a value of 0.005 mg/L for
statistical analysis, unless an MDL value was also furnished by the utility; 20 of 44
facilities reported non-detect for the average distribution system water Mn.
During the initial surveys most of the utilities contacted were asked how they measured
Mn. In some cases they were not sure, or the question was not asked. This resulted in 90 of the
participating utilities (158 utilities) giving a useful response. More than half, 57 out of 90 (63%),
used an onsite colorimetric assay (e.g. Hach PAN method) while the remaining 36% used a more
advanced atomizing process (e.g. AA, ICP-AE, or ICP-MS). As one would imagine, the majority
of colorimetric analysis was done onsite while most of the atomizing analysis was done in a
74
Since oxidation is the primary method of Mn control, and more specifically, since
chlorine is a necessary component of oxide-coated media control, we asked each facility to
describe the oxidants used in their process and to describe which they used as the primary
disinfection. The answers to these questions are presented in Figures 4.7 (primary disinfection)
and 4.8 (oxidants as a whole).
3.3%
Chlorine
0.8%
Ozone
0.4%
Chloramines
0.4%
None
90% 11% 0.4%
Advanced Oxidation
5.8%
UV
not given
The overwhelming majority of facilities (90%) use chlorine as the primary disinfectant;
even some plants that use ozone indicate that they use chlorine as the primary disinfectant.
Almost 6% of the facilities did not reveal the primary disinfectant. The next largest disinfectant
(oxidant) grouping was ozone (3%). One facility, a membrane plant, did not use an oxidant as its
primary disinfectant. The main pie chart wedges are 90% and 11%, totaling 101% due to
rounding.
In terms of oxidants in general, 53% of the facilities have nothing other than chlorine in
their process (Figure 4.8). The rest have other oxidants used in conjunction with chlorine at
75
We asked all the utility participants to answer the question, Do you consider yourself to
have a Mn problem/issue? Of the facilities, 125 indicated that they did not have a Mn problem
while 117 indicated that they did. That translates into 52% no and 48% yes. Since we were
targeting facilities with Mn issues, we were somewhat disconcerted with more no than yes
responses.
Chlorine only
29% 5%
No oxidant used
Figure 4.8 Facilities grouped by oxidant and oxidant combination within WTP (n = 242)
Although we did not intend this to be a trick question, we did leave it open ended. One of
the ideas of the project was to get a feel for what people perceived about Mn and Mn-related
problems. If a utility has the Mn issue under control, then the issue may be perceived to no
longer be a problem. Sometimes Mn has been an issue for such a long time that the facility no
longer considers it an issue. A great story is that of a pumping station operator who has to put on
boots to inspect a certain area of the station, and has been doing it for so long that he no longer
considers a foot of water on the floor an issue. The initial survey was not a sophisticated
psychological tool with repeat or confirming questions, though, so only so much can be gleaned
from this analysis.
76
Of the 242 facilities that were surveyed, 128 of them (53%) have specific Mn treatment.
Of these 128 facilities, 41 (32%) use KMnO4 to oxidize Mn; 38 (29%) use some sort of
trademark pressure filtration system (Manganese Greensand, Pyrolusite, Filtronics); 26 (20%)
use induced oxide-coated media; 12 (1%) use sequestration alone. The other processes are
chlorine and/or chlorine dioxide (4), biological removal (2), ozone (2), and aeration only (2). We
found through additional inquiries that some facilities treat Mn with induced oxide-coated media
but simply did not know it. Interestingly enough, some of these facilities are controlling Mn on
GAC filters; that is, using chlorine to form a layer of oxide-coated media.
Casale, LeChevallier, and Pontius, in their AwwaRF report (2002) said that the 1996
WaterStats Database revealed that 18.1% of GW and 7.9% of SW systems specifically used
iron/manganese control processes, and that 6.9% of the GW systems and 0.2% of SW systems
used greensand or oxide-coated media. Those percentages are lower than those presented in this
data set; therefore the PIs believe that the goal of targeting facilities with Mn issues was met.
The results of this and the previous question reveal something about utility perception. Of
all the respondents to the initial surveys, 48% of facilities said they had a Mn problem yet 53%
said they had specific Mn treatment. As previously mentioned, this makes sense if one assumes
that successfully treating Mn means there is no remaining problem.
However, if one makes a similar comparison to the modified Mn issue percentage, then
67% have a Mn issue while only 53% specifically treat for Mn. That is, only 79%, of the
facilities are aware of how they are actively handling Mn. This may indicate that there are as
many as 1 in 5 facilities that treat for Mn without really knowing it. Again, this data set is from a
focused survey, and should not be projected to the industry as a whole.
So, it appears from our initial survey sample that most utilities know if they have Mn
issues and know how they are handling them. Yet, there is a substantial fraction of utilities that
appear to have Mn issues or potential issues, but since there is not currently an active unresolved
problem that translates into consumer dissatisfaction, the issue is not perceived as a problem.
While the semantic issue of some interviewees considering a known and fixed problem as a non-
problem may be trivial, the issue of utilities having a Mn problem they are unaware of, and
treating it by accident, is more important.
DETAILED SURVEYS
The initial surveys provided an interesting look into what utilities were experiencing
relative to source water Mn occurrence, method used for Mn treatment, and methods used to
measure Mn. To gather more in-depth information, the research team developed a detailed
survey. The source of contacts for this survey was the large group of initial survey participants.
The detailed survey participants were a subset of those from the initial survey.
77
1 1
1
1 2
NH-1
3
1 1 MA-6
1
2 NJ-2
1
8 2 MD-1
1
1 1
1
Figure 4.9 Geographic distribution of detailed surveys in U.S. (numbers) (n = 42) and
location of the 12 facilities that participated in seasonal distribution system sampling for
Mn (dots)
78
Surface Water
6%
Ground Water
GWUDI
56%
Figure 4.10 Types of source water treated by facilities in detailed survey (n = 52)
79
PACl
37%
Figure 4.12 Type of primary coagulant used to treat water in detailed surveys (n = 52)
Compared to the initial surveys there is a notable difference, in that more surface water
sources participated in the detailed survey than groundwater sources. This has to do with the SW
facilities utilizing a wider range of technology, having more varied stories, and often being large
enough (having enough staff) to participate in the study on a deeper level. For similar reasons,
disinfection only treatment facilities did not have as strong a representation in the detailed
survey statistics as they did in the initial survey.
The PIs believe the demographic goals of the detailed survey were met, and that the
detailed survey participants are a reasonable subset of the larger initial survey.
For the detailed survey the researchers asked for more water quality data along with more
detailed and substantive Mn data. Each utility was asked to submit a full years worth of Mn data
along with various other water quality parameters.
The facilities that participated in the detailed survey were a little more likely to provide
water quality data than those that participated in the initial survey, 80% to 86% as compared to
76% to 78% for source and finished water respectively (see Table 4.4). The quantity of water
quality data requested was substantial, however, and about 14% did not complete the task. Only
a few sent distribution system water quality data, mostly because they did not have it. This was
also observed in the initial survey. Most utilities do not collect distribution system water quality
information. The information required to comply with the total coliform rule (TCR) and the lead
and copper rule does not provide the kind of water quality data the authors were looking for.
The self-reported data was collected and analyzed in two major ways. The first and most
obvious was a correlation analysis, in which average (mean) Mn values for each facility were
correlated with each of a number of other water quality parameters. The second was a look at the
distribution of Mn concentrations themselves, including minimum, maximum, and average
values, overall and using the stories told by each facility.
80
The authors were hoping to find a profound correlation between annual water quality data
and the Mn concentration. For each facility, an average of each non-Mn water quality parameter
(on an annual basis) was determined, as well as the average total Mn concentration. This annual
average Mn concentration was then plotted as a function of one annual average water quality
parameter at a time. Therefore, each facility contributed one data point per plot. We did this for
source water, finished water, and distribution system water.
A significant drawback for this type of analysis is that the water quality data was supplied
on an annual basis and it was not sent as coupled data. So, correlating a specific Mn
concentration with a specific value of another water quality parameter taken at the same time
was not possible. (Collection and analysis of such coupled data, however, was done as part of
this research project in the seasonal occurrence sampling of distribution systems, discussed later
in this chapter.)
In the correlation analysis, 16 separate plots were created for each water type (source,
finished, and distribution system water). Figure 4.13 is an example of the analysis, done for
finished water. All three sets of plots can be found in Appendix C. Each plot contains the n value
along with the R2 value of the regression analysis.
Table 4.4
Facilities providing Mn concentration data in detailed surveys
Water Number of facilities that provided data Percent out of 52
Source 42 80%
Finished 45 86%
Distribution 12 23%
For the 16 source water correlation plots, none of the R2 values were above 0.50, save
one, dissolved oxygen (DO). It had an R2 of 0.64 but n value was 10 which is low. However,
the trend makes sense as there was more Mn associated with lower D.O. Likewise the 16
finished water plots had low R2 values. There was one with an R2 of 0.798 (Mn as a function of
DO), but this too had a low n (n = 6). These two correlations seem to indicate that the oxidation
reduction potential as characterized by DO could be significant. If more DO data was supplied
there could have been more conclusive comments made.
For the 16 distribution system plots, where self-reported data was scarce, the highest n
value plot (n = 13) was total Mn as a function of pH, yielding a very low R2 of 0.056. The
distribution turbidity plot has n = 11 with an R2 of 0.405. There is another plot with a fairly high
R2 (R2 = 0.60) but the n value is so extremely low (n=4) that it is difficult to infer much meaning.
This parameter was Total Mn as a function of apparent color. Of interest is that this parameter
has the strongest correlation in the seasonal distribution sampling data, presented later.
When looking at all the utilities at once, with annual data being summarized into one
average value, there were no strong correlations. Mn concentration cannot be predicted by a
single water quality parameter.
81
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
0.060 0.060 0.060 0.060
2
R = 0.1715 0.050
0.050 0.050 0.050
R2 = 0.0002
0.040 2 0.040 0.040 0.040
R = 0.0084
0.030 0.030 0.030 0.030
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
0.060 0.060 0.060 0.060
R2 = 0.0728
0.050 0.050 0.050 0.050
2
R = 0.0096 R2 = 2E-05
0.040 0.040 0.040 0.040
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
0.060 0.060 0.060 0.060
R2 = 0.0002
R2 = 0.798 0.050
0.050 0.050 0.050
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Figure 4.13 Correlation analysis of finished water Mn concentrations to specific water quality parameters, from detailed surveys
83
Overall Explanation of Table 4.5. A years worth of total self-reported Mn data from the
detailed surveys was sorted into minimum, average, and maximum for each facility, as shown in
Table 4.5. This was done for source water and for finished water. A ratio of max to average Mn
concentration was generated for each set; that is, the maximum value divided by the average.
This was done to get an idea of how large a difference there was between the average condition
and a large excursion. Also, the percentage of Mn removal (from source to finished water) based
on average data was calculated. The left-hand box of Table 4.5 is utility description information;
each facility that also participated in the seasonal distribution system testing for Mn is identified
with an X. The middle box is source water information and the third is finished water, with the
far right-hand box being percent Mn removal during treatment.
At the bottom of several of the columns are totals. There are 44 separate facilities
represented on the table, representing 44 of the 52 detailed surveysthose that reported
sufficient Mn data for this analysis. Two of them are entered twice (i.e., ID Nos. 2 and 2a, also
28 and 28a; see below), so there is a possible total of 46 data points per column. At bottom right
there is also a matrix of counts above 0.050 mg/L and at or below 0.020 mg/L for the finished
water values. Note that not every utility that participated in the detailed survey provided min,
max, and average data. Fields were left blank where no data was offered. All of this data is
presented in Table 4.5 along with each utilitys n values denoting the total number of Mn
concentrations reported for source and finished water.
The analysis of the table can be done from left to right for overall treatment analysis or it
can be analyzed vertically, looking for high and low values. The table is color-coded to aid in
analysis. Utilities that have no in-plant Mn treatment or that use sequestering alone were
identified with a pink box. A utility that has a raw water Max:Avg ratio greater than 10 was
identified by brown shading and those that have a finished water Max:Avg ratio greater than 10
are shaded in blue. Yellow shading was used to identify finished water concentrations that were
less than or equal to 20 g/L, while a finished water value of greater than 50 g/L was left white
but boxed with a black border. Aqua green shading is used to identify facilities that use KMnO4
alone to control Mn.
Utility 2 is listed twice as 2 and 2a because one treatment process (i.e., 2) is used all year
long while 2a is used only part of the year, yet both processes are within one treatment plant and
enter the same distribution system. Utility 5 has two distinct process trains within the one
treatment plant but since they are both used constantly the plant overall is thought of as one
process. Utility 28 is listed twice (as 28 and 28a) because it has two distinct sources of water yet
the same treatment train, so data was generated for each source and compared to the common
finished water.
Looking at the n values on Table 4.5 can tell you something about the size of the data set
and also something about the utility. Certain utilities provided more than one years worth of
data. For example the highest n was 1,885 (source) and 2,382 (finished) from a UK facility,
which represents at least 3 years worth of data So this utility collects a little under two Mn
samples per day of source water and over two per day of finished. The next highest n value was
904 (source) and 908 (finished) for Utility 400; this utility intends to measure Mn three times a
day and almost achieved it (which would be 1,095), less monitoring on weekends. The source
water n value for Utility 2 is only 5 while it is 365 for finished. This utility controls Mn using a
sample location within the process, both north and south, measured daily. They have several
85
86
87
89
90
91
One of the sections in the detailed survey focused on customer interactions. We asked
four specific questions about this. (Refer to detailed survey form in Appendix A.) Of the 52
detailed surveys completed, 49 (94%) of the facilities track customer complaints, and 44 (85%)
can differentiate one type of complaint from another, such as color vs. taste & odor vs. pressure,
etc. Of the respondents, 43 indicated that they follow up with complaints and 40 (77%) test for
Mn.
In retrospect, the authors feel that this survey instrument was not the best tool to gather
this information. The interrelations of water treatment staff, distribution staff, and administrative
staff along with the wide range of response to complaints was too complex to be assessed by
these questions. As one might imagine, there was a wide range of ability to track and respond to
complaints. As can be seen in the data just mentioned, almost everyone tracks complaints. The
three that indicated they did not were courageous in admitting that they did not track them. In
two cases the utility responds to complaints as they happen (e.g. flushing) but makes no record of
it. In one case the complaints are handled by another entity so the utility could only answer with
no they did not. With almost everyone saying yes to each question, the differentiation
anticipated was not seen.
The best picture of the utilities process regarding complaints was seen in the comment
section associated with the questions. For example, in the United Kingdom (UK) customer
complaints are maintained in computerized files and are part of the regulatory environment, i.e.,
92
Overall Findings
An analysis of the overall data set produced by this research task yielded the following
observations.
93
Introduction
From the detailed survey participants, 11 utilities (12 facilities) were selected to sample
water from within their distribution systems. Facility selection was based on diversity of Mn-
related customer complaints, geographic location, source water type, and treatment type, along
with the most important qualifier, willingness to conduct this elaborate sampling. The geographic
regions of the U.S., source water type, and treatment type are summarized in Table 4.6. The
approximate locations of these facilities were presented in Figure 4.9.
The sampling was scheduled to occur four times (seasonally) over the course of one year.
Utilities were to collect water samples from three distribution system locations, filter through a
0.22-m and a 30-kDa filter, and ship to Philadelphia for metals analysis as described
previously. Each sample (total and filtrates) was collected in triplicate. Split samples were also
collected for in-house analyses of other water quality parameters. The full study protocol is in
Appendix B.
As with the detailed survey data, these data were examined to determine if any water
quality parameters correlated to distribution system Mn concentrations. For various reasons, not
all of the participants were able to complete four sample sets. Because of this, an extra set of
samples was requested from some participants; this extra sample set was collected in winter
2005. A synopsis of seasonal utility participation is given in Table 4.7.
The purpose of the sampling was to determine Mn concentrations and speciation in actual
water distribution systems, and to examine the data for spatial trends in Mn behavior throughout
distribution systems and correlations between Mn and ancillary water quality parameters. Each
utility sampled its plant effluent (representing the distribution system entry sampling point) and
then sampled at three locations in the system: near, mid, and far from the entry point. The actual
Table 4.6
U.S. region, source water type, and Mn treatment type for utilities participating in
distribution system occurrence sampling for Mn
Utility ID Region Source Mn-specific treatment process
2, 2a Midwest GW Aeration, KMnO4, and manganese greensand
7 South SW KMnO4
9 Mid-Atlantic SW Induced oxide-coated media effect (IOCME)
21 Northeast GW Greensand
22 Mid-Atlantic SW IOCME with auxiliary KMnO4
216 Northeast SW None
269 Northwest GW Sequestration
315 Mid-Atlantic SW IOCME on GAC
318 West GW Sequestration
336 Mid-Atlantic SW KMnO4, IOCME on GAC
400 West SW KMnO4
401 West Reservoir oxygenation system (HOS) / none
94
location of each of these points was selected by the utility. Two utilities with small distribution
systems collected only two distribution system locations.
The plots generated to analyze this data have been compiled in Appendix D. Due to the
extensive amount of data, it was not practical to present all the data in the text of this report, nor
is it practical to discuss each utility separately. Rather, we discuss general observations. A subset
of the data is presented and discussed in the following subsections, which cover the two main
methods used to analyze the datathe spatial relations of Mn concentrations, and Mn
concentration correlations with other water quality data.
95
96
97
Total Manganese
0.050 0.22 m Filtered Manganese 0.050
30 kDa Filtered Manganese
Manganese (mg/L)
0.040 0.040
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
8/31/2004 11/9/2004
0.060 0.060
0.050 0.050
Manganese (mg/L)
0.040 0.040
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID :2
U.S. Geographic location : Midwest
Source water : Ground Water
Treatment type : Parallel conventional gravity settling and manganese greensand
Mn Specific Treatment : Aeration and KMnO4 / Greensand
Figure 4.14 Results of distribution system seasonal Mn occurrence sampling for Utility 2
(data presented as mean and of triplicate samples)
98
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
9/10/2004 12/8/2004
0.050 0.050
0.040 0.040
Manganese (mg/L)
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID :9
U.S. Geographic location : Mid-Atlantic
Source water : Surface Water
Treatment type : Conventional Gravity Settling
Mn Specific Treatment : Induced Oxide Coated Media
Figure 4.15 Results of distribution system seasonal Mn occurrence sampling for Utility 9
(data presented as mean and of triplicate samples)
99
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
8/27/2004 11/12/2005
0.050 0.050
0.040 0.040
Manganese (mg/L)
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID : 22
U.S. Geographic location : Mid-Atlantic
Source water : Surface water
Treatment type : Advanced clarification with intermediate ozone
Mn Specific Treatment : Induced oxide coated media - auxiliary KMnO4
Figure 4.16 Results of distribution system seasonal Mn occurrence sampling for Utility 22
(data presented as mean and of triplicate samples)
100
0.200
Manganese (mg/L)
0.150
0.100
0.050
0.000
Entry Near Mid Far
12/20/2004
0.200
0.150
Manganese (mg/L)
0.100
0.050
30 kDa Filtered Manganese
0.22 m Filtered Manganese
Total Manganese
0.000
Entry Near Mid Far
Utility ID : 269
U.S. Geographic location : Northwest
Source water : Groundwater
Treatment type : Disinfection
Mn Specific Treatment : Sequestration
Figure 4.17 Results of distribution system seasonal Mn occurrence sampling for Utility 269
(data presented as mean and of triplicate samples)
101
A graphical representation of all the essential seasonal testing data was produced for each
utility. This required the generation of three figures with three plots per figure. The top plot of
each figure is the Mn concentration, total and dissolved. The next two plots are of associated
water quality parameters. All are presented in bar chart format. The data are grouped by sample
point and sequenced by date. The bottom plots x-axis has data that applies to all three plots
(temperature, pH, date, and location of the sample). All of this was done in an attempt to increase
the data density per figure. By looking at one page you can see the Mn concentrations as a
function of location, temperature, pH, and date while looking at other water quality parameters in
similar plots. An example of this representation is shown for Utility 2 in Figures 4.18 through
4.20.
These figures were used by the research team to analyze the data. They provided an
opportunity for an initial look at possible correlations between Mn and other water quality
parameters. Unlike the self-reported data from the detailed surveys, this water quality data is
directly associated to the Mn concentration data on a per sample basis. These figures are
presented for only one utility (No. 2) in this chapter, for the purpose of illustration. We refer the
reader to the complete set of data, all utilities, presented in Appendix D.
Figure 4.18 illustrates the interesting hump that occurs at Utility 2 when the utility is
using an auxiliary source water to meet demand and is pushing water through the older half of
the plant at greater rates. The hump is the increase in Mn concentration entering the system
during the spring and summer. The winter and fall concentrations are much lower making a
pattern of low, high, high, low (in other words a hump). The hump gets smaller as we move
through the distribution system. Also the amount of dissolved Mn for each sample date decreases
as one moves through the distribution system from near to far.
Another interesting point about Utility #2 is the temperature data. One of the reasons the
PIs designed the experiment to last over one year was because seasonally the temperature would
change. Since this utility uses a groundwater source, the temperature does not change that
significantly from season to season. Yet this utility does display a significant difference in Mn
concentrations from season to season. As discussed previously, this is due to water source and
water treatment process capacity. Another interesting thing about the temperature data is that the
water temperature changed less than 3C at the entry point while the far sample point changed
9C.
The TDS was extremely high (Figure 4.18), in fact so high we had to confirm the values.
The PIs were not use to seeing such values. The utility has been producing more and more water
and the TDS values have been going up over the years. The citys success has lead to increase in
population and more water use and a gradual change in water quality. The TDS are so high that
a visitor to the city might experience some gastrointestinal anomalies, especially if they live in an
area with low TDS.
Although this utility uses many wells and puts into production the ones with high Mn
when water demand forces them too, they have no arsenic. The plot reveals that there was not
even detectable arsenic; all results were less than 0.001 mg/L (Figure 4.20).
All the utilities studied were unique and interesting. It is highly recommend that the
reader spend time looking at the data in Appendix D.
102
0.060
Manganese (mg/L) .
0.045
0.030
0.015
0.000
4.50
TOC Turbidity 4.50
4.00 4.00
3.50 3.50
Turbidity (NTU)
TOC (mg/L)
3.00 3.00
2.50 2.50
2.00 2.00
1.50 1.50
1.00 1.00
0.50 0.50
0.00 0.00
700 700
TDS (mg/L)
600 600
500 500
400 400
300 300
200 200
100 100
0 0
10.5 12.5 13.3 10.5 6.0 13.0 14.7 16.5 6.5 14.0 17.6 14.5 9.5 13.5 18.5 16.0
6.8 6.8 6.0 6.6 6.50 6.80 6.30 7.00 6.80 6.80 6.60 6.50 6.70 7.00 6.50 7.10
2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure 4.18 Individual water quality parameters associated with Mn concentrations from
distribution system sampling
103
0.060
Manganese (mg/L) .
0.045
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
140.0 18.0
16.0
120.0
Sodium (mg/L)
14.0
Calcium (mg/L)
100.0 12.0
80.0 10.0
60.0 8.0
6.0
40.0
4.0
20.0 2.0
0.0 0.0
10.5 12.5 13.3 10.5 6.0 13.0 14.7 16.5 6.5 14.0 17.6 14.5 9.5 13.5 18.5 16.0
6.8 6.8 6.0 6.6 6.50 6.80 6.30 7.00 6.80 6.80 6.60 6.50 6.70 7.00 6.50 7.10
2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure 4.19 Individual water quality parameters associated with Mn concentrations from
distribution system sampling (continued)
104
0.060
Manganese (mg/L) .
0.045
0.030
0.015
0.000
0.0050 Arsenic
0.0040
Arsenic (mg/L)
0.0030
0.0020
0.0010
0.0000
0.6
0.5
0.4
0.3
0.2
0.1
0.0
10.5 12.5 13.3 10.5 6.0 13.0 14.7 16.5 6.5 14.0 17.6 14.5 9.5 13.5 18.5 16.0
6.8 6.8 6.0 6.6 6.50 6.80 6.30 7.00 6.80 6.80 6.60 6.50 6.70 7.00 6.50 7.10
2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure 4.20 Individual water quality parameters associated with Mn concentrations from
distribution system sampling (continued)
105
Each Mn concentration was plotted as a function of a water quality parameter. This was
done to determine the strength of correlations. Because these samples represent a variety of
water types, treatment types, and seasons, a strong correlation between Mn and any water quality
parameters would be significant. However, the authors did not find any, save a few weak ones.
An example of the plots used to determine the strength of the correlations is shown in
Figure 4.21. The different shapes of data points are coded to legends of utility numbers. In this
figure there are 16 plots. In each, the total Mn concentration is plotted on the y-axis and the other
water quality parameter is plotted along the x-axis; that is, y = f(x). This same type of analysis
was done for the other forms of Mn (particulate, dissolved, and truly) as well; and for each plot,
a regression analysis was performed. Table 4.8 lists the R2 values of the regression analyses. This
table represents 114 correlations. The table itself has three sections; correlations of Mn to water
quality parameters, to other metals, and to various fractions of Mn. The R2 above 0.5 are in bold;
there were only five. Only one water quality parameter, i.e., apparent color, correlated with total
and particulate Mn in the distribution system. It did not correlate to the dissolved or truly
dissolved fractions (<0.22-m or <30-kDa Mn, respectively).
A larger plot of both total and particulate Mn as a function of apparent color (Figures
4.22 and 4.23) reveals that the correlation is weaker than it first seems. First, the number of
facilities that collected apparent color data was only five (n = 56), which is one of the smaller
data sets. Second, there is one high Mn and color value that strengthens the correlation but that
can be logically removed. During events in the distribution when Mn increases, it is most often
in particulate form (oxidized) and will show up in apparent color analysis (as will particulate iron
in the water). The dashed line in each figure represents the regression line with the one (high)
point excluded.
Figure 4.24 is a plot of the dissolved (<0.22 m) Mn fraction as a function of the truly
dissolved (<30 kDa) Mn fraction. A strong correlation was observed (R2 = 0.9304). Data lying
above the 1:1 line indicate the presence of a colloidal fraction, and the only two utilities with a
significant measure of this colloidal fraction were Utilities #2 and #269 (both using
polyphosphates, one as a sequestering agent and the other as a corrosion inhibitor). However,
they are not the only two plants that used sequestering agents in this study. Data below the line is
not possible, as there cannot be less dissolved than truly dissolved. So the few points below the
line may represent sampling error or variability in analysis. The significance of this plot is that it
shows that a 0.22-m filter provides a good measure of the truly dissolved concentration.
From our literature review we found out that one might expect to find colloidal Mn
immediately after ozone use. However, we only found colloidal Mn in the distribution system
when sequestration was used. One utility (No. 400, see Appendix D) which uses ozone had some
colloidal Mn in one entry point sample but there was none in the distribution system. Two other
facilities that use ozone (Nos. 22 and 401, see Appendix D) did not have colloidal Mn in the
entry sample point or in the distribution system.
From detailed survey data presented earlier in this chapter, one utility (in Australia)
reported having colloidal Mn in the distribution system when chlorine had died off and
biological activity had started. This change in Mn speciation is attributed to Mn-utilizing bacteria
present in non-chlorinated water.
106
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315 315 318
318 318 318 336
0.10 336 0.10 336 0.10 336 0.10
2
Total Manganese vs Total Chlorine Total Manganese vs Orthophosphate Total Manganese vs Oxidation Reduction Potential 2 Total Manganese vs Dissolved Oxygen 2
0.20 7 0.20 2 0.20 0.20
9
9 9
21 22
22 216
0.15 0.15 0.15 0.15
216 269
269
Total Mn (mg/L)
315
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315 318
0.10 318 0.10 336 0.10 0.10
336
2 2
Total Manganese vs Free Chlorine 2 Total Manganese vs Total Phosphate Total Manganese vs Sulfate Total Manganese vs Total Dissolved Solids
0.20 0.20 0.20 22 0.20 7
7
318 22
9
269
21
269 336
0.15 269 0.15 0.15 0.15
216 318
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315
318
0.10 336 0.10 0.10 0.10
2 2 2
Total Manganese vs pH Total Manganese vs UV254 Absorbance Total Manganese vs Apparent Color 2 Total Manganese vs Temperature
0.20 7 0.20 7 0.20 0.20 7
9 7 9
9
21 9 21
22
22 22 22
0.15 0.15 216 0.15 0.15
216 216 269
269
269 216
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315
315 318 315
0.10 318 0.10 336 0.10 0.10 318
336 336
Figure 4.21 Seasonal distribution system testing: correlation of total Mn to various water quality parameters collected at the entry, near, mid, and far points of the distribution system
107
109
22
2
R = 0.79 216
0.10
0.05
2
R = 0.58
0.00
0 10 20 30
Apparent Color (PtCo Units)
Figure 4.22 Total Mn versus apparent color. The solid regression line is for all data, the
second, dashed regression omits the single data point at 25 color units and 0.131 mg/L Mn.
0.20
2
7
0.15 9
Particulate Mn (mg/L
22
2 216
0.10 R = 0.80
0.05
2
R = 0.65
0.00
0 10 20 30
Apparent Color (PtCo Units)
Figure 4.23 Particulate Mn as a function of apparent color. The second, dashed regression
line omits the single data point at 25 color units and 0.131 mg/L Mn.
110
0.00
0.00 0.05 0.10 0.15 0.20
Manganese < 30k Da (mg/L)
Figure 4.24 Mn that passes through a 0.22-m filter as a function of Mn that passes
through a 30-kDa filter
After performing the correlation analyses described above, the overall data set from the
distribution system sampling was subdivided into two smaller sets defined by source water. An
analysis of correlations between Mn concentrations and water quality parameters was then
conducted separately for surface water sources and groundwater sources. While there were a few
strong correlations for groundwater, these were from the parameters with the smallest data sets.
Also a known high flow period event was removed from the data set. The parameters that had
a strong correlation to Mn in groundwater were alkalinity, conductivity, sulfate, and TDS.
Sodium had an R2 value of greater than 0.5 when correlated to the <30-kDa fraction. For the
surface water sources, the only parameter to maintain a correlation with an R2 value greater than
0.5 was apparent color.
There were three hundred correlation plots generated to discern this information, yet
there did not seem to be any correlations that hold up as statistically valid.
Figure 4.25 is a plot of the concentration of Mn (total and dissolved) at the far sample
point as a function of the total Mn concentration at the entry point, and illustrates that there is a
strong correlation. This implies that the two are related, that the more Mn entering the system the
more will be found in the far sample point. Within the plot there is also a 1:1 reference line,
dotted line from corner to corner. When a sample point lies on this line it indicates that there is
neither a net loss nor gain of total or dissolved manganese through distribution. When it lies
111
0.20
Mn(Total)
Mn (Diss.)
Mn (Total) - sequestration
Far Manganese (mg/L)
0.15
Mn (Diss.) - sequestration
0.10 2
R = 0.87
0.05 2
R = 0.81
0.00
0.00 0.05 0.10 0.15 0.20
Entry Total Manganese (mg/L)
Figure 4.25 Seasonal distribution system testing: correlation of manganese concentration
(total and dissolved) at the far point to the entry point (total) of the distribution system. 1:1
line plotted as reference.
112
Mn(Total)
Mn (Diss.)
0.05
Far Mn (mg/L)
2
R = 0.53
0.025
2
R = 0.14
0
0 0.025 0.05 0.075
Entry Total Mn (mg/L)
Figure 4.26 Seasonal distribution system testing: correlation of manganese concentration
(total and dissolved) at the far point to the entry point (total) of the distribution system. 1:1
line plotted as reference. Sequestration Facilities omitted
Figure 4.26 presents the same data but with the sequestering plants removed. The
strength of the correlations drops significantly. Only the total Mn has an R2 value of above 0.5.
The trend lines associated with this data have greater slopes than in the previous figure.
Removing sequestration from the data set reveals an even greater tendency for Mn to accumulate
in the system. The dissolved Mn data indicates that dissolved Mn will not be present even when
high levels of Mn are introduced into the system. One can expect to find dissolved Mn in the
distribution system if one applies a sequestering agent.
Figure 4.27 presents dissolved Mn at entry versus the dissolved Mn at far point of the
distribution system. A 1:1 ratio line is provided and the legend identifies which utilities use
sequestration to control Mn. Here again the utilities that use sequestration have the highest Mn
concentrations. Most of the data points lie below the 1:1 line indicating that dissolved Mn
concentration decreases as it passes through the distribution system.
When data from the sequestration facilities are omitted, there is a very weak correlation
between entry and far point (Figure 4.28). The regression line is almost flat indicating that there
tends to be very little dissolved Mn at the far sample point regardless of the entry point
concentration. For one sample set, 0.038 mg/L of dissolved manganese entered the distribution
system and <0.001 mg/L was present at the far point. The decrease in dissolved manganese is
offset by an increase in particulate manganese. However, this offset is not complete, as shown
earlier; there is a decrease in total Mn too. A few samples were slightly greater in dissolved
manganese from entry to the far point, but this was limited to samples with less than a 0.005
mg/L of Mn at the entry point. Also the increase was always less than 0.005 mg/L too. It is hard
113
0.15 Mn (Diss.)
Far Dissolved (mg/L
Mn (Diss.) - sequestration
0.10
2
R = 0.88
0.05
0.00
0.00 0.05 0.10 0.15 0.20
Entry Dissolved Mn (mg/L)
Figure 4.27 Seasonal distribution system testing: Dissolved manganese at the distribution
system far point as a function of the entry point; 1:1 line reference line
0.05
Mn (Diss.)
0.04
Far Dissolved (mg/L
0.03
0.02
0.01 2
R = 0.03
0.00
0.00 0.01 0.02 0.03 0.04 0.05
Entry Dissolved Mn (mg/L)
Figure 4.28 Seasonal distribution system testing: Dissolved manganese at the distribution
system far point as a function of the entry point; 1:1 line reference line. Sequestration
facilities omitted.
114
The authors noticed an odd occurrence when looking at the seasonal distribution data.
The manganese concentration seemed to increase from the entry point to the near sample point.
A simple table was constructed to see if this was actually happening (Table 4.9). If the
concentration of near was within 0.002 mg/L of the entry then there was considered to be no
change. If it was greater or less, it was considered different and noted. Clearly there is a trend.
There is more total Mn in the near points as opposed to the entry points. The trend is even
stronger for particulate Mn. However, there is no such trend when looking at the dissolved
numbers where more often than not, there is no change.
The PIs investigated if there was a fundamental difference in the sample collection. Most
utilities used a continuously running sample tap to collect the sample at entry to the distribution
system, and drew from the distribution system points from non-continuously running taps (Table
4.10). The most likely explanation for higher Mn levels at the near sampling point is that the
process of opening the tap disturbed sedimentary material in the pipes that was then captured in
the sample. This explanation makes even more sense considering that the trend is for total and
particulate, and not for dissolved Mn. It should be noted that the utilities had been instructed to
run the taps for several minutes before sample collection and there is no reason to suppose that
this did not occur. It may be that several minutes of running sample water was insufficient
To look further, Utilities #269 and #318 did not have a continuously running tap for their
entry point sample. For Utility #269 one of the two sample sets that they collected had higher Mn
at the near then entry. Utility #318 did not sample the near location but at a location they deemed
mid, using that location one of the three sample sets collected had a higher mid than entry value.
Both Utility #269 and #318 had small distribution systems, so small they could not easily
distinguish between near and mid. Also Utility #216 has both a continuous running entry and
near sample tap and it has a greater concentration of Mn in the near as opposed to the entry for
all three of the sample sets. Therefore the explanation, that the sample collection method
disturbed the particulate Mn, although reasonable, does not seem to be wholly complete.
Additional entry-to-near analysis is shown in Figure 4.29. The near Mn concentration
data is plotted as a function of entry Mn. This plot is slightly different than previous plots, that is,
total near Mn concentration is correlated to total entry and dissolved near is correlated to
dissolved entry, as opposed to both being correlated to total.
Table 4.9
Number of occurrences of near Mn concentrations being more than entry
(n = 33) Total Mn Particulate Mn Dissolved Mn
Near < Entry 6 4 9
No Change 8 9 15
Near > Entry 19 20 9
115
There is a correlation between the total Mn concentrations of the two locations and a
strong correlation for dissolved Mn. These correlations are made even stronger by removing the
sequestration plant data and one outlier due to a known distribution system high flow event
(Figure 4.30) However, the trend lines seem to reveal some interesting information. For both
figures the dissolved trend lines are below the 1:1 line, meaning that there is always more
dissolved Mn entering the system than appears even in the near sample. This seems true for the
total line until one removes the plants that use sequestering to control Mn. Then the trend line
0.20
Mn (Total) - sequestration
Mn (Diss.) - sequestration
0.10
2
R = 0.83
0.05
0.00
0.00 0.05 0.10 0.15 0.20
Entry Manganese (mg/L)
Figure 4.29 Seasonal distribution system testing: correlation of total and dissolved
manganese at the distribution system near point to the entry point, and 1:1 line reference
line.
116
Mn (Total)
Near Manganese (mg/L)
Mn (Diss.) 2
R = 0.93
0.04
2
R = 0.94
0.02
0.00
0.00 0.02 0.04 0.06
Entry Manganese (mg/L)
Figure 4.30 Seasonal distribution system testing: correlation of total and dissolved
manganese at the distribution system near point to the entry point, and 1:1 line reference
line. Omitted sequestration plant data, plus one system event data point corresponding
to 0.006 mg/L total Mn at entry and 0.131 mg/L total Mn at the near point
0.06
Sequestration facilities omitted
Near Particulate Manganese
Mn (Particulate)
0.04
(mg/L)
2
R = 0.86
0.02
0.00
0.00 0.02 0.04 0.06
Entry Particulate Manganese (mg/L)
117
Overall
All of this implies that there is an overall process of conversion of dissolved to particulate
and then later a settling of the particulate Mn (loss of total Mn). The settled Mn can then be
suspended in high flow periods (high total Mn events).
The authors do not believe this explains the fate and transport of all the Mn that enters the
distribution system; however, we do believe it is the predominant fate for distribution systems
that maintain a chlorine residual of some kind. There were no samples taken from a system that
had demonstrable biological activity.
Background
The Philadelphia Water Department (PWD) has two pilot-scale research facilities, one on
the Delaware River and one on the Schuylkill River. During certain ozone related work it was
noticed that Mn can bleed through the filters. This was new to PWD since Mn had never been an
issue.
At full-scale, PWD produces finished water with Mn concentrations mostly of non-detect
(<0.001 mg/L), even though there is Mn in source water and in the coagulant. PWD chlorinates
with free chlorine prior to filtration and has substantial amounts of Mn in the sedimentation basin
effluent. PWD unknowingly relied upon induced oxide-coated media effect (IOCME).
Prior to the initiation of this research project several observations were made at pilot
scale about the ability of certain filters to control Mn. Filters without chlorine could not control
Mn. Chlorine alone was not always sufficient to control Mn. The lower the pH of filtration, the
less stable the IOCME process was. If the water was very cold the IOCME process was not
stable even with significant amounts of free chlorine. If an oxide-coated media (OCM) filter was
operated without chlorine, Mn would be removed at the beginning of the run but later it would
come out in concentrations often higher than it was coming into it. When using ozone,
particulate Mn would be formed and enter the filter, and for filters without chlorine, dissolved
Mn would exit the filter. The amount of ozone used and the ozone contact time seemed to have
an impact on the ability of the filters to control Mn.
These observations led to much discussion and experimentation, and ultimately this
research project. The control of Mn via IOCME, or induced greensand effect as per Knockes
118
IOCME Mn Control
119
Filter pH 6.5
Filter pH 7.0
0.045
Total Manganese (mg/L)
Filter pH 7.5
Filter pH 8.0 and 8.5
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
Figure 4.32 Pilot plant filter effluent Mn concentration as a function of temperature:
Coagulation pH 6.5 for filtration pH of 6.5, 7.0, 7.5, 8.0, and 8.5 (0.25) with a free chlorine
residual of 0.4 mg/L or greater. (n = 149)
Looking specifically at each filtration pH series, Figures 4.33 through 4.35, we can see
that as the pH increases, the variability of Mn control starts at a lower temperature. Using PWDs
internal goal of 15 g/L of Mn as a criterion, a line can be drawn that indicates the temperature
at which this variability starts. For pH of filtration of 6.5 the start of variability seems to be 8C,
for pH 7.0 the start of variability is 4C and for pH 7.5 it is 3C. There is not enough cold water
data to make a similar observation for filtration pH of 8.0 and 8.5, n = 9 and 5 respectively, with
none of it being below 8C. Yet it can be inferred that the temperature limit would be even lower
than 3C.
Another interesting pattern is that as the pH increases, the variability of the effluent Mn
decreases. Since our play book calls for all ND data to be plotted as the MDL, the values show
on the plot as 1 g/L but in reality the values for the higher pH values are all Non Detects. As the
pH increase from 6.5 to 8.5, the effluent Mn concentrations go from low but measurable to non-
detect. The pH of filtration is a significant parameter for IOCME.
120
Filter pH 6.5
0.045
Total Manganese (mg/L)
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
0.060
Filter pH 7.0
0.045
Total Manganese (mg/L)
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
121
Filter pH 7.5
0.045
Total Manganese (mg/L)
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
Looking at the same data set (IOCME filters, coagulation using ferric salts at a pH of 6.5)
in a different way, we attempted to see if there was a lower limit of free chlorine residual that
resulted in a loss of Mn control. We sorted the data into groups using filtration pH and
temperature. For each pH the researchers used the cut off temperature established in the
previous section. Figure 4.36 is an example of the pH 6.5 data. From this plot one can see that
filter effluent free chlorine can drop to below 0.1 mg/L before Mn control becomes variable.
Even at no free chlorine residual there was both high and low Mn concentrations in the effluent.
These points represent conditions where chlorine was applied and were total chlorine residual
was measurable, just not free chlorine. This specific data point was generated at temperature of
17C.
For the other pH values (7.0, 7.5, 8.0, 8.5 - data not shown) the Mn was controlled for all
data points, however, the free chlorine residual was never below 0.3 mg/L. Therefore the PIs
could not present information confirming a limit below 0.3 mg/L of free chlorine. However, as
occurred in the pH 6.5 data set, they believe a lower limit of zero free chlorine residual leaving
the filter is possible. That is to say, if a free chlorine concentration is applied to an IOCME filter,
the free chlorine residual need not be maintained through the filter to achieve Mn control. This
was corroborated by full-scale work done at two utilities that apply chlorine to GAC media
filters. There is no free chlorine residual, but Mn is controlled on the media.
122
0.060
0.045
0.030
0.015
0.000
0.0 0.2 0.4 0.6 0.8 1.0
Free Chlorine (mg/L)
Figure 4.36 Pilot plant filter effluent Mn concentration as a function of free chlorine
concentration: Coagulation pH 6.5, filtration pH 6.5 (0.25) for temperature greater than
8C. (n = 53)
123
124
The authors then performed a more qualitative analysis of the figures. The mass of Mn
that was leaving the filter was subtracted from the mass of Mn loading onto the filters. This value
was then normalized using the filter run time. This analysis was done for each filter used in each
filter run, and then sequential run data was combined to account for the backwash and restart of
each filter. These results were translated into a mass capture rate (mg/hr) and percent removal
and are shown in Table 4.11. The capture rate is both a function of the amount of Mn loaded and
Table 4.11
Mass capture rate and % removal of Mn for IOCME process once chlorine is terminated
Temperature pH of Mass capture Removal
Pilot Plant
(C) filtration (mg/hr) percent
18 8.2 6.20 96%
Baxter 20 7.5 5.10 84%
22 6.6 2.30 31%
22 8.5 15.2 99%
Belmont 24 7.5 13.6 98%
26 6.7 12.1 99%
8 8.4 9.60 98%
Baxter 8 7.5 5.70 83%
5 6.6 2.17 20%
12 8.5 8.30 100%
Belmont 13 7.5 6.78 74%
8 6.6 2.31 22%
125
126
Filter 1
-18.1 -8.1 1.9 11.9 21.9 31.9 41.9 51.9 61.9 71.9
Inflow EH Outflow EH Dissolved Manganese Total Manganese PWD Mn Goal
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/10/04 05/10/04 05/11/04 05/11/04 05/11/04 05/11/04 05/12/04 05/12/04 05/12/04 05/12/04 05/13/04 05/13/04 05/13/04 05/13/04 05/14/04 05/14/04
Date & Time
04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM
Elapsed Time Since Chlorine
3.5
4.5
25.0
2.5
5.5
24.0
26.0
27.0
29.0
23.5
48.5
50.5
52.5
1.5
47.5
70.8
72.5
0.0
0.5
Shutoff (hours)
0.0
1.0
3.0
4.0
6.0
2.0
24.5
27.5
0.0
0.5
18.1
18.6
19.6
20.6
21.6
22.6
23.6
25.5
29.5
47.8
49.5
Filter 6
-18.1 -8.1 1.9 11.9 21.9 31.9 41.9 51.9 61.9 71.9
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/10/04 05/10/04 05/11/04 05/11/04 05/11/04 05/11/04 05/12/04 05/12/04 05/12/04 05/12/04 05/13/04 05/13/04 05/13/04 05/13/04 05/14/04 05/14/04
Date & Time
04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM
27.0
3.5
4.5
26.0
29.0
2.5
5.5
23.5
1.5
48.5
50.5
52.5
47.5
70.8
72.5
0.0
0.5
Shutoff (hours)
0.5
2.0
1.0
0.0
0.0
6.0
3.0
4.0
24.5
27.5
18.1
25.5
18.6
29.5
47.8
49.5
20.6
23.6
19.6
21.6
22.6
h Both Run 040510 and Run 040512 were terminated due to TM - time constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure 4.37 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss and pH on Mn control.
127
Filter 1
-18.6 -8.6 Inflow EH 1.4 11.4
Outflow EH 21.4
Dissolved 31.4
Manganese (mg/L) 41.4 51.4
Total Manganese (mg/L) 61.4
PWD Mn Goal 71.4
900 0.090
700 0.060
Starting Run 040517
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
17/05/04 17/05/04 18/05/04 18/05/04 18/05/04 18/05/04 19/05/04 19/05/04 19/05/04 19/05/04 20/05/04 20/05/04 20/05/04 20/05/04 21/05/04 21/05/04
Date & Time
03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM
29.7
49.5
51.5
24.0
47.5
73.5
71.5
0.0
0.5
1.0
2.0
3.0
4.0
5.0
30.2
53.5
Shutoff (hours)
0.0
42.6
18.0
20.0
22.0
24.0
42.0
44.0
0.3
0.8
0.0
900
Filter 6 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
17/05/04 17/05/04 18/05/04 18/05/04 18/05/04 18/05/04 19/05/04 19/05/04 19/05/04 19/05/04 20/05/04 20/05/04 20/05/04 20/05/04 21/05/04 21/05/04
Date & Time
03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM
Elapsed Time Since Chlorine
1.0
47.5
0.0
0.5
2.0
3.0
4.0
5.0
29.7
73.5
24.0
30.2
49.5
51.5
53.5
71.5
Shutoff (hours)
0.0
42.6
18.0
20.0
22.0
24.0
42.0
44.0
0.8
0.3
0.0
h High headloss rates were observed during Run 040517. Further investigation determined that the high headloss rate was a function of a slight coagulant overdose. The ferric dose was decreased and the headloss rates dropped to a range considered "normal".
h Run 040519 terminated due to TM - Time constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure 4.38 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss and pH on Mn control.
128
Filter 1
-19.2 -9.2 0.8 10.8 20.8 30.8 40.8 50.8 60.8 70.8
Inflow EH Outflow EH Dissolved Manganese Total Manganese PWD Mn Goal
1000 0.090
800 0.060
Mn (mg/L)
EH (mV)
700 0.045
600 0.030
500 0.015
400 0.000
05/24/04 05/24/04 05/25/04 05/25/04 05/25/04 05/25/04 05/26/04 05/26/04 05/26/04 05/26/04 05/27/04 05/27/04 05/27/04 05/27/04 05/28/04 05/28/04
Date & Time
03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM
49.6
50.1
51.6
3.0
4.0
5.0
53.1
1.0
2.0
-0.2
71.6
Shutoff (hours)
0.0
0.0
0.9
22.2
23.2
19.0
2.4
20.2
21.2
24.2
0.4
3.8
22.4
Run Time (hours)
-19.2 -9.2 0.8 10.8 20.8 30.8Filter 3 40.8 50.8 60.8 70.8
1000 0.090
800 0.060
Mn (mg/L)
EH (mV)
700 0.045
600 0.030
500 0.015
400 0.000
05/24/04 05/24/04 05/25/04 05/25/04 05/25/04 05/25/04 05/26/04 05/26/04 05/26/04 05/26/04 05/27/04 05/27/04 05/27/04 05/27/04 05/28/04 05/28/04
Date & Time
03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM
49.3
49.8
-0.2
1.0
2.0
3.0
23.8
27.8
4.0
52.7
51.3
5.0
71.3
Shutoff (hours)
22.4
0.0
0.0
19.0
20.2
21.2
22.2
23.2
24.2
43.0
47.0
0.9
2.4
3.8
0.4
Run Time (hours)
h Run 040524 was terminated due to HL - headloss. Run 040527 was terminated due to TM - Time Constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001 mg/L) for Mn data.
h EH value is assumed to be in steady state before chlorine shutoff.
Figure 4.39 Baxter pilot plant; Mn and EH as a function of time. Effect of chlorine loss and pH on Mn control.
129
Filter 1
-22.9 -12.9Inflow EH -2.9 Outflow EH 7.1 Dissolved17.1
Manganese 27.1 Total Manganese 37.1 PWD47.1
Mn Goal 57.1
900 0.090
700 0.060
Starting Run 041025
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
10/25/04 10/25/04 10/26/04 10/26/04 10/26/04 10/26/04 10/27/04 10/27/04 10/27/04 10/27/04 10/28/04 10/28/04 10/28/04 10/28/04
03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM Date & Time
49.0
26.5
28.5
45.0
25.5
26.0
27.5
30.5
39.0
41.0
43.0
47.0
51.0
54.5
53.0
0.0
2.0
3.0
0.5
1.0
Elapsed Time Since Chlorine
Shutoff (hours)
1.1
6.1
14.6
16.6
18.6
20.6
26.6
28.6
30.1
22.6
1.6
2.1
3.1
4.1
24.6
22.9
23.4
24.9
25.9
23.9
0.0
0.0
-22.9 -12.9 -2.9 7.1 17.1
Filter 6 27.1 37.1 47.1 57.1
900 0.090
700 0.060
Starting Run 041025
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
10/25/04 10/25/04 10/26/04 10/26/04 10/26/04 10/26/04 10/27/04 10/27/04 10/27/04 10/27/04 10/28/04 10/28/04 10/28/04 10/28/04
Date & Time
03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM
49.0
54.5
27.5
30.5
39.0
41.0
47.0
53.0
0.0
43.0
45.0
0.5
25.5
26.5
28.5
51.0
26.0
2.0
4.0
1.0
3.0
22.6
6.1
22.6
3.1
4.1
Run Time (hours)
30.1
2.1
1.1
1.6
14.6
22.9
23.4
23.9
24.9
25.9
16.6
18.6
20.6
24.6
26.6
28.6
0.0
h Both Run 041025 and Run 041027 were terminated due to TB - turbidity breakthrough.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure 4.40 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss and pH on Mn control.
130
Filter 1
-3.6 6.4
Inflow EH 16.4Outflow EH 26.4 Dissolved Manganese36.4 46.4
Total Manganese 56.4PWD Mn Goal 66.4
900 0.090
End Reason - TM
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
11/02/04 11/02/04 11/02/04 11/03/04 11/03/04 11/03/04 11/03/04 11/04/04 11/04/04 11/04/04 11/04/04 11/05/04
11:24 AM 05:24 PM 11:24 PM 05:24 AM 11:24 AM 05:24 PM 11:24 PM 05:24 AM 11:24 AM 05:24 PM 11:24 PM 05:24 AM Date & Time
48.5
0.5
18.5
22.5
26.5
46.5
50.5
52.5
14.5
16.5
24.5
28.5
30.0
66.5
2.0
20.5
54.5
64.5
0.0
3.0
5.0
1.0
Shutoff (hours)
30.1
20.1
24.1
26.1
32.1
19.9
18.1
5.9
9.9
21.9
3.6
4.6
5.6
28.1
33.6
1.9
3.9
4.1
6.6
8.6
21.1
7.9
0.0
Run Time (hours)
0.0
Filter 6
-3.6 6.4 16.4 26.4 36.4 46.4 56.4 66.4
900 0.090
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
11/02/04 11/02/04 11/02/04 11/03/04 11/03/04 11/03/04 11/03/04 11/04/04 11/04/04 11/04/04 11/04/04 11/05/04
Date & Time
11:24 AM 05:24 PM 11:24 PM 05:24 AM 11:24 AM 05:24 PM 11:24 PM 05:24 AM 11:24 AM 05:24 PM 11:24 PM 05:24 AM
Elapsed Time Since Chlorine
50.5
1.0
24.5
20.5
54.5
0.0
3.0
14.5
16.5
18.5
22.5
26.5
28.5
30.0
38.5
42.5
48.5
52.5
66.5
0.5
2.0
5.0
40.5
64.5
46.5
Shutoff (hours)
0.0
5.9
8.6
18.1
20.1
46.1
4.6
26.1
28.1
32.1
33.6
19.9
21.9
3.6
5.6
22.1
24.1
0.0
4.1
6.6
30.1
42.1
44.1
1.9
3.9
9.9
7.9
Run Time (hours)
h Run 041102 terminated due to TB - turbidity breakthrough, and Run 041104 terminated due to TM - time constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure 4.41 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss and pH on Mn control.
131
Filter 1
-19.4 -14.4 Inflow EH -9.4 -4.4
Outflow EH 0.6 5.6
Dissolved Manganese 10.6 Total Manganese 15.6 20.6Mn Goal
PWD 25.6
900 0.090
700 0.060
Starting Run 041220
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
12/20/04 03:04 PM 12/20/04 09:04 PM 12/21/04 03:04 AM 12/21/04 09:04 AM 12/21/04 03:04 PM 12/21/04 09:04 PM 12/22/04 03:04 AM 12/22/04 09:04 AM Date & Time
10.3
22.5
1.3
20.5
24.5
6.2
26.5
0.0
2.3
4.3
0.8
3.2
8.3
Elapsed Time Since Chlorine
Shutoff (hours)
19.4
22.7
20.7
20.2
21.7
23.7
27.7
41.9
45.9
25.7
39.9
43.9
29.7
0.0
-19.4 -14.4 -9.4 -4.4 0.6 5.6 Filter 3 10.6 15.6 20.6 25.6
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
12/20/04 03:04 PM 12/20/04 09:04 PM 12/21/04 03:04 AM 12/21/04 09:04 AM 12/21/04 03:04 PM 12/21/04 09:04 PM 12/22/04 03:04 AM 12/22/04 09:04 AM Date & Time
10.3
20.5
24.5
1.3
22.5
6.2
0.8
3.2
2.3
4.3
8.3
0.0
Shutoff (hours)
19.4
20.2
20.7
21.7
22.7
23.7
25.7
27.7
29.7
39.9
41.9
43.9
0.0
Figure 4.42 Baxter pilot plant; Mn and EH as a function of time. Effect of chlorine loss and pH on Mn control.
132
Filter 1
-18.1 -8.1 Inflow EH 1.9 Outflow11.9
EH 21.9
Dissolved Manganese31.9 41.9 Manganese
Total 51.9 PWD Mn61.9
Goal 71.9
1000 0.120
Mn (mg/L)
700 0.075
EH (mV)
600 0.060
500 0.045
400 0.030
300 0.015
200 0.000
11/15/04 11/15/04 11/16/04 11/16/04 11/16/04 11/16/04 11/17/04 11/17/04 11/17/04 11/17/04 11/18/04 11/18/04 11/18/04 11/18/04 11/19/04 11/19/04
Date & Time
03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM
2.0 Elapsed Time Since Chlorine
6.3
28.8
32.8
58.3
0.0
4.0
26.8
24.8
34.8
47.3
49.3
8.3
30.8
36.5
45.3
70.3
1.0
3.0
51.3
60.3
0.5
Shutoff (hours)
24.3
26.3
11.5
13.3
22.0
24.0
26.0
28.0
13.1
3.5
1.1
7.5
3.1
5.5
1.5
9.5
0.0
0.0
0.0
Filter 6
-18.1 -8.1 1.9 11.9 21.9 31.9 41.9 51.9 61.9 71.9
1000 0.120
Mn (mg/L)
700 0.075
EH (mV)
600 0.060
500 0.045
400 0.030
300 0.015
200 0.000
11/15/04 11/15/04 11/16/04 11/16/04 11/16/04 11/16/04 11/17/04 11/17/04 11/17/04 11/17/04 11/18/04 11/18/04 11/18/04 11/18/04 11/19/04 11/19/04
Date & Time
03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM
72.3
70.3
26.8
32.8
34.8
36.5
58.3
28.8
30.8
10.3
45.3
0.0
4.0
6.3
47.3
49.3
55.3
60.3
1.0
8.3
3.0
24.8
2.0
12.3
0.5
51.3
53.3
Shutoff (hours)
13.3
19.1
21.1
3.5
1.1
18.1
30.0
32.0
13.1
18.6
28.4
30.4
1.5
5.5
22.0
26.0
3.1
15.1
22.1
24.3
20.1
26.3
11.5
24.0
28.0
9.5
7.5
0.0
0.
0.0
h Runs 041115 and 041117 terminated due to TB - turbidity breakthrough; run 040518 terminated due to TM - time constraint.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure 4.43 Belmont pilot plant; Mn and EH as a function of time. Effect of chlorine loss and pH on Mn control.
133
A case study presented at the 2005 AWWA WQTC showed some interesting insight into
what happens once a filter used in the IOCME mode losses chlorine (Gabelich et al. 2005). This
study was done in response to Mn related water quality issues that revealed themselves in the
distribution system. The filters had been previously chlorinated but chlorine was terminated and
the filters allowed to become biologically active since the plant had upgraded primary
disinfection from chlorine to ozone.
Mn that was once captured on the surface of the anthracite filter media migrated to lower
layers in the filter (sand, hematite and garnet). The authors of that presentation suspected that the
Mn oxide coating on the anthracite was a mixture of Mn(III) and Mn(IV), as opposed to all
Mn(IV), and that the Mn(III) was held in place by the presence of chlorine. It was also suspected
that Mn(III), a soluble form of Mn, desorbed off the media by cation exchange with Fe+3 and
Al+3. The liberated Mn(III) was then oxidized to Mn(IV) in the sand and hematite layers.
With this new information, the IOCME data for Case Study I was reanalyzed. The idea
was to investigate whether the change in Mn adsorptive capacity was a function of water
temperature or the Fe+3 loading. Originally the PIs had interpreted the change in behavior
associated with decreased temperature as a function of temperature, however, this may have been
a secondary observation. The primary influence could have been that the lower temperatures lead
to less efficient coagulation and therefore more cation loading on the filter.
Table 4.12 presents the concentrations of iron being added to the filters for each of the
runs conducted. Both total and dissolved iron concentrations are presented. There is more total
iron being added to the filters in the colder water. This reveals that more floc particles are being
passed onto the filters in cold weather. The floc particles were presumed to be bound, ferric
hydroxide. The amount of dissolved iron, presumed to be free, trivalent cationic iron, that is
being loaded to the filters is about the same for all runs.
Table 4.12
Fe loading onto filters
Temperature pH of Dissolved Fe Total Fe
Pilot Plant
(C) filtration loading (mg/L) loading (mg/L)
18 8.2 0.009 0.674
Baxter 20 7.5 0.005 0.739
22 6.6 <0.005 0.595
22 8.5 0.007 1.043
Belmont 24 7.5 0.007 0.990
26 6.7 0.006 0.792
8 8.4 0.006 0.939
Baxter 8 7.5 0.006 0.851
5 6.6 0.007 0.932
12 8.5 0.005 1.582
Belmont 13 7.5 0.012 1.755
8 6.6 0.008 1.959
135
Control of Mn with pH
We analyzed the No Chlorine filter data (both dual media and GAC) for actual Mn
concentration in the effluent, as opposed to percent Mn removal. There were occasions in which
the Mn effluent was below 0.020 mg/L but these usually corresponded to low Mn loading (i.e.,
<0.020 mg/L). Out of a total of 253 filter runs conducted without chlorine, only three (1%) were
less than or equal to 0.020 mg/L. The pH and temperature of the three sample points are
presented in Table 4.14.
Table 4.13
Avg. percent Mn removal by GAC and dual media filters depending upon applied chlorine
Dual media GAC Dual media Dual media
no chlorine no chlorine [Cl2] < 0.4 [Cl2] 0.4
Pilot plant n Removal n Removal n Removal n Removal
Belmont 99 6% 53 15% 0 NA 109 91%
Baxter 67 6% 34 11% 14 64% 56 89%
136
For the Baxter pilot plant, only two dual media filter runs effectively controlled Mn to
below 0.020 mg/L. These were the highest filtration pH runs conducted at the Baxter pilot plant.
Once the filter pH dropped below 7.75, Mn control was no longer effective. There were no GAC
filter runs that produced a filter effluent below 0.020 mg/L.
For the Belmont pilot plant, none of the dual media filters effectively controlled Mn even
though there were two runs at high pH values, i.e., above 7.75. Only one No Chlorine filter run
at Belmont controlled Mn, a GAC filter and the pH at which it did, was not the highest pH value
of all the GAC filter runs.
The PIs were not able to achieve effective Mn control across filter media using filtration
pH alone.
The authors then asked, If a utility uses ozone as it primary disinfectant, is it possible to
control Mn without chlorine? That is, will a filter hold Mn dioxide without chlorine? An
experiment was designed to answer this question. Ozone was used to fully oxidize water,
converting all the Mn(II) to Mn(IV), and then pass this water through a chlorinated and non-
chlorinated filter at various pHs.
Details of the experiment are listed in Chapter Three. The major points of the design are:
(1) ozonation was conducted with a high dose, at pH 6.5 so that Mn is oxidized by molecular
ozone, (2) when the pH needed to be raised, it was raised after ozonation, (3) Mn was analyzed
in three size ranges, total, <0.22 m and <30 kDa. The results showed that ozone was effective in
converting dissolved Mn to oxidized Mn and on occasion, some of the oxidized Mn was in the
colloidal form.
The answer to the previous question is yes. A utility can control Mn (without chlorine)
via pH once the Mn has been converted to Mn(IV). The higher the pH the more stable the Mn
dioxide is and the more effective the control. The percent removal as a function of media type,
with or without chlorine, with or without ozone can be seen in Appendix E. The pH at which
effective control was achieved is different for the Belmont pilot plant and the Baxter pilot plant.
The Belmont pilot plant achieved over 90% removal of Mn at pH 7 and above, while the Baxter
pilot plant achieved over 90% at pH 8 or greater. The Belmont and Baxter plants receive
different source water (Schuylkill River and Delaware River respectively). There is more
alkalinity in the Schuylkill River compared to the Delaware River.
Since ozone was used to oxidize the Mn, and it is generated from oxygen, the water had a
high dissolved oxygen concentration, in many cases above saturation. It may be the presence of
dissolved oxygen (an oxidant) at the pH values mentioned that helps keep the Mn oxidized on
the media surface. In other words, once Mn is oxidized to Mn(IV), the presence of dissolved
137
From previous pilot plant work (Kohl 2002) it was shown that even if Mn entered a filter
completely oxidized, i.e., Mn(IV), without chlorination (and at pH 6.5) it would leave the filter
in soluble form, Mn(II). This led the team to investigate the use of EH to determine if the
reduction of Mn(IV) to Mn(II) in the filter was measurable. After 2 years of attempts, it was
determined that EH could not be used as a predictive tool. There is Mn reduction occurring within
the filter but this reduction could not be correlated to bulk water EH. Both reduction and
oxidation seem to take place on the filter media surface so that the overall change in bulk water
ORP, as measured by EH, did not change enough or consistently enough to be predictive.
A full scale test was conducted at one of the participating facilities. The facility examined
its ability to control Mn across GAC filters in comparison to anthracite filters using chlorine and
pH. The experiments as conceived were not fully realized; therefore, a certain amount of the data
collected is not included in this report, and the analysis of the data was limited. The results of
each of the experiments along with a process flow chart are included in Appendix F, and several
very interesting observations can be made.
Background
The full-scale facility was designed as a conventional water treatment plant used to treat
surface water. It was also designed to control taste and odor issues, and as such, was fitted with
GAC filters that treated high pH water. When Stage 1 D/DBP rule came into effect, the plant had
to lower the pH of coagulation (to allow for the removal of TOC) and limit prechlorination. This
has changed the effectiveness of the sedimentation basin to control Mn. Also, the source water
from the river seems to have more Mn spikes, a cumulative result of acid mine drainage.
Figure 4.44 presents a full-scale WTP sampling event. The sampling locations and time
are shown on the x-axis. Mn data was collected using three separate means. The triangles
represent the ICP-MS data which is considered to be the most accurate. The other two data
points are Mn concentrations gathered using on-site, colorimetric analytical methods. The
squares present bench top analysis using PAN, and the diamonds are on-line data points. The
graphic shows the Mn concentration at three sampling times for each unit process. The units
process from left to right represent source water to finished drinking water. The two filter
effluent data sets are for separate filters being operated in parallel. The pretreatment consisted of
coagulation/flocculation followed by sedimentation. The pH is raised at the sedimentation basin
effluent with NaOH and chlorine as added via NaOCl to control Mn across the filters. Because of
138
139
0.80
Spetember 14-16, 2004 On-Line
0.70
Filtration pH = 6.5-7.4
Grab - PAN
Total Manganese (mg/L)
0.60
Grab - ICP-MS
0.50
0.40
0.30
0.20
0.10
0.00
2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 2 24 46 2 24 46
hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr
Source Sed Basin Filter Anthracite GAC Clearwell Mid- Clearwell
Water Effluent Influent Filter Eff Filter Eff Influent Clearwell Effluent
140
0.12
Grab - ICP-MS
0.10
0.08
0.06
0.04
0.02
0.00
2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 2 24 46 2 24 46
hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr
Source Sed Basin Filter Anthracite GAC Clearwell Mid- Clearwell
Water Effluent Influent Filter Eff Filter Eff Influent Clearwell Effluent
0.16
December 28-30, 2004 On-Line
0.14
Filtration pH = 6.5
Grab - PAN
Total Manganese (mg/L)
0.12
Grab - ICP-MS
0.10
0.08
0.06
0.04
0.02
0.00
2 24 48 . 2 24 48 . 2 24 48 . 2 24 48 . 2 24 48 . 2 24 48 2 24 48 2 24 48
hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr
Source Sed Basin Filter Anthracite GAC Clearwell Mid- Clearwell
Water Effluent Influent Filter Eff Filter Influent Clearwell Effluent
141
The cost model presented on the cost and benefit tables is based on reasonable capital and
operating cost assumptions that a utility may experience when faced with a manganese problem.
The assumptions for the model have been previously presented. The bases for the model are:
The authors thought it prudent to expand upon the use of 0.5 mg/L as an influent water
quality assumption. This value is reasonable for ground water sources, however, it seems high
for surface water sources, and on average it is, please refer to Figure 4.5. The PIs used the
worse case scenario idea in the selection of design criteria of surface water Mn treatment. The
thought process being that ground water sources tend to be stable and surface water sources can
be flashy. The average of the maximum surface Mn concentration is 0.4 mg/L (self reported
initial survey data). The other advantage to using 0.5 mg/L for all the influent water conditions is
that is makes analyzing the tables easier.
These figures will vary tremendously from utility to utility and, of course,
geographically. However, the cost tables can be used to judge the relative differences in cost that
may result if the Mn treatment goal at a particular plant is reduced or if a particular process is to
be modified for Mn treatment. All calculations and a complete set of analysis are located in
appendix G. There are also graphic representations of comparative cost presented in that
appendix.
The cost tables (Tables 4.15 through 4.18) present the total capital cost for building a
treatment plant for manganese with a capacity of 1 mgd, 10 mgd, or 100 mgd or for upgrading an
142
A complete set of tables is located in Appendix G. The cost for treating water does not
seem to vary significantly depending on the source of Mn. Most treatment processes rely on
converting the dissolved, soluble Mn to the less soluble, particulate form for subsequent
separation using filtration or clarification. Some processes rely on attachment and then
oxidation, such as manganese greensand, in most cases the Mn is oxidized and then removed.
Two processes which can remove dissolved Mn directly are ion exchange and membranes.
For the purpose of the cost model, specific costs associated with utility expenses as a
consequence of elevated Mn were not included other than the actual operating and capital costs
associated with treatment. Therefore, the cost tables presented in this report tend to understate
143
144
149
INTRODUCTION
As with the other chapters this will follow the sequence of the major investigations.
However, each section will include knowledge gained during all the investigations.
INITIAL SURVEY
Most utilities are aware of whether or not they have a Mn issue. The strongest source of
Mn feedback comes from their customers. Since Mn is an aesthetic issue, the first people to
notice problems are the consumers.
Most utilities are quite capable of dealing with Mn. However, if there is no history of
customer complaints regarding Mn, the utility may be unaware of latent Mn issues. Specifically,
if a utility controls Mn without recognizing the mechanism, say, by way of induced-oxide coated
media effect (IOCME) then a Mn problem may occur if that process is disturbed. This
disturbance is more likely to occur today than in previous years, since many utilities are seeking
ways to reduce DBPs. In many instances, the initial point of chlorine application is being moved
further back in the process, and in some cases this initial point of chlorination is after the filters
eliminating the benefits of IOCME.
Mn is an issue for both surface water and groundwater systems. Most utilities measure
both source water and finished water for Mn while few routinely measure the Mn in distribution
system. The utilities that routinely sample and monitor Mn are those utilities that experience
complaints. Our initial survey results indicated that less than one quarter actually sample
distribution system Mn concentration. This may reflect a prevailing thought process that the
distribution system concentration is equal to the finished water concentration. This thought
process is incorrect.
On a side note, there are utilities whose source water is affected by acid mine drainage
(AMD), that used to have only a little Mn or only a few episodes, however, now seem to have
more Mn and more frequent episodes. Such utilities are working with their watershed
associations as best they can to combat the trend of increased Mn occurrence in source water.
The analysis of the finished water concentration of the surveyed facilities revealed that
for all source waters and all treatment types, the average amount of Mn is 22 g/L in the treated
water leaving the plant. The 90th percentile of the data was below 50 g/L. Currently, Mn is
being controlled at many utilities to below the SMCL, yet customer complaints still exist. This
suggests that utilities respond to Mn issues as part of customer service as opposed to regulatory
compliance.
Pressure filtration for iron and Mn removal is used in many smaller systems especially
those with groundwater sources. This treatment process becomes prohibitively expensive as the
system size increases. Pressure filtration is designed to primarily remove iron and Mn, therefore
if other treatment requirements are imposed on a utility, then that utility has to utilize additional
unit processes. This need for additional treatment tends to move the process selection process
away from treatment for iron and Mn removal only, and toward alternative processes for which
iron and Mn is removed (or reduced) subsequent to (or in addition to) the primary design. For
larger water treatment plants, particularly those that rely on surface water, several unit processes
151
DETAILED SURVEY
152
Both high and low concentrations of manganese in treated water result in either chemical
or biochemical deposition of manganese oxides on pipeline surfaces. Biochemical deposition
occurs in systems that have no chlorine or the chlorine residual dies off before the end of the
distribution system. Chemical deposition occurs when Mn (II) enters the distribution system and
is oxidized to Mn (IV) by chlorine used for disinfection. Manganese deposition generally
decreases with distance from the treatment plant. The progression of deposition through the
distribution system is generally affected by the concentration of manganese and the capacity of
the pipeline surface to adsorb the manganese oxide. This capacity depends on the average water
velocity, which determines the shear force and the width of the boundary layer within which the
manganese oxide remains protected. Once the capacity of the pipeline is exceeded or when
higher flow rates occur, manganese oxide coating will detach until equilibrium is reached,
possibly causing deterioration in water quality at the tap. Evidence of this was gathered from
some excursion sampling, when a distribution systems Mn concentration was 5 to 10 times
higher than the Mn entering the system.
There were no strong correlations between Mn concentration and other water quality
parameters within a distribution system. Therefore, no surrogate water quality parameter was
found. The study suggests that there is no substitute for Mn sampling nor is there a good
predictor of Mn concentration. The parameter with the most promise of producing a strong
correlation was apparent color. The occurrence of Mn within the distribution system is a function
of how much Mn enters from the source. It is also a function of the local conditions, most
notably the velocity since it stirs up the settled particulate Mn. The predominance of MnO2
during these high velocity (re-suspension) episodes adds to the availability of adsorption sites
and an increase in catalytic action thereby decreasing the concentration of any soluble Mn.
Therefore, at high flow conditions MnO2 is the predominant form of Mn, and this causes colored
water. This is advantageous for flushing because Mn is removed from the distribution system
when local velocities increase. Yet it can detrimental because this suspension of Mn particles
increases complaints as it is highly visible.
The need to define Mn speciation after ozone is based on informing the operator whether
or not the ozone process has oxidized the Mn. If colloidal Mn is formed and the water tested via
a 0.22 m filter it would seem as if there was dissolved Mn ergo not enough oxidant present.
This would be a misinterpretation of the reality of the situation. The PIs took this one step
further and tested to see how far into a distribution system colloidal Mn could be found. In this
study, only the facilities that use sequestration to control Mn problems had colloidal Mn in their
distribution system. The study did not indicate that ozone use results in colloidal Mn in the
153
CASE STUDY I
Under certain raw water conditions, IOCME did not maintain Mn below acceptable
levels. Factors which influenced this were dose of chlorine and filtration pH. The ability of the
filters to remove Mn was, as expected, also influenced by seasonal temperature variations.
Between the tested pH values of 6.5 and 8.5, the lower the pH, the less reliable the process of Mn
removal. Mn oxidizes more readily at elevated pH. Also, the ratio of soluble Mn to particulate
Mn will vary with raw water conditions and with coagulant dose. Particulate Mn will be
coagulated, settled and filtered, while soluble Mn must be oxidized either in the pretreatment
basins or through IOCME on the media grains, if not it will pass through the treatment process.
The oxidation reaction of Mn is a kinetic one (i.e., time and temperature dependent); the colder
the water the slower the reaction and, consequently, the process of Mn removal is less efficient
when the raw water is colder in the winter.
The use of ozone to control Mn was possible even if no chlorine was applied to the filter.
When ozone was applied to the incoming water, the Mn was oxidized from the soluble to the
insoluble form and subsequently removed by filtration. Any Mn that was not oxidized by the
ozone passed through the filters, unless chlorine was applied to the filters. It is possible to apply
ozone to water and not convert the Mn to the particulate form. In order for Mn to be oxidized it
must have sufficient contact with molecular ozone. Since ozone is very reactive and is
scavenged there must be enough ozone applied to overcome this competition. Lowering the pH
of ozonation helps to promote the presence of molecular ozone by having less scavenging by
OH-. For this research a pH of 6.45 was chosen to accomplish this.
Another benefit of using ozone to oxidize Mn from Mn(II) to Mn (IV) is that there is an
overall increase in oxidation reduction potential (ORP), making the capture of MnO2 more
successful. That is, once particulate Mn is produced it can remain stable in the filter. We
hypothesize that the presence of dissolved oxygen, at or above saturation, after the water has
been ozonated was enough to keep it in this oxidized form. Empirical evidence also indicated
that more alkalinity in the water lead to better control of Mn using ozone. This we believe to be a
result of MnO2 stability, as opposed to ozone interaction, as Ca2+ is itself, an ozone scavenger. It
is possible to combine the use of ozone and free chlorine. The dose need for both would be
reduced as compared to the use of either alone.
The research conducted for the Case Study I demonstrated that a nominal dose of
chlorine applied to the settled water will generate a manganese dioxide coating on filter media
grains. The manganese dioxide coating will further enhance Mn removal by adsorbing dissolved
Mn and then providing further oxidation and removal. This observation should not be unique to
the type of raw river water at Philadelphia but rather should be applicable to many waters that
use conventional treatment and chlorinate the water just prior to filtration.
CASE STUDY II
154
COST MODEL
The interviews conducted during this research strongly suggest that many consumers,
perhaps the majority, will experience episodic difficulties if the Mn concentration in the
household water remains at 0.05 mg/L. From the work completed for this study, the investigators
believe that a 0.02 mg/L Mn target reasonably balances benefits to the cost of producing water at
a low Mn concentration. Some utilities, such as the Philadelphia Water Department, have
established an even lower internal goal of 0.015 mg/L.
The cost to benefit ratios in Appendix G tables and figures suggest that several treatment
technologies can cost effectively remove manganese in drinking water, based on the models and
assumptions developed for this study. A complicating factor is that many states do not enforce
the secondary standards and rely on consumer pressure to drive utility action. Many utilities are
sensitive to public pressure, but still have difficulty justifying treatment costs on the basis of
reducing consumer complaints if it means producing water at a lower standard than the minimum
required. The intangible costs to both utilities and customers, although difficult to quantify,
would strongly suggest that most customers would be willing to pay an additional price for water
if the water were aesthetically acceptable the majority of the time. Today, many people have
become much more sensitive to aesthetic water quality and tend to judge the quality of service
that a utility is providing on the basis of water palatability. In addition, many consumers today
tend to equate the safety of water with taste, odor, and appearance.
Many systems that have Mn problems are small groundwater utilities that may not have
the financial resources to support new treatment especially if that new treatment is to treat water
beyond that required for public health. Even larger systems may not respond to the need for
additional Mn treatment if that additional treatment requires the building of new treatment.
Utilities are more likely to accept small increases in operational cost than they are to incur capital
debt to improve upon parameters that meet existing suggested limits.
Since the Safe Drinking Water Act was signed in 1974, there have been numerous
regulations and standards that have been implemented to deal with such issues as disinfection
byproducts, synthetic organics, radionuclides and metals; very nominal attention has been given
to the impacts and reasonableness of the secondary standards including Mn. This research has
concluded that the Mn standard of 0.05 mg/l, as it now exists, is not adequate to control
consumer complaints associated with household problems. Yet, the cost of treating water to a
lower level than the SMCL is not justified solely on the basis of cost savings to the consumer as
compared to the capital and operating treatment costs. However, many utilities do operate their
treatment facilities to produce as low a Mn concentration as affordably possible. There seems to
155
156
OPERATIONAL
It is the opinion of the PIs that controlling Mn prior to the distribution system is the best
option. The distribution system will adsorb Mn over a long period of time and will release it
from time to time as conditions dictate. However, the frequency and intensity of this release will
be less if less Mn enters the distribution system. Once the water enters the distribution system
there is very little that can be done to control it.
Sequestering agents if used properly can control Mn. However, the use of sequestering
agents is more complex than most people are led to believe. Establishing the correct chemistry is
often difficult because of constantly changing water quality and conditions in the distribution
system. In many distribution systems, what is just right for near may not be right for far, and
what is just right for far may not be right for near. Even with the correct chemistry, if Mn enters
the home where laundry is being done with hot water and bleach, the sequestration breaks down.
This will release Mn(II) that will then be oxidized to Mn(IV) directly on the material surface,
making black spots.
The amount of Mn present and the frequency of its presence in the water are the main
factors in selecting the best method of control (as well as understanding how Mn control occurs).
Oddly enough, the more Mn, and the more constant its presence, the simpler the design and the
more effective the operation will be. The oxidation of Mn is a kinetic reaction so the more Mn,
the more oxidation will occur. The less advantageous aspect of this is that the treatment cost
money and some utilities are so used to having little to no treatment that even this modest step
seems extremely expensive. Under constant Mn loading, consider using a Mn specific filter
media either self-generated induced oxide coated media (IOCM) or proprietary filter media.
The use of KMnO4 to oxidize Mn is effective under these conditions too but it requires
monitoring as well as good settled solids control.
The selection of treatment options for other scenarios becomes harder as the Mn
concentration decreases and become less frequent. The main driving force is economic. Effect
treatment, built for only occasional use, is inherently expensive. When the capacity of treatment
systems, sized to handle a specific loads, is exceeded, Mn pass through occurs. For these
situations the most effect process was the IOCME. This process has a large capacity and is
always active. The prerequisites for this process are: granular filter media, chlorine, and Mn (at
least enough to have an oxide coating on media). The down side of this is the continued reliance
on the DBP forming chlorine within the treatment process. Even if a treatment plant converts to
ozone disinfection the use of IOCME can keep the treated water Mn free.
Distribution systems that experience a seasonal change in delivered water volumes have
additional Mn issues. During periods of low flow, the Mn loading into the system seems to be
low enough so as to have no effect on the water quality; however, as the flow rate increases the
systems ability to hold a specific amount of Mn decreases. The Mn is then released and the
customers see it. The problem can be severely exacerbated when the seasonal change in flow is
great and the low flow period allows for sections of the distribution to have no chlorine. These
zones become biologically active and the mechanisms of Mn oxidation reduction change. Even
more Mn is released than predicted by the increase in water velocity alone.
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Control of Mn by way of IOCME is so effective that we know little about it. It works so
well over such a wide range of conditions that it calls little attention to itself. If not for the work
of Dr. Knocke et. al. much of what little we know would be still be a mystery.
However, when we do approach the limits of the effectiveness of IOCM, we get a
glimpse at how complex it is. The effectiveness of IOCM results from the combination of two
mechanisms which are interrelated oxidation and adsorption. The parameters that control these
processes overlap. The pH of the filtered water is the most significant water quality parameter
these two processes share. The higher the pH, the more rapid the oxidation process, and the
higher the pH, the greater the adsorption capacity of the oxide coated media. Another water
quality parameter that affects both processes, but no so obviously, is temperature. The warmer
the water, the more rapid the oxidation process, and the greater the media adsorptive capacity
will be. For temperatures above 10C, IOCME worked very well. For temperatures below 8C
(free chlorine residual leaving the filter in excess of 0.4 mg/L), the pH had to be greater than 6.5
for IOCME to be reliable. IOCME was effective for water temperatures down to 3C as long as
the pH was raised to 8.0 or above.
A water quality parameter that seems to only be important to oxidation but has an effect
on adsorption is free chlorine. The presence of free chlorine oxidizes the adsorbed Mn and
converts it to MnO2 thus yielding more sites for future adsorption, thereby increasing the
adsorptive capacity. Free chlorine is required to be present and available when Mn is adsorbed
onto the media surface. However, IOCM can occur even when there is no free chlorine residual
leaving the filter. This explains why GAC can be used as a media for IOCM. Although the
effect of each parameter on the separate process is related, it is not proportional. For example,
water temperature is much more significant to the oxidation process than the adsorption process.
Utilities should expect reduced Mn control across IOCM filters in colder water and to offset this
reduced performance by increasing the pH and/or increasing chlorine.
Ozone
If a utility uses intermediate ozone and has intermittent Mn issues, it should consider
applying more ozone during the high Mn event so that all the Mn is MnO2. The oxidation of
Mn(II) to Mn(IV) requires the presence of molecular ozone. In the application of ozone there is
either not enough ozone applied, or it is applied in such a scavenger rich environment that
molecule ozone is in solution for only a short period of time. One may wish to speciate the
ozonation process effluent using 30K Dalton filters to see if oxidation is complete. The presence
of colloidal Mn indicates there has been enough oxidant used. The presence of colloidal Mn in
the distribution system was not found to be an issue for the utilities that participated in this study.
Once the Mn(IV) is formed, granular filter media seems to be able to retain it in. The presence
of dissolved oxygen above saturation seemed to be enough to keep it stable on the media. Pilot
results indicated that the higher the pH the more stable the filtration process and better Mn
capture even without chlorine.
The other consideration is to simply keep a filter in the IOCME mode to capture Mn even
if ozone is used. For one utility, the filter that used to be operated in IOCME mode (albeit
unknowingly) was the source of distribution system Mn occurrence. The Mn appeared once the
plant converted to ozone disinfection and stopped chlorinating the filters. The utility eventually
replaced the media as opposed to continued chlorine application.
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The authors are not suggesting that the USEPA change the current SMCL. Our findings
indicate that the SMCL was rarely the basis for utility action. The wide range of responses to the
federal SMCL by the individual states further illustrates the variety of opinions about the Mn
SMCL. However, the authors have, after some consideration, come to the conclusion that most
utilities would be well served to adopt a finished water Mn goal of 0.02 mg/L. This level is
achievable and measurable. While achieving the goal does not guarantee a worry-free life, it
severely limits the distribution systems ability to accumulate troublesome levels of Mn.
Friendly Quote
When discussing Mn treatment our Australian friend, who indicated he was quoting the
English, said Do not be greedy. By this he meant that when one is treating for the removal of
Mn, go ahead and plan, build and operate for it. Although Mn removal can be achieved
incidentally by a unit process, if the process is not designed and operated for it, then there will be
occasions that Mn control is lost. Also, the operation of a unit process can be severely restricted
if it has multiple functions. Therefore, at times, when a seemingly simple solution to a problem
cannot be made because of incidental implications, one may feel the pinch. Worse yet, one
forgets the incidental implications and makes a decision that results in system upset. The
sentiment is valid (a bit harsh) and if used wisely (gently) will enable the utility to best discern
how to handle their Mn issues.
When one builds in more treatment and has more testing, one is spending more money, is
more likely to be successful at treatment, and the community is likely to benefit. The utility is
less likely to have customer complaints associated with Mn and therefore reduce costs associated
with those complaints.
The cost model shows how much less consumers would have to spend for each dollar
spent by the utility. The idea is sort of communal in as much as the centralized entity betters the
life of the community at a cost to itself. It is not so much that reducing the Mn levels pays for
itself by reducing the utilities expenses, although there is some benefit. The utility treats the
water to a level that improves the overall water quality for the community even though it does
not have to.
To better understand the Australian mindset the PIs encourage the reader to study the
water quality system in that country. The government has not established itself as the champion
of the people by mandating water quality standards so much as it has set itself up as the mediator
between consumers and utilities, giving the consumer a way of asking for water quality
improvements to be made and an ability to understand what that will cost them.
MN TESTING
Mn analysis is thought to be simple, and it can be. There are several techniques
available. Choosing one is not complicated, but it is important. There are several aspects that
should be considered before applying a specific technique.
159
The method detection limit (more importantly the reporting limit) of the analysis being
performed for your utility is very important. On several occasions, utilities provided the PIs with
Mn concentration below detection limits. This may have given some a good feeling or even
satisfied some internal requirement. However, the ND or < symbol are hard to use for data
analysis and therefore have limited use, especially if the reporting limit is high. For example,
<50 g/L lets the utility know that Mn is below the SMCL but little else. Most analysis can
achieve a much better resolution. The PIs recommend you look at Mn at 0.010 mg/L or less.
It is acceptable to use wet chemical assays for routine operational work, but always have
a series of confirmatory analytical assays. As with any measurement system, it is best to know
the limits of the method.
Mn Filtering
For this project 0.45m, 0.22m, and 30 K Dalton filters were used. It is the PIs opinion
that 0.22m filters offer the best choice. Although it makes little difference between the filters
for Mn, with Fe it does, and since Fe and Mn often occur together it was thought best that
0.22m filters be used. The appearance of colloidal Mn is not common and usually associated
with ozonation, high Mn levels within a system that uses a chelating agent or has lost all chlorine
residual at the end of the system. So unless you have these conditions, there is no need to use the
30 K Dalton filter as it requires significant effort. However, to be certain about levels that are
truly dissolved, using the 30K Dalton filter is a good choice.
ADDITIONAL RESEARCH
The PIs would like to know if the presence of saturated dissolved oxygen is chemically
(thermodynamically) capable of keeping MnO2 as a solid on a filter surface once it has been
captured.
The use of apparent color to discern the concentration of Mn has merit and it may be
prudent to look into its use more substantially.
The PIs want to know if the soil chemistry associated with the reduction of MnO2 is
congruent with aqueous chemistry by investigating the intermediate step of Mn(III) in the
oxidationreduction process. It is still a mystery to the PIs as to how a filter is able to capture
oxidized Mn yet release dissolved Mn. Is this process biological, chemical, or a combination of
both?
In the not too distant past and in the minds of many consumers, a distribution system was
nothing more than a clean vessel (in some minds sterile) used to hold and deliver water. It is
clean, but not sterile and it has films and sediments. The water industry has known this and has
acted on this knowledge. This is simply one more of those occasions. The distribution system is
not an inert unit process but an interactive one. There are many physical and biochemical
processes at work within them.
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169
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172
175
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177
AA atomic adsorption
AAS atomic adsorption spectrometry
AC advanced clarification
ACGIH American Conference of Governmental Industrial Hygienists
Ag/Ag-Cl silver/silver chloride
AI adequate intake
Alk alkalinity
AMD acid mine drainage
amu atomic mass unit
AO aesthetic objective
AOC assimilable organic carbon
APDC ammonium l-pyrrolidine carbodithioate
APHA American Public Health Association
app. apparent (color)
aq. aqueous
AS air stripping
ASTM American Society for Testing and Materials
ASV anodic stripping voltammetry
atm atmosphere
ATSDR Agency for Toxic Substances and Disease Registry
aux. auxiliary
Avg average
AWRC Australian Water Resources Council
AWWA American Water Works Association
AwwaRF Awwa Research Foundation
C degrees Celsius
Calif. California
CCR consumer confidence report
CERCLA Comprehensive Environmental Response, Compensation, and Liability Act
CFR Code of Federal Regulations
CDM Camp Dresser & McKee
CD-ROM compact disc read only memory
CGS conventional gravity settling
CRC Cooperative Research Center an Australian research entity
CRU Central Receiving Unit (Philadelphia Water Department)
CW clear well
179
FI filterability index
FSTRAC Federal-State Toxicology Risk Analysis Committee
IC ion chromatographic
IAC Idaho Administrative Code
ICP inductively coupled plasma
ICP-AES inductively coupled plasma - atomic emission spectrometry
ICP-MS inductively coupled plasma - mass spectrometry
IDAPA Idaho Administrative Procedure Act
IDL instrument detection limit
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K kilo
kDa kilodalton
kg kilogram
Mass. Massachusetts
MCE mixed cellulose ester
MCL maximum contaminant level
MDL method detection limit
meq/L milliequivalents per liter
MF membrane filtration
MG malachite green
2
m /g square meters per gram
mg/day milligrams per day
mgd million gallons per day
mg/kg milligrams per kilogram
mg/kg-day milligrams per kilogram day
mg/kg/day milligrams per kilogram per day
mg/L milligrams per liter
mg/L as CaCO3 milligrams per liter as calcium carbonate
mg/L as P milligrams per liter as phosphorus
mg/m3 milligrams per cubic meter
MIBK methyl isobutyl ketone
mL milliliter
ML/d megaliters per day
mm millimeter
MS mass spectrometer
MUD Municipal Utility District
mV millivolts
MWCO molecular weight cutoff
g/g microgram per gram
g/kg microgram per kilogram
g/L microgram per liter
g/m3 microgram per cubic meter
m micrometer
mho/cm micromho per centimeter
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QA quality assurance
QC quality control
R2 proportion of variation
RfD reference dose
RL reporting limit
RO reverse osmosis
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T(4-CP)P ,,,-tetrakis(4-carboxyphenyl)porphine
TAG technical advisory group
TB pilot plant filter run end reason turbidity breakthrough
TCR Total Coliform Rule
TDS total dissolved solids
THM trihalomethane
TMB 3,3',5,5'-tetramethylbenzidine
T&O taste and odor
TOC total organic carbon
TM pilot plant filter run end reason time constraints
TRI Toxic Release Inventory
TSS total suspended solids
UF ultra filtration
UK United Kingdom
UL tolerable upper level intake
US United States of America
USA United States of America
USEPA United States Environmental Protection Agency
USFDA United States Food and Drug Administration
USGS United States Geological Survey
USPHS United States Public Health Service
UV ultraviolet
UV254 ultraviolet absorbance at 254 nm
vs. versus
VT DEC Vermont Department of Environmental Conservation
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Utility Information
Name of Utility:
Contact Name:
Title of Contact Person:
Contact Information:
I am calling regarding an AwwaRF project. The project is entitled The occurrence of Manganese in Drinking water
and Benefits of Enhanced Manganese Control.
Are you familiar with AwwaRF and its work? [If not describe it to them.]
The American Water Works Research Foundation is a nonprofit organization that exists to
conduct research for the water industry and share that research among its many members. Their
membership consists of utility participants, consultant participants and manufacturing participants.
The purpose of my call is to ask you a few questions about your experience with Mn and to see if you are (your
utility is) willing to help us with this task. This project is projected to run for two years. We are attempting to put
together information based on geographic location (national and international), source water types and facility
treatment types as well as Mn specific technology. The information we are gathering has to do with the occurrence
and speciation of Mn in our drinking water systems.
The survey will be completed over the phone with you, based on our information we believe that
you are the correct contact person, however, if you are not, can you give me the correct contact
information?
Name / Title / Phone Number
FYI: The results of this survey will be recorded in a database. This database is part of the project
but will not be released to AWWARF or other entities as a whole. The project team will be the
only people to use it in its entirety.
Is there more than one water treatment plant in your utility? What are their names?
185
In order to help up analysis the survey results I will need to categorize your water treatment
process. In a broad sense how would you categorize your water treatment process?
May I ask you to describe you water treatment process in a little more detail? Y / N
Do you use a coagulant?
If they did not list this please specifically ask if they use KMnO4 anywhere in their process and
for what purpose?
Do you filter your water? If yes, what is the filter media you use, how deep?
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As we analyze our initial survey data we may find it necessary to call you back, is that OK?
This may involve a more in-depth survey. Yes No Maybe
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Utility Name:
Facility Name:
What is the type of source water for your facility? (Circle one)
Surface GW GWUDI Blend (Multiple) Consecutive System
Name of Source(s):
If GW:
- Ask them to describe the ground water supply
- Comments/Description
- Comments/Description
If River:
- Seasonal / Climatic Issues?
- Comments/Description
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Comments on above:
We will ask for average with min and max for the last year.
While discussing source water quality see if you can get plant effluent water quality and
distribution water quality. Remember that these are different and that distribution water quality
is harder to get information on.
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Mark-up schematic: (Use a separate piece of paper and the system we agreed upon)
{CGS, Advanced Clarification (AC), DF, MF, RO, Softening, Disinfection only, Treatment for
Fe/Mn only, Air Stripping (AS)}
Please be sure to include:
- Size of plant Design and average flow (MGD) This should be done at beginning
- When was the plant built
- When were major modifications made
- List all Major Unit processes
- Chemical addition, points of application, typical dosage (#/MG or mg/L)
- Disinfection (focus on where it is used and why)
- Filter bed material and depth
- pH of coagulation, filtration, distribution
What is its ultimate fate of your solids? (Sewer or processed on site, etc.)
Do you have special Mn treatment? What benefits do you see from Mn Treatment (less
Customer complaints)?
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How much distribution storage do you have? (We are looking for a volume)
Do you have a regular flushing program for the distribution system? Yes No
- Comments
191
Can you see clusters of complaints within your distribution system? Yes No
Comments:
Closure
Thanks for spending the time to answer this survey. If we have additional questions is it all right
to call you back for clarification of information? Yes No
Let me give you the address again for sending your Source Water and CCR information.
I will send you (OR) I have already sent you a list of parameters requested for both raw water
and finished water.
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Name of Utility:
You may report your information in whatever units you normally use
However, please make sure you note what those units are.
Number of
Additional info samples
Parameter Units or comments Min Max Average "N" value
Name (e.g. 0.2 m or 0.45 etc)
pH
Temp (C)
Turbidity (NTU)
D. O. (mg/L)
Conductivity (mho-cm)
Hardness (mg/L)
Alkalinity (mg/L)
TOC (mg/L)
DOC (mg/L)
-1
UV254 Absorbance (cm )
Apparent Color (PtCo)
Tru Color (PtCo)
Total Mn (mg/L)
Dissolved Mn (mg/L)
Total Fe (mg/L)
Dissolved Fe (mg/L)
Total As (mg/L)
Dissolved As (mg/L)
Hydrogen Sulfide (mg/L)
Phospate (mg/L)
Sulfate (mg/L)
Total Na (mg/L)
Phosphorus (mg/L)
ORP measure (Eh)
Biostability Measure
SUVA (L/mg-m)
Total Calcium (mg/L)
TDS (mg/L)
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Field Sampling
1. Collect the water sample into three 250 mL Grab Sample bottles.
2. Carry 9 pre-labeled 50mL bottles to the field; total metal, pre-ultra filtration and
0.22m analysis.
3. Make sure to have your field blank samples with you.
For each one of the 250 mL bottles follow the below procedure
From the 250 mL bottles, rinse the Total metal bottle with 10 mL of sample water.
Discard rinse water as waste.
(Lid of the 250-mL sample bottle should be returned to bottle it need not be re-threaded
but should cover the bottle to reduce the possibility of dust entering the bottle. The cap
of the 50 mL bottles should be placed face up to avoid contamination if no clean area is
available, and returned to the bottle as soon as possible.)
Pour 50 mL of sample water into Total metal bottle. (Do not filter this sample)
Preparation of syringe
The remaining two 50 mL bottles will contain filtered water.
Attach the 0.22m filter to the syringe, remove the plunger and pour 10 mL of Grab
Sample water into the syringe, replace plunger.
(Try to avoid the pulling of the sample out of the Grab Sample bottle by use of syringe
sucking action.)
Rinse syringe swirl back and forth all around then dump rinse to waste.
Conditioning of 0.22m filter and the bottle
Fill syringe will 50 mL of Grab Sample water.
Filter 5 mL to waste
Filter 10 mL into the first 0.22m bottle to rinse it. Dump the waste into the second bottle
to rinse and then discard the waste. During this time the syringe should be rested on clean
low lint wipes or cloths.
Filtration through 0.22m filter
Place combination( syringe and filter) onto the bottle and being to push on syringe to
begin filtering.
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A. Assembling of Parts
B. Rinsing of cell body and spout tubing and collection of 1st sample
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D. Apparatus Clean-up
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1.0 Introduction
To achieve very low manganese concentrations in the finished water, PWD relies upon
contact oxidation and adsorption on oxide coated filter media in the presence of pre-filter free
chlorine residual. Strategies to reduce disinfection by-product formation such as use of
alternative disinfectants, reduction of chlorine residuals, and delaying the point of chlorination
downstream in the treatment process could impede the existing manganese removal mechanisms.
The investigations for Phase VII pilot testing are designed to characterize the effects of pH, pre-
filter chlorine, coagulant type, filter media, and seasonal raw water quality on the ability to
remove and retain manganese.
Manganese control was a major element of Phase III (2000 to 2001), Phase IV (2001 to
2002), and Phase VI (2003) piloting. The effects of pH, chlorine residual, intermediate
ozonation, biologically active filtration (BAF), and coagulant type on manganese control were
evaluated. Contact oxidation and adsorption in the presence of adequate free chlorine residual
(about 0.5 mg/L over breakpoint) was found to be the most effect method of achieving the 0.015
mg/L total manganese goal. Intermediate ozone and BAF were not found to be effective for
manganese control.
Phase VII piloting will include four major and two minor investigations which are
summarized as follows:
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2.0 Investigations
The PWD has two pilot plants, each located full scale water treatment plants; these plants
draw water from two different river sources, the Schuylkill River and the Delaware River. A
schematic of the Belmont WTP pilot plant (Schuylkill River source) is presented Figure B.2
The pilot plants draw water from the river source, without any pretreatment. About 20
gpm of river water enters a 600 gallon raw water basin that provides about 30 minutes of contact
time to model pre-treatment chemical addition.
The water is pumped and split into two parallel 8 gpm process trains. First the flow
enters two small rapid mix basins, followed by two (Belmont pilot) or five (Baxter pilot)
flocculation basins, with a tapered floc mixing scheme. The water then flows through a lamella
plate, upflow clarifier for settling; the full scale plants have gravity settling basins.
Depending the investigation protocol, the settled water from one of the two process trains
may enter an 8 column, counter current, intermediate ozone contactor. Ozone is typically added
in the first column only, and then quenched if necessary in the last column.
The settled water, or post ozone contact water, is then filtered by gravity. Each train has
two dual media filters (21 anthracite and 9 sand) and one biologically active GAC filter.
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Schedule
The schedule for Phase VII is from March 2004 to February 2005. Pilot Plant
information relevant to AwwaRF 2863 will be forwarded to the PIs for inclusion in the final
report by November 2004. At least two of the investigations will be repeated twice to obtain
seasonal data. Investigations 1 and 3 are complex and labor-intensive and will require the
piloting staff from both Baxter and Belmont to work together first at one plant then at the other
to complete the experiment. Investigations 2, 4, and 6 may be performed at each plant with its
own staff.
New Measurements
Oxidation-reduction potential was added to the sampling regimen during previous Phase
VI testing. Technical problems with the instrumentation prevented collection of useful data
during Phase VI piloting. The piloting staff changed the ORP equipment to new (Orion) probes
and are able to produce reliable data for Phase VII testing. Redox potential may prove to be a
valuable operational tool to determine the level at which manganese will oxidize or reduce and to
draw correlations to manganese breakthrough. Measurements will be taken at the applied water
after ozonation or chlorination and at the filtered water. Redox potential measurements are
temperature dependent so all Eh measurements will be accompanied by a temperature. The Eh
will be taken along with pH, chlorine residual, and manganese measurements.
The detailed standard operating procedure for the determination of redox potential is
provided in the next section of this appendix . The data are measured and recorded as:
Eh = ORP + Eref
where Eh is the reported redox potential, ORP is the half-cell potential in millivolts of the
sample measured with an inert (platinum) indicator electrode at the given temperature, and Eref is
the reference potential measured with a reference (Ag-AgCl) electrode at that same temperature.
Chemical doses will be established based on previous testing experience, full scale
plant operations, and jar testing in accordance with the judgment of the pilot plant
staff.
Both Train A and Train B will be in service with equal influent flow of 8 gpm to each
train. Both pilot plants will run at 8 gpm through flocculation and waste 2 gpm
before sedimentation.
Rapid mixing and flocculation will be set to optimized G-values as determined from
previous investigations.
The coagulation and filtration pH will be varied as described in Section 2.2.
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203
Objective: The objective of this investigation will be to study the effect of pH on manganese
control using ferric chloride as the primary coagulant over a range of filtration pH
values from 6.5 to 9.0.
Description: Both Baxter and Belmont plant staffs will work at each plant in turn due to the
complexity and labor intensiveness of the investigation. Due to the difficulty of
filtered manganese and redox potential measurement, only three filters will be
operated a time. Both Train A and Train B pretreatment will be started up
together to facilitate a smooth transition from the Train A filters to the Train B
filters. Both trains will be coagulated at pH 6.5 using ferric chloride throughout
the investigation.
Intermediate ozone will be used at pH 6.5 with an applied dose of 2 mg/L and all
8 columns in service providing a total HRT of about 17 minutes at 6 gpm. The
dose is expected to yield a measurable ozone residual after the given contact time,
ensuring that all the manganese has been oxidized. If ozone residual is not
detected prior to quenching, increase the ozone dose until a residual is detected.
At the effluent of the 6th ozone column, add caustic soda for pH adjustment, as
described below. At the influent to the 8th column, the ozone residual will be
quenched with sodium bisulfite such that an ozone residual of > 0.0 but < 0.1
mg/L remains at the effluent of the 8th column. This trace ozone residual will
verify that there is no carry over of reducing agent (bisulfite) into the filters which
could potentially cause a manganese breakthrough. The ozone system will first
be connected to receive the settled water from Train A and supply ozonated water
to the three Train A filters. Then, the ozone system will be switched over to
receive settled water from Train B and supply ozonated water to the three Train B
filters.
The pH of the ozonated water will be adjusted using caustic soda added at the
effluent of the 6th ozone contact column (influent to the 7th column) to attain the
desired range of experimental values in a series of three sub-investigations. The
post-ozonation filtration pH will be monitored at the effluent of the 7th column. In
Investigation 1A, Train A will remain at pH 6.5 post-ozonation while Train B will
be adjusted to pH 7.0. In Investigation 1B, Train A will be adjusted to pH 7.5 and
Train B to pH 8.0. In Investigation 1C, Train A will be adjusted to pH 8.5 and
Train B to pH 9.0.
Note that it may be difficult to impossible to maintain ozone residual in the 7th
column at the highest pH tested due to rapid conversion of ozone to hydroxyl
radical. If this proves to be the case, monitor the residual upstream of the pH
adjustment point to ensure proper dosing. Under such conditions, it will not be
necessary to use the quenching agent.
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Investigation 2 Effect of pH on Oxide Coated Filter Media without Pre-Filter Chlorine (Ferric
Coagulation)
Objective: The objective of this investigation will be to characterize the manganese retention
of a previously chlorinated filter which has a developed manganese oxide coating
upon cessation of pre-filter chlorine over a range of filtration pH levels from 6.5
to 8.5. This investigation will be performed using coagulation with ferric chloride
following Investigation 1.
Establish steady state, normal operations with pre-filter chlorination yielding a 0.5
mg/L free residual at the effluent. After 2 hours of run time, the chlorine will be
shut off, and the manganese concentration over the course of the filter run
established by taking measurements at various time intervals, e.g., time zero, 30
minutes, and thereafter hourly increments. After one run, the filter will be
backwashed and restarted without chlorine with measurement of the manganese
profile. Based on the judgment of piloting staff, if unsteady conditions are still
evident, repeat runs will be conducted.
Objective: The objective of this investigation will be to study the effect of pH on manganese
control using a non-manganese containing primary coagulant, such as PACl. The
manganese loading to the treatment process will therefore consist of the
background levels present in the raw water.
Description: The experiments will be as described above for Investigation 1, with the
exception of the substitution of the alternative coagulant such as PACl instead of
ferric as the primary coagulant.
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Objective: The objective of this investigation will be to characterize the manganese retention
of a previously chlorinated filter which has developed manganese oxide coating
upon cessation of pre-filter chlorine over a range of filtration pH levels from 6.5
to 8.5. This investigation will be performed with a non-manganese containing
coagulant, such as PACl, following Investigation 3.
Description: The experiments will be as described above for Investigation 2, with the
exception of the substitution of alternative coagulant such as PACl instead of
ferric as the primary coagulant, as well as timing of the investigation to follow
Investigation 3.
Objective: The objective of this investigation will be to determine the effect on iron and
manganese of filtering samples through 0.45 m, 0.22 m, and 30K Dalton
membrane filters.
Description: The evaluation will consist of an analysis of supplementary data collected during
the experiments conducted under Investigations 1 and 3. At least once per
seasonal investigation, and more frequently if possible, collect a 0.45 m metals
sample, from the settled, ozonated, and filtered water. This collection should
coincide with the sampling for 0.22 m and 30K Dalton samples. The effect of
membrane size on manganese and iron will be quantified.
Objective: The objective of this QA investigation will be to determine whether the ozone
quenching agent, sodium metabisulfite, liberates manganese from oxide coated
filters.
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Communication of results between pilot plant staff, WTP managers and engineers,
project managers, and the Technical Advisory Committee (TAC) is an important aspect of the
pilot program. Reports to be produced for Phase VII pilot study are described below.
A progress report summarizing the investigation will be due 4 to 5 weeks after completion of the
investigation, depending upon receipt of analytical results from Bureau of Laboratory Services
(BLS). Weekly run reports are delivered to the PWD project manager for review and for
compilation in the Phase VII reference binder.
Components of the weekly run report include pilot plant as well as full scale plant
operating parameters including point of chemical application, chemical dose, flowrate through
each process unit, number of units in service, mixing intensity, HRTs, projected loading rates,
and filtration rates. Pilot plant water quality parameters will be summarized including raw,
settled and filtered water quality, profiles of on-line filter headloss, turbidity, and particle counts,
water quality data from BLS, and a summary of filter run production data.
A technical memorandum report will be prepared for review by the TAC summarizing
the results of investigations on manganese control. The report will be based on the analysis
completed in the seasonal objective summary reports, augmented as needed by weekly report
information. After a review period, a conference call will be held with the Pilot Plant TAC, the
pilot plant team leaders, and project managers. Based upon the results of the conference call, the
report may be revised or conference call minutes appended.
A technical memorandum report will be prepared for review by the PIs summarizing the
results of investigations on manganese control. The report will be based on the Technical
Memorandum already written as described in section 3.2. This report will be completed in time
for inclusion in the AwwaRF 2863 report. As per the AwwaRF 2863 schedule that will be the
end of November 2004.
207
208
5 Effect of Determine the effect on iron - Filter pore size - Utilization of data generated in - metals fractions (0.45
membrane and manganese used to determine Investigations 1 and 3 m,
filter nominal measurement of filtering fractionation 0.22 m, 30K Dalton)
pore size on metals samples through 0.45 m,
fractionation 0.22 m, and 30K Dalton
membrane filters.
Information will be
collected via investigations
1 and 3.
6 Effect of sodium Determine whether the - bisulfite dose - Flowrate, HRTs - - iron, manganese
metabisulfite on ozone quenching agent, - Pre-filter - Rapid mix &flocculation G- (Total and 0.22 m)
manganese oxide sodium metabisulfite, chlorine value
coated filter liberates manganese from (with/without) - Coagulant type and dose
media oxide coated filters. - Coagulation and filtration pH
- Sedimentation loading rate
- Ozone dose and contact time
- Chlorine residual
- Filtration rate
209
GENERAL PARAMETERS
Dissolved Oxygen
Ozone Residual
Apparent Color
Total Chlorine
Free Chlorine
Temperature
True Color
Alkalinity
Turbidity
SAMPLING LOCATION
Particles
UV254
ORP
Raw water, pre-chemicals O, 2R pH
O, 4R 4R 4R O, 4R 1R 1R 2R
Settled water O, 4R 4R 4R O, 4R O
Applied water
4R 2R 4R 4R 2R O, 4R
(ozonated/chlorinated)
Filtered water S, 2R 4R 2R 4R 4R O, 4R D D O 4R 4R 2R
210
BLS PARAMETERS
Investigations 1, 3, 5 Investigations 2, 4, 6
Total Manganese
Total Manganese
Total Iron/Al
Total Iron/Al
LOCATION
[1]
[1]
Raw water, pre-
2R 2R 2R 2R 2R 2R
chemicals
Rapid mix, post-
chemicals
Settled water 2R 2R D 2R 2R 2R D 2R 2R 2R 2R 2R 2R 2R
Applied water
2R 2R D 2R 2R 2R D 2R 2R 2R 2R 2R 2R 2R
(ozonated/chlorinated)
Filtered water 2R 2R D 2R 2R 2R D 2R 2R 2R F F F F
1R = once per run, 2R = twice per run, D = discretionary, F = frequent, see protocol
[1] Dissolved metals to be sampled at least once per run and, if possible, twice per run to obtain a replicate sample.
211
212
213
214
215
The Huntington Water Treatment Plant treats water for drinking-water compliance using
traditional treatment techniques. Prior to the D/DBP Rule they coagulated at a high pH and
relied on GAC filter to reduce Taste and Odor compounds. They have changed their operational
practices to remove more TOC via coagulation and moved the initial point of chlorination further
back into their water treatment process.
Water from the Ohio River is pumped into a holding reservoir where solids are allowed
to settle. Following the initial settling of solids, sulfuric acid (to enhance removal of TOC in
coagulation), ferric sulfate (coagulant) and a polymer coagulant aid are added at the mixing tank,
before the water splits into two settling basins. In each of the settling basins, there are four
flocculation chambers consisting of baffling, settling, and plate settlers. As the water leaves the
sedimentation basin, caustic is added to increase the pH to 7.0, followed by addition of a filter
aid and chlorine. The addition of chlorine (2 mg/L) prior to filtration aids in Mn oxidation and
subsequent removal via filtration. To remove taste and odor causing organics, the plant has
historically used GAC filters and had twelve of these on site. Recently, one of the GAC filters
was replaced with anthracite. Depending on other water quality parameters, occasionally some
Mn (which we think remains dissolved) passes through the filter even with the raising of pH and
addition of chlorine. The Mn that does pass through the filters manifests itself in increased
turbidity in the clearwell. There is no chlorine residual leaving the GAC filters. Since a chlorine
residual can be maintained across an anthracite filter, making it better filter for removal of Mn,
one of filter has been changed to anthracite.
By comparing the levels of Mn in the sedimentation effluent with the water in the filter
effluents of the anthracite filter and an adjacent GAC filter, we will compare directly the
performance of the two filter types on Mn removal ability. Because the only variable in the filter
effluent samples will be the filters themselves, this study will allow for a direct full-scale
comparison of Mn removal efficiency between the two filter types.
As a result of conducting the detailed survey and continued dialogue with Sandra
Johnson it was thought that the amount of alkalinity in the process water has something to do
with the efficacy of Mn removal. It seems that the more alkalinity that is in the water the better
removal they achieve. This was supported by an observation that at very low source water
alkalinity, alkalinity so low that treatment cannot be conducted, they add lime pre rapid mix.
During these times, Mn removal is much.
216
217
218
Table B.4.
Plant treatment process and parameters to be tested throughout the treatment process.
Where metals are requested, Mn, Fe, Na, P, Ca, Mg, and Hardness will be measured by
ICP-AES. For metals, three size fractions of sample will be collected: unfiltered (total), filtered
(<0.22m filter), ultrafiltered (<30 kDa). Iron and Mn will be measured in the two filtered size
fractions. Where Mn is the only metal requested, Mn will be measured by the Grab PAN method
and/or the plants on-line Mn measuring instrumentat
s samples will be further processed via
filtration through a 0.22m filter and a 30kDa filter. Iron and Mn will be measured in the
filtered samples. Following collection, the metals samples will be returned to the Philadelphia
Water Department, Bureau of Laboratory Services (PWD-BLS) for analysis. For some samples,
a grab sample will also be collected for determination of Mn concentration by the Hach PAN
method at the treatment plant. The reliability of the PAN method will be confirmed by
comparing results with the results obtained by ICP-AES analysis at PWD-BLS. Figure B.4
depicts locations of on-line Mn measuring instrumentation. Where applicable, samples collected
for metals determinations will also have corresponding Mn measurements obtained by the on-
line instrumentation.
219
220
Table C.1
Detailed Survey: Facility - Average Flow, Design Flow, and Population Served
Utility/Facility Distribution System - Average and Maximum Residence Time and Length
221
222
52 Totals 49 44 43 40
94% 85% 83% 77%
223
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
1.5 1.5 1.5 1.5
n = 30 n = 24 n = 14 n = 14
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
1.5 1.5 1.5 1.5
2
R = 0.3691
n = 10 n = 17 n=4 n = 17
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
1.5 1.5 1.5 1.5
2
R = 0.6397
1.0 1.0 1.0 1.0
2
R = 0.0199 2 2
R = 0.3625 R = 9E-06
0.5 0.5 0.5 0.5
n = 25 n=5 n = 14 n = 14
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
1.5 1.5 1.5 1.5
2
2 R = 0.0951
R = 0.162
1.0 1.0 1.0 1.0
2
R = 0.0241
0.5 0.5 0.5 0.5
2
R = 0.37
Figure C.1 Correlations of raw water total Mn with single water quality parameters. Using the detailed survey self reported data
224
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
0.060 0.060 0.060 0.060
R2 = 0.1715
0.050 0.050 0.050 0.050
R2 = 0.0002
0.040 2 0.040 0.040 0.040
R = 0.0084
0.030 0.030 0.030 0.030
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
0.060 0.060 0.060 0.060
R2 = 0.0728
0.050 0.050 0.050 0.050
2
R = 0.0096 R2 = 2E-05
0.040 0.040 0.040 0.040
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
0.060 0.060 0.060 0.060
R2 = 0.0002
R2 = 0.798
0.050 0.050 0.050 0.050
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Figure C.2 Correlations of finished water total Mn with single water quality parameters. Using the detailed survey self reported data
225
n=9 2 n = 10
n = 13 R n==1 2
0.100 0.100 0.100 0.100
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
2 2
R = 0.0002 R = 0.3761
0.060 0.060 0.060 0.060
R2 = 0.0564
0.040 0.040 0.040 0.040
Distribution System Water Distribution System Water Distribution System Water Distribution System Water
Turbidity vs Total Manganese Alkalinity vs Total Manganese Apparent Color vs Total Manganese Sodium vs Total Manganese
0.120 0.120 0.120 0.120
2 n = 11
R = 0.4052 n=9 n=6
0.100 0.100 0.100 n=4 0.100
2
R = 0.6000
0.080 0.080 0.080 0.080
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
2
0.060 0.060 R = 0.0039 0.060 0.060
Distribution System Water Distribution System Water Distribution System Water Distribution System Water
Dissolved Oxygen vs Total Manganese Total Organic Carbon vs Total Manganese Orthophosphate vs Total Manganese Calcium vs Total Manganese
0.120 0.120 0.120 0.120
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
0.060 0.060 0.060 0.060
2
R = 0.1039
0.040 0.040 0.040 0.040
Distribution System Water Distribution System Water Distribution System Water Distribution System Water
Conductivity vs Total Manganese Dissolved Organic Carbon vs Total Manganese Sulfate vs Total Manganese Total Dissolved Solids vs Total Manganese
0.120 0.120 0.120 0.120
n=5
n=8 n=1 n=1
0.100 0.100 0.100 0.100
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
2
R = 0.0274
0.060 0.060 0.060 0.060
2
R = 0.0014
0.040 0.040 0.040 0.040
Figure C.3Correlations of distribution system water total Mn with single water quality parameters. Using the detailed survey self reported data
226
227
Total Manganese
0.050 0.22 m Filtered Manganese 0.050
30 kDa Filtered Manganese
Manganese (mg/L)
0.040 0.040
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
8/31/2004 11/9/2004
0.060 0.060
0.050 0.050
Manganese (mg/L)
0.040 0.040
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID :2
U.S. Geographic location : Midwest
Source water : Ground Water
Treatment type : Parallel conventional gravity settling and manganese greensand
Mn Specific Treatment : Aeration and KMnO4 / Greensand
Figure D.1 Results of distribution system seasonal occurrence sampling. Data presented as
mean and of triplicate samples.
228
0.090 0.090
0.060 0.060
0.030 0.030
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
11/18/2004 1/10/2005
0.150 0.150
0.120 0.120
Manganese (mg/L)
0.090 0.090
0.060 0.060
0.030 0.030
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID :7
U.S. Geographic location : South
Source water : Surface Water
Treatment type : Conventional Gravity Settling
Mn Specific Treatment : KMnO4
Figure D.2 Results of distribution system seasonal occurrence sampling. Data presented as
mean and of triplicate samples.
229
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
9/10/2004 12/8/2004
0.050 0.050
0.040 0.040
Manganese (mg/L)
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID :9
U.S. Geographic location : Mid-Atlantic
Source water : Surface Water
Treatment type : Conventional Gravity Settling
Mn Specific Treatment : Induced Oxide Coated Media
Figure D.3 Results of distribution system seasonal occurrence sampling. Data presented as
mean and of triplicate samples.
230
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
11/3/2004 1/4/2005
0.050 0.050
0.040 0.040
Manganese (mg/L)
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID : 21
U.S. Geographic location : Northeast
Source water : Groundwater
Treatment type : Manganese Greensand
Mn Specific Treatment : Greensand
Figure D.4 Results of distribution system seasonal occurrence sampling. Data presented as
mean and of triplicate samples.
231
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
8/27/2004 11/12/2005
0.050 0.050
0.040 0.040
Manganese (mg/L)
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID : 22
U.S. Geographic location : Mid-Atlantic
Source water : Surface water
Treatment type : Advanced clarification with intermediate ozone
Mn Specific Treatment : Induced oxide coated media - auxiliary KMnO4
Figure D.5 Results of distribution system seasonal occurrence sampling. Data presented as
mean and of triplicate samples.
232
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
8/19/2004
0.050
0.040
Manganese (mg/L)
0.030
0.020
0.010
0.000
Entry Near Mid Far
Utility ID : 216
U.S. Geographic location : Northeast
Source water : Surface Water
Treatment type : Disinfection
Mn Specific Treatment : None
Figure D.6 Results of distribution system seasonal occurrence sampling. Data presented as
mean and of triplicate samples.
233
0.200
Manganese (mg/L)
0.150
0.100
0.050
0.000
Entry Near Mid Far
12/20/2004
0.200
0.150
Manganese (mg/L)
0.100
0.050
30 kDa Filtered Manganese
0.22 m Filtered Manganese
Total Manganese
0.000
Entry Near Mid Far
Utility ID : 269
U.S. Geographic location : Northwest
Source water : Groundwater
Treatment type : Disinfection
Mn Specific Treatment : Sequestration
Figure D.7 Results of distribution system seasonal occurrence sampling. Data presented as
mean and of triplicate samples.
234
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
6 27 e2 27
Entry Near Mid Far y2 ay Jun - May
- Ma - M d -
Ent
ry Ne
ar Mi Far
8/26/2004 11/1/2005
0.050 0.050
0.040 0.040
Manganese (mg/L)
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID : 315
U.S. Geographic location : Mid-Atlantic
Source water : Surface Water
Treatment type : Conventional gravity settling
Mn Specific Treatment : Induced oxide coated media on GAC
Figure D.8 Results of distribution system seasonal occurrence sampling. Data presented as
mean and of triplicate samples.
235
0.060 0.060
0.040 0.040
0.020 0.020
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
1/7/2005
0.100
0.080
Manganese (mg/L)
0.060
0.040
0.020
236
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
11/23/2004 12/22/2004
0.050 0.050
0.040 0.040
Manganese (mg/L)
0.030 0.030
0.020 0.020
0.010 0.010
0.000 0.000
Entry Near Mid Far Entry Near Mid Far
Utility ID : 336
U.S. Geographic location : Mid-Atlantic
Source water : Surface Water
Treatment type : Conventional gravity settling
Mn Specific Treatment : Induced oxide coated media on GAC
Figure D.10 Results of distribution system seasonal occurrence sampling. Data presented
as mean and of triplicate samples.
237
Manganese (mg/L)
0.030
0.020
0.010
0.000
Entry Near Mid Far
12/29/2004
0.050
0.040
Manganese (mg/L)
0.030
0.020
0.010
0.000
Entry Near Mid Far
Utility ID : 400
U.S. Geographic location : West
Source water : Surface water
Treatment type : Conventional gravity settling with intermediate ozone
Mn Specific Treatment : KMnO4
Figure D.11 Results of distribution system seasonal occurrence sampling. Data presented
as mean and of triplicate samples.
238
Manganese (mg/L)
0.030
0.020
0.010
0.000
Entry Near Mid Far
2/9/2005
0.050
0.040
Manganese (mg/L)
0.030
0.020
0.010
0.000
Entry Near Mid Far
Utility ID : 401
U.S. Geographic location : West
Source water : Surface water
Treatment type : Advanced clarification with intermediate ozone
Mn Specific Treatment : Reservoir hypolimnic oxygenation system / none
Figure D.12 Results of distribution system seasonal occurrence sampling. Data presented
as mean and of triplicate samples.
239
Table D.1 Utility 2 Winter 2004 distribution system sample (entry, near, mid, and far) metals data
Near 2/26/2004 1 < 0.001 12.9 117 42 465 0.005 0.007 0.006 < 0.001 < 0.001
Near 2/26/2004 2 < 0.001 13.0 117 42 464 < 0.005 0.007 0.007 0.007 < 0.001 < 0.001
Near 2/26/2004 3 < 0.001 13.1 125 45 496 < 0.005 0.009 < 0.005 0.007 < 0.001 < 0.001
Mid 2/26/2004 1 < 0.001 12.7 117 41 462 0.005 < 0.005 0.020 0.006 < 0.001 < 0.001
Mid 2/26/2004 2 < 0.001 13.1 119 42 472 < 0.005 < 0.005 0.007 < 0.001 < 0.001
Mid 2/26/2004 3 < 0.001 13.3 126 45 500 < 0.005 < 0.005 0.006 0.009 < 0.001 < 0.001
Far 2/26/2004 1 < 0.001 12.8 126 45 501 < 0.005 < 0.005 < 0.005 0.007 < 0.001 < 0.001
Far 2/26/2004 2 < 0.001 13.1 117 42 465 0.007 < 0.005 0.007 0.007 < 0.001 < 0.001
Far 2/26/2004 3 < 0.001 13.6 126 45 498 0.008 0.007 0.009 0.008 < 0.001 < 0.001
DI/MQ BLANK 2/26/2004 < 0.001 < 0.05 < 0.662 0.009 0.002
FIELD BLANK 2/26/2004 0.001 < 0.05 < 0.662 < 0.005 0.002
FILTER BLANK 2/26/2004 0.011 < 0.001
PRE-ULTRA FILTER BLANK 2/26/2004 0.006 < 0.001
POST-ULTRA FILTER BLANK 2/26/2004 < 0.006 < 0.001
240
Near 5/20/2004 1 <0.001 13.0 122 42 480 < 0.005 < 0.005 < 0.005 0.036 0.026 0.004
Near 5/20/2004 2 <0.001 12.9 122 42 477 < 0.005 < 0.005 < 0.005 0.033 0.023 0.007
Near 5/20/2004 3 <0.001 12.7 122 42 476 < 0.005 < 0.005 < 0.005 0.033 0.024 0.006
Mid 5/20/2004 1 <0.001 12.2 117 41 461 < 0.005 < 0.005 < 0.005 0.014 0.001 < 0.001
Mid 5/20/2004 2 <0.001 12.4 120 41 471 < 0.005 < 0.005 < 0.005 0.012 0.001 < 0.001
Mid 5/20/2004 3 <0.001 12.5 119 41 467 < 0.005 < 0.005 < 0.005 0.013 0.001 < 0.001
Far 5/20/2004 1 <0.001 11.9 116 40 456 0.009 < 0.005 < 0.005 0.022 < 0.001 < 0.001
Far 5/20/2004 2 <0.001 12.0 117 41 461 0.010 < 0.005 < 0.005 0.024 0.005 < 0.001
Far 5/20/2004 3 <0.001 12.7 126 44 495 0.009 < 0.005 < 0.005 0.024 < 0.001 < 0.001
DI/MQ BLANK 5/20/2004 < 0.001 < 0.05 < 1.66 < 0.005 0.002
FIELD BLANK 5/20/2004 < 0.001 < 0.05 < 1.66 < 0.005 0.002
FILTER BLANK 5/20/2004 <0.006 <0.001
PRE-ULTRA FILTER BLANK 5/20/2004 <0.005 <0.001
POST-ULTRA FILTER BLANK 5/20/2004 <0.005 <0.001
241
Near 8/31/2004 1 <0.001 10.6 116 38 446 < 0.005 < 0.005 < 0.005 0.055 0.038 0.031
Near 8/31/2004 2 <0.001 10.6 113 38 439 < 0.005 < 0.005 < 0.005 0.058 0.036 0.032
Near 8/31/2004 3 <0.001 10.8 115 39 446 < 0.006 < 0.005 < 0.005 0.057 0.037 0.032
Mid 8/31/2004 1 <0.001 11.1 119 40 461 0.013 < 0.005 < 0.005 0.007 0.005
Mid 8/31/2004 2 <0.001 10.8 114 39 445 < 0.005 < 0.005 < 0.005 0.025 0.006 0.006
Mid 8/31/2004 3 <0.001 10.5 112 38 434 < 0.006 < 0.005 < 0.005 0.026 0.006 0.006
Far 8/31/2004 1 <0.001 11.0 117 40 455 0.007 < 0.005 < 0.005 0.011 < 0.001 < 0.001
Far 8/31/2004 2 <0.001 11.0 117 40 458 0.007 < 0.005 < 0.005 0.011 < 0.001 0.003
Far 8/31/2004 3 <0.001 10.8 113 38 442 0.007 < 0.005 < 0.005 0.010 < 0.001 < 0.001
DI/MQ BLANK 8/31/2004 < 0.001 < 0.05 <1 < 0.005 0.002
FIELD BLANK 8/31/2004 < 0.001 < 0.05 <1 < 0.005 0.002
FILTER BLANK 8/31/2004 < 0.005 0.002
PRE-ULTRA FILTER BLANK 8/31/2004 < 0.005 0.002
POST-ULTRA FILTER BLANK 8/31/2004 < 0.005 < 0.001
242
Near 11/9/2004 1 < 0.001 15.3 137 44 521 0.142 < 0.005 < 0.005 0.004 < 0.001 < 0.001
Near 11/9/2004 2 < 0.001 14.3 137 40 506 < 0.005 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Near 11/9/2004 3 < 0.001 15.9 135 41 506 < 0.006 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Mid 11/9/2004 1 < 0.001 16.2 141 44 534 < 0.005 < 0.005 < 0.005 0.004 < 0.001 0.001
Mid 11/9/2004 2 < 0.001 16.5 143 46 543 < 0.005 < 0.005 < 0.005 0.007 < 0.001 < 0.001
Mid 11/9/2004 3 < 0.001 15.5 141 43 529 < 0.006 < 0.005 < 0.005 0.007 < 0.001 < 0.001
Far 11/9/2004 1 < 0.001 15.3 139 44 526 < 0.005 < 0.005 < 0.005 0.002 < 0.001 < 0.001
Far 11/9/2004 2 < 0.001 15.4 139 43 525 < 0.005 < 0.005 < 0.005 0.002 < 0.001 < 0.001
Far 11/9/2004 3 < 0.001 15.5 139 44 527 < 0.006 < 0.005 < 0.005 0.002 < 0.001 < 0.001
DI/MQ BLANK 11/9/2004 < 0.001 < 0.05 <1 < 0.005 0.002
FIELD BLANK 11/9/2004 < 0.001 < 0.05 <1 < 0.005 0.002
FILTER BLANK 11/9/2004 < 0.005 0.001
PRE-ULTRA FILTER BLANK 11/9/2004 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 11/9/2004 < 0.006 0.001
243
244
Near 5/26/2004 1 < 0.001 4 12.2 17 < 0.005 < 0.005 0.005 0.027 0.007 0.004
Near 5/26/2004 2 < 0.001 4 12.0 16 0.006 < 0.005 < 0.005 0.034 0.007 0.003
Near 5/26/2004 3 < 0.001 4 11.7 16 < 0.005 < 0.005 0.010 0.028 0.006 0.003
Mid 5/26/2004 1 < 0.001 13 9.4 37 0.015 < 0.006 < 0.005 0.034 0.002 0.002
Mid 5/26/2004 2 < 0.001 13 9.5 36 0.008 < 0.005 < 0.005 0.020 0.001 0.001
Mid 5/26/2004 3 < 0.001 12 9.3 35 0.006 < 0.005 < 0.005 0.021 0.001 0.001
Far 5/26/2004 1 < 0.001 8 10.1 24 0.018 < 0.005 0.006 0.022 < 0.001 0.002
Far 5/26/2004 2 < 0.001 8 9.8 24 0.017 < 0.005 < 0.005 0.022 < 0.001 < 0.001
Far 5/26/2004 3 < 0.001 8 9.7 24 0.018 < 0.005 < 0.005 0.023 < 0.001 0.002
DI/MQ BLANK 5/26/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 5/26/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 5/26/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 5/26/2004 <0.005 <0.001
POST-ULTRA FILTER BLANK 5/26/2004 <0.005 <0.001
245
Near 11/18/2004 1 < 0.005 4 12.4 17 < 0.005 < 0.005 0.005 0.020 0.008 0.007
Near 11/18/2004 2 < 0.005 4 11.6 16 < 0.005 < 0.005 < 0.006 0.020 0.007 0.009
Near 11/18/2004 3 < 0.005 4 11.9 16 < 0.005 < 0.005 < 0.005 0.020 0.007 0.007
Mid 11/18/2004 1 < 0.006 26 5.3 71 0.010 < 0.005 0.011 0.016 0.002 0.002
Mid 11/18/2004 2 < 0.005 25 4.7 69 0.016 < 0.006 < 0.005 0.016 0.002 0.002
Mid 11/18/2004 3 < 0.005 25 5.7 70 0.007 < 0.005 < 0.005 0.016 0.002 0.003
Far 11/18/2004 1 < 0.005 8 13.3 26 0.012 < 0.005 < 0.005 0.013 0.007 0.008
Far 11/18/2004 2 < 0.005 8 12.3 26 0.012 < 0.005 < 0.005 0.014 0.007 0.007
Far 11/18/2004 3 < 0.005 8 0.015 0.008 0.015 0.013 0.007 0.007
DI/MQ BLANK 11/18/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 11/18/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 11/18/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 11/18/2004 0.006 < 0.001
POST-ULTRA FILTER BLANK 11/18/2004 < 0.006 < 0.001
246
Near 1/10/2005 1 < 0.001 3 10.3 10 < 0.005 < 0.005 < 0.005 0.016 0.005 0.005
Near 1/10/2005 2 < 0.001 3 10.5 10 0.006 < 0.005 < 0.005 0.016 0.005 0.002
Near 1/10/2005 3 < 0.001 3 9.8 10 < 0.006 < 0.005 < 0.005 0.016 0.006 0.005
Mid 1/10/2005 1 < 0.001 28 2.8 74 0.016 < 0.005 < 0.005 0.049 0.023 0.019
Mid 1/10/2005 2 < 0.001 26 2.5 70 0.014 < 0.005 < 0.005 0.041 0.021 0.020
Mid 1/10/2005 3 < 0.001 26 2.3 67 0.020 < 0.005 < 0.005 0.047 0.021 0.019
Far 1/10/2005 1 < 0.001 6 9.8 17 0.136 0.099 < 0.005 0.011 0.005 0.004
Far 1/10/2005 2 < 0.001 6 9.7 18 0.138 0.087 < 0.005 0.012 0.005 0.004
Far 1/10/2005 3 < 0.001 6 9.8 17 0.140 0.040 < 0.005 0.011 0.004 0.005
DI/MQ BLANK 1/10/2005 < 0.001 0.1 <1 < 0.005 < 0.001
FIELD BLANK 1/10/2005 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 1/10/2005 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 1/10/2005 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 1/10/2005 < 0.006 < 0.001
247
Mid 3/9/2004 1 <0.001 30 19.3 109 0.014 0.001 < 0.001 0.001
Mid 3/9/2004 2 <0.001 28 19.0 106 0.010 0.001 < 0.001 < 0.001
Mid 3/9/2004 3 <0.001 30 19.5 110 0.001 < 0.001 < 0.001
Far 3/9/2004 1 <0.001 31 19.2 109 0.009 0.001 < 0.001 0.003
Far 3/9/2004 2 <0.001 31 19.2 109 0.009 0.001 < 0.001 < 0.001
Far 3/9/2004 3 <0.001 31 NR 110 0.001 < 0.001 < 0.001
DI/MQ BLANK 3/9/2004 <0.001 < 0.05 <1 < 0.006 <0.001
FIELD BLANK 3/9/2004 <0.001 < 0.05 <1 < 0.005 <0.001
FILTER BLANK 3/9/2004 <0.001
PRE-ULTRA FILTER BLANK 3/9/2004 < 0.005 <0.001
POST-ULTRA FILTER BLANK 3/9/2004 < 0.005 <0.001
248
Near 6/16/2004 1 <0.001 26 13.2 88 0.012 0.006 < 0.005 0.002 0.001 0.001
Near 6/16/2004 2 <0.001 25 13.2 86 0.011 < 0.005 < 0.005 0.002 0.001 0.001
Near 6/16/2004 3 < 0.001 25 12.9 85 0.010 < 0.005 < 0.005 0.001 0.001 0.001
Mid 6/16/2004 1 <0.001 27 13.5 90 0.007 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Mid 6/16/2004 2 <0.001 24 12.6 83 0.006 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Mid 6/16/2004 3 <0.001 27 13.5 91 0.006 < 0.005 < 0.005 < 0.001 < 0.001 0.001
Far 6/16/2004 1 <0.001 25 13.0 85 0.005 < 0.005 < 0.006 < 0.001 < 0.001 < 0.001
Far 6/16/2004 2 <0.001 26 13.0 88 0.006 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Far 6/16/2004 3 <0.001 27 13.4 90 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
DI/MQ BLANK 6/16/2004 <0.001 < 0.05 < 1.66 < 0.005 <0.001
FIELD BLANK 6/16/2004 <0.001 < 0.05 < 1.66 < 0.006 <0.001
FILTER BLANK 6/16/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 6/16/2004 < 0.005 <0.001
POST-ULTRA FILTER BLANK 6/16/2004 < 0.005 <0.001
249
Near 9/10/2004 1 <0.001 30 11.0 94 0.012 0.009 0.006 0.002 0.002 0.001
Near 9/10/2004 2 <0.001 29 10.8 91 0.013 < 0.005 < 0.005 0.002 0.002 0.002
Near 9/10/2004 3 < 0.001 30 11.3 94 0.015 0.010 < 0.005 0.002 0.002 0.002
Mid 9/10/2004 1 <0.001 29 11.0 93 0.006 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Mid 9/10/2004 2 <0.001 30 10.8 93 0.006 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Mid 9/10/2004 3 <0.001 30 11.1 94 0.006 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Far 9/10/2004 1 <0.001 30 10.8 95 0.006 0.009 < 0.005 0.001 < 0.001 < 0.001
Far 9/10/2004 2 <0.001 30 11.0 94 < 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Far 9/10/2004 3 <0.001 31 11.0 96 < 0.006 < 0.005 < 0.005 0.001 < 0.001 < 0.001
DI/MQ BLANK 9/10/2004 <0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 9/10/2004 <0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 9/10/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 9/10/2004 < 0.005 <0.001
POST-ULTRA FILTER BLANK 9/10/2004 < 0.005 <0.001
250
Near 12/8/2004 1 < 0.006 25 7.75 77 0.011 0.006 0.008 < 0.001 < 0.001 0.001
Near 12/8/2004 2 < 0.005 25 7.77 76 0.010 0.007 0.007 0.001 0.001 0.001
Near 12/8/2004 3 < 0.005 25 7.67 76 0.010 0.007 0.005 0.001 0.001 0.001
Mid 12/8/2004 1 < 0.005 25 7.46 76 0.010 0.007 < 0.005 0.001 < 0.001 < 0.001
Mid 12/8/2004 2 < 0.005 25 7.61 76 0.011 0.007 0.005 0.001 < 0.001 < 0.001
Mid 12/8/2004 3 < 0.005 25 7.63 76 0.010 0.006 0.007 0.001 < 0.001 < 0.001
Far 12/8/2004 1 < 0.005 26 8.99 83 0.010 < 0.005 0.006 0.001 < 0.001 0.001
Far 12/8/2004 2 < 0.006 26 9.26 83 0.009 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Far 12/8/2004 3 < 0.005 27 8.75 84 0.010 < 0.005 < 0.005 0.001 < 0.001 < 0.001
DI/MQ BLANK 12/8/2004 < 0.005 < 0.05 <1 0.014 < 0.001
FIELD BLANK 12/8/2004 < 0.005 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 12/8/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 12/8/2004 < 0.005 0.001
POST-ULTRA FILTER BLANK 12/8/2004 < 0.006 < 0.001
251
Near 4/29/2004 1 0.003 15 17.4 44 < 0.005 0.005 < 0.005 0.007 0.001 0.001
Near 4/29/2004 2 0.003 19 17.1 55 0.005 < 0.005 < 0.005 0.009 0.001 0.001
Near 4/29/2004 3 0.003 19 17.8 54 < 0.006 < 0.005 < 0.005 0.009 0.001 < 0.001
Mid 4/29/2004 1 0.004 18 17.8 53 < 0.005 0.006 < 0.005 0.006 0.001 < 0.001
Mid 4/29/2004 2 0.004 20 17.4 57 < 0.005 < 0.005 < 0.005 0.007 0.001 < 0.001
Mid 4/29/2004 3 0.004 18 17.5 53 < 0.005 0.006 < 0.005 0.006 0.001 0.001
Far 4/29/2004 1 0.004 18 18.4 53 0.008 0.009 < 0.006 0.007 < 0.001 < 0.001
Far 4/29/2004 2 0.004 18 18.0 53 0.008 < 0.005 < 0.005 0.007 < 0.001 < 0.001
Far 4/29/2004 3 0.004 18 17.8 53 0.008 < 0.005 < 0.005 0.008 < 0.001 < 0.001
252
Near 7/15/2004 1 0.003 18 17.4 52 < 0.005 < 0.005 < 0.005 0.010 0.004 0.001
Near 7/15/2004 2 0.003 18 16.7 51 < 0.005 < 0.005 < 0.005 0.011 0.004 0.001
Near 7/15/2004 3 0.003 18 17.3 52 < 0.006 < 0.005 < 0.005 0.011 0.004 0.002
Mid 7/15/2004 1 0.004 19 16.9 54 0.017 0.013 < 0.005 0.005 0.002 0.001
Mid 7/15/2004 2 0.003 18 16.9 52 0.018 0.013 < 0.005 0.005 0.002 0.001
Mid 7/15/2004 3 0.003 18 17.0 52 0.019 0.014 < 0.005 0.005 0.002 0.001
Far 7/15/2004 1 0.004 18 16.7 53 < 0.005 < 0.005 < 0.005 0.005 < 0.001 0.002
Far 7/15/2004 2 0.003 18 16.9 53 < 0.005 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Far 7/15/2004 3 0.003 18 16.7 52 < 0.006 < 0.005 < 0.005 0.005 < 0.001 < 0.001
DI/MQ BLANK 7/15/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 7/15/2004 < 0.001 0.1 <1 < 0.005 < 0.001
FILTER BLANK 7/15/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 7/15/2004 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 7/15/2004 < 0.005 < 0.001
253
Near 11/3/2004 1 0.003 20 17.9 57 < 0.005 < 0.005 < 0.005 0.010 0.004 0.003
Near 11/3/2004 2 0.003 20 18.3 58 < 0.005 < 0.005 < 0.005 0.010 0.005 0.003
Near 11/3/2004 3 0.003 20 18.4 57 < 0.006 < 0.005 < 0.005 0.010 0.005 0.003
Mid 11/3/2004 1 0.003 20 17.9 57 0.029 0.017 0.011 0.007 0.002 0.002
Mid 11/3/2004 2 0.003 20 18.0 58 0.029 0.016 0.008 0.007 0.002 0.002
Mid 11/3/2004 3 0.004 20 17.7 57 0.029 0.016 0.009 0.006 0.002 0.002
Far 11/3/2004 1 0.003 20 18.3 58 0.008 < 0.005 < 0.005 0.007 0.002 0.002
Far 11/3/2004 2 0.003 20 18.6 58 0.008 < 0.005 < 0.005 0.007 0.002 0.002
Far 11/3/2004 3 0.003 20 17.8 57 0.008 0.006 0.011 0.007 0.002 0.002
DI/MQ BLANK 11/3/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 11/3/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 11/3/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 11/3/2004 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 11/3/2004 < 0.005 < 0.001
254
Near 1/4/2005 1 0.004 19 19.9 56 < 0.005 < 0.005 < 0.005 0.002 0.002 0.001
Near 1/4/2005 2 0.004 19 19.8 55 < 0.005 0.008 < 0.005 0.002 0.002 0.001
Near 1/4/2005 3 0.004 19 19.8 56 < 0.006 < 0.005 < 0.005 0.002 0.002 0.001
Mid 1/4/2005 1 0.003 19 19.7 55 0.008 0.007 < 0.005 0.001 0.009 0.001
Mid 1/4/2005 2 0.003 19 19.1 55 0.007 0.007 < 0.005 0.001 0.001 0.001
Mid 1/4/2005 3 0.003 19 19.2 55 0.008 0.007 < 0.005 0.001 0.001 0.001
Far 1/4/2005 1 0.003 19 19.6 55 0.006 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Far 1/4/2005 2 0.003 19 19.1 56 < 0.005 0.006 < 0.005 < 0.001 0.002 < 0.001
Far 1/4/2005 3 0.004 20 19.0 57 < 0.006 < 0.005 < 0.005 < 0.001 < 0.001 0.001
DI/MQ BLANK 1/4/2005 < 0.001 < 0.25 <1 < 0.005 < 0.001
FIELD BLANK 1/4/2005 < 0.001 < 0.25 <1 < 0.005 < 0.001
FILTER BLANK 1/4/2005 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 1/4/2005 0.007 0.001
POST-ULTRA FILTER BLANK 1/4/2005 < 0.005 < 0.001
255
256
Near 4/20/2004 1 <0.001 29 9.60 81 0.012 < 0.005 < 0.006 0.005 0.004 0.004
Near 4/20/2004 2 <0.001 29 9.58 80 0.010 < 0.005 < 0.005 0.005 0.004 0.004
Near 4/20/2004 3 <0.001 29 9.29 79 0.009 < 0.005 < 0.005 0.005 0.004 0.004
Mid 4/20/2004 1 <0.001 29 9.40 80 0.010 < 0.005 < 0.005 0.004 0.003 0.003
Mid 4/20/2004 2 <0.001 29 9.90 80 0.009 < 0.005 < 0.005 0.004 0.003 0.003
Mid 4/20/2004 3 <0.001 30 9.60 81 0.007 < 0.006 < 0.005 0.004 0.003 0.003
Far 4/20/2004 1 <0.001 34 9.69 91 0.014 < 0.005 < 0.005 0.003 0.002 0.002
Far 4/20/2004 2 <0.001 33 9.30 89 0.015 0.005 < 0.005 0.003 0.002 0.002
Far 4/20/2004 3 <0.001 33 9.42 90 0.015 < 0.005 < 0.005 0.003 0.002 0.002
257
Near 8/27/2004 1 < 0.001 32 3.79 86 0.009 < 0.005 < 0.005 0.015 0.004 0.004
Near 8/27/2004 2 < 0.001 32 3.62 85 0.009 < 0.005 < 0.005 0.015 0.004 0.004
Near 8/27/2004 3 < 0.001 32 3.52 85 0.009 < 0.005 < 0.005 0.015 0.004 0.004
Mid 8/27/2004 1 < 0.001 31 3.67 82 0.005 < 0.005 < 0.005 0.008 0.003 0.003
Mid 8/27/2004 2 < 0.001 31 3.52 82 0.006 < 0.005 0.005 0.009 0.003 0.003
Mid 8/27/2004 3 < 0.001 31 3.64 82 < 0.006 < 0.005 0.005 0.009 0.003 0.003
Far 8/27/2004 1 < 0.001 32 3.67 83 0.015 0.006 < 0.005 0.005 0.003 0.003
Far 8/27/2004 2 < 0.001 32 3.70 83 0.013 < 0.005 < 0.005 0.005 0.003 0.003
Far 8/27/2004 3 < 0.001 32 3.71 84 0.013 < 0.005 0.006 0.005 0.003 0.003
DI/MQ BLANK 8/27/2004 < 0.001 <1 <2 < 0.005 < 0.001
FIELD BLANK 8/27/2004 < 0.001 <1 <2 < 0.005 < 0.001
FILTER BLANK 8/27/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 8/27/2004 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 8/27/2004 < 0.005 < 0.001
258
Near 11/12/2004 1 < 0.001 33.6 5.80 91 0.016 < 0.005 < 0.005 0.018 0.009 0.008
Near 11/12/2004 2 < 0.001 33.3 5.70 90 0.006 < 0.005 < 0.005 0.018 0.009 0.009
Near 11/12/2004 3 < 0.001 33.8 5.77 91 0.014 < 0.005 < 0.005 0.019 0.009 0.009
Mid 11/12/2004 1 < 0.001 32.7 5.69 88 0.010 < 0.005 < 0.005 0.013 0.005 0.005
Mid 11/12/2004 2 < 0.001 36.3 7.07 99 0.014 < 0.005 < 0.005 0.013 0.006 0.005
Mid 11/12/2004 3 < 0.001 33.0 5.74 89 < 0.006 < 0.005 < 0.005 0.013 0.006 0.005
Far 11/12/2004 1 < 0.001 33.3 5.54 89 0.013 < 0.005 < 0.005 0.008 0.005 0.005
Far 11/12/2004 2 < 0.001 33.9 5.62 91 0.015 < 0.005 < 0.005 0.008 0.005 0.005
Far 11/12/2004 3 < 0.001 33.8 5.67 91 0.014 < 0.005 < 0.005 0.008 0.005 0.005
DI/MQ BLANK 11/12/2004 < 0.001 < 0.05 <1 0.010 < 0.001
FIELD BLANK 11/12/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 11/12/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 11/12/2004 < 0.005 0.001
POST-ULTRA FILTER BLANK 11/12/2004 < 0.005 < 0.001
259
Near 2/11/2004 1 <0.001 23 > 30.0 89 0.075 0.011 0.007 0.026 0.009 0.009
Near 2/11/2004 2 <0.001 21 28.1 82 0.075 0.011 0.007 0.022 0.008 0.009
Near 2/11/2004 3 <0.001 21 > 25.0 82 0.073 0.009 0.008 0.020 0.009 0.008
Mid 2/11/2004 1 <0.001 21 27.5 83 0.082 0.012 0.007 0.023 0.008 0.008
Mid 2/11/2004 2 <0.001 21 >25.0 82 0.074 0.013 0.007 0.020 0.007 0.008
Mid 2/11/2004 3 <0.001 21 >25.0 81 0.077 0.012 0.008 0.021 0.008 0.008
Far 2/11/2004 1 <0.001 12 16.2 46 0.076 0.017 0.012 0.012 0.003 0.003
Far 2/11/2004 2 <0.001 11 15.0 41 0.079 0.015 0.012 0.011 0.003 0.003
Far 2/11/2004 3 <0.001 13 17.3 50 0.081 0.017 0.028 0.014 0.003 0.003
260
Near 5/27/2004 1 <0.001 26 35.6 101 0.038 < 0.005 < 0.005 0.020 0.005 0.005
Near 5/27/2004 2 <0.001 26 34.9 98 0.035 < 0.005 < 0.005 0.021 0.005 0.005
Near 5/27/2004 3 <0.001 25 33.6 98 0.033 < 0.005 < 0.005 0.022 0.005 0.005
Mid 5/27/2004 1 <0.001 26 34.2 99 0.033 < 0.005 < 0.005 0.023 0.005 0.005
Mid 5/27/2004 2 <0.001 26 34.5 98 0.033 < 0.005 < 0.005 0.022 0.005 0.005
Mid 5/27/2004 3 <0.001 25 34.5 97 0.030 < 0.005 < 0.005 0.022 0.005 0.005
Far 5/27/2004 1 <0.001 23 30.9 87 0.062 0.010 < 0.005 0.020 0.007 0.007
Far 5/27/2004 2 <0.001 23 31.2 88 0.064 0.010 < 0.005 0.019 0.008 0.008
Far 5/27/2004 3 <0.001 24 32.2 91 0.072 0.010 < 0.005 0.020 0.008 0.008
DI/MQ BLANK 5/27/2004 <0.001 < 0.05 < 1.66 < 0.005 <0.001
FIELD BLANK 5/27/2004 <0.001 0.06 < 1.66 < 0.005 <0.001
FILTER BLANK 5/27/2004 0.005 <0.001
PRE-ULTRA FILTER BLANK 5/27/2004 < 0.005 <0.001
POST-ULTRA FILTER BLANK 5/27/2004 < 0.006 <0.001
261
Near 8/19/2004 1 <0.001 24.0 34.7 94 0.032 < 0.005 < 0.005 0.043 0.009 0.009
Near 8/19/2004 2 <0.001 24.0 34.5 93 0.032 < 0.005 < 0.005 0.044 0.009 0.009
Near 8/19/2004 3 <0.001 24.0 34.3 95 0.032 < 0.005 < 0.005 0.044 0.009 0.009
Mid 8/19/2004 1 <0.001 24.0 34.6 95 0.037 < 0.005 < 0.005 0.041 0.009 0.008
Mid 8/19/2004 2 <0.001 24.0 34.3 94 0.037 0.008 < 0.005 0.041 0.009 0.008
Mid 8/19/2004 3 <0.001 24.0 34.4 94 0.037 < 0.005 < 0.005 0.042 0.009 0.009
Far 8/19/2004 1 <0.001 24.0 34.4 95 0.066 0.012 < 0.005 0.030 0.004 0.004
Far 8/19/2004 2 <0.001 24.0 34.0 94 0.064 0.007 < 0.005 0.027 0.004 0.004
Far 8/19/2004 3 <0.001 24.0 34.2 94 0.063 0.006 < 0.005 0.027 0.004 0.004
DI/MQ BLANK 8/19/2004 <0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 8/19/2004 <0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 8/19/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 8/20/2004 < 0.005 <0.001
POST-ULTRA FILTER BLANK 8/20/2004 < 0.006 <0.001
262
Near 7/23/2004 1 < 0.001 30 31.6 87 0.042 0.021 < 0.005 0.211 0.096 0.039
Near 7/23/2004 2 < 0.001 30 33.0 87 0.036 0.021 < 0.005 0.200 0.103 0.024
Near 7/23/2004 3 < 0.001 30 32.2 88 0.029 0.019 < 0.005 0.161 0.091 0.041
Far 7/23/2004 1 < 0.001 30 33.1 86 0.029 0.013 < 0.005 0.093 0.067 0.038
Far 7/23/2004 2 < 0.001 30 31.5 87 0.029 0.013 < 0.005 0.094 0.068 0.038
Far 7/23/2004 3 < 0.001 30 31.7 86 0.029 0.007 < 0.005 0.092 0.053 0.042
DI/MQ BLANK 7/22/2004 < 0.001 0.3 <1 < 0.005 0.002
FIELD BLANK 7/22/2004 < 0.001 0.4 <1 < 0.005 0.002
FILTER BLANK 7/22/2004 < 0.005 0.002
PRE-ULTRA FILTER BLANK 7/23/2004 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 7/23/2004 < 0.005 0.005
263
Near 12/20/2004 1 < 0.001 30 32.9 88 0.020 0.018 0.019 0.088 0.089 0.080
Near 12/20/2004 2 < 0.001 30 32.4 88 0.019 0.018 0.014 0.084 0.084 0.080
Near 12/20/2004 3 < 0.001 30 32.7 89 0.020 0.020 0.015 0.087 0.092 0.085
Far 12/20/2004 1 < 0.001 30 32.7 89 0.019 0.020 0.018 0.094 0.096 0.094
Far 12/20/2004 2 < 0.001 30 32.2 88 0.027 0.018 0.023 0.089 0.096 0.091
Far 12/20/2004 3 < 0.001 30 32.1 88 0.024 0.019 0.020 0.090 0.097 0.090
DI/MQ BLANK 12/20/2004 < 0.001 < 0.25 <1 < 0.005 0.002
FIELD BLANK 12/20/2004 < 0.001 < 0.25 <1 < 0.005 0.002
FILTER BLANK 12/20/2004 < 0.005 0.002
PRE-ULTRA FILTER BLANK
POST-ULTRA FILTER BLANK
264
Near 2/11/2004 1 <0.001 23 >25 110 0.014 0.023 0.022 < 0.001 0.001 0.003
Near 2/11/2004 2 <0.001 28 >25 118 0.015 0.024 0.038 < 0.001 < 0.001 0.003
Near 2/11/2004 3 <0.001 29 >25 121 0.046 0.025 0.045 < 0.001 < 0.001 < 0.001
Mid 2/11/2004 1 <0.001 26 >25 100 0.034 0.014 0.021 0.004 < 0.001 < 0.001
Mid 2/11/2004 2 <0.001 23 >25 100 0.036 0.016 0.021 0.004 < 0.001 < 0.001
Mid 2/11/2004 3 <0.001 28 >25 103 0.040 0.016 0.027 0.005 < 0.001 < 0.001
Far 2/11/2004 1 <0.001 31 >25 87 0.049 0.020 0.022 0.005 0.004 0.004
Far 2/11/2004 2 <0.001 27 >25 90 0.050 0.020 0.026 0.005 0.005 0.004
Far 2/11/2004 3 <0.001 25 >25 93 0.055 0.023 0.029 0.007 0.007 0.006
DI/MQ BLANK 2/11/2004 <0.001 < 0.05 <1 < 0.01 <0.005
FIELD BLANK 2/11/2004 <0.001 < 0.05 <1 < 0.01 <0.005
FILTER BLANK 2/11/2004 < 0.01 <0.001
PRE-ULTRA FILTER BLANK 2/12/2004 < 0.01 <0.001
POST-ULTRA FILTER BLANK 2/12/2004
265
Near 5/27/2004 1 < 0.001 34 21.8 122 0.010 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Near 5/27/2004 2 < 0.001 33 20.2 110 0.010 < 0.005 < 0.005 0.002 < 0.001 < 0.001
Near 5/27/2004 3 < 0.001 34 21.0 117 0.009 < 0.005 < 0.005 0.002 < 0.001 < 0.001
Mid 6/2/2004 1 < 0.001 23 27.7 84 0.016 < 0.005 < 0.006 0.012 < 0.001 < 0.001
Mid 6/2/2004 2 < 0.001 23 28.0 83 0.013 < 0.005 < 0.005 0.010 < 0.001 < 0.001
Mid 6/2/2004 3 < 0.001 24 27.7 84 0.014 < 0.005 < 0.005 0.011 < 0.001 < 0.001
Far 5/27/2004 1 < 0.001 33 24.0 120 0.033 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Far 5/27/2004 2 < 0.001 34 25.9 118 0.033 < 0.005 < 0.006 0.005 < 0.001 < 0.001
Far 5/27/2004 3 < 0.001 35 24.7 122 0.031 < 0.005 < 0.005 0.006 < 0.001 < 0.001
DI/MQ BLANK 5/26/2004 < 0.001 < 0.05 < 1.66 < 0.005 < 0.001
FIELD BLANK 5/26/2004 < 0.001 0.07 < 1.66 < 0.005 < 0.001
FILTER BLANK 5/26/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 5/26/2004 < 0.006 < 0.001
POST-ULTRA FILTER BLANK 5/26/2004 < 0.005 < 0.001
Episode 5/27/2004 1 < 0.001 35 19.80 112 1.208 < 0.005 < 0.005 0.121 < 0.001 < 0.001
Episode 5/27/2004 2 < 0.001 34 21.10 127 1.151 < 0.005 < 0.006 0.089 < 0.001 < 0.001
Episode 5/27/2004 3 < 0.001 37 20.90 121 1.066 < 0.005 < 0.005 0.165 < 0.001 < 0.001
266
Near 8/26/2004 1 < 0.001 34 38.4 122 0.035 < 0.005 < 0.005 0.014 < 0.001 < 0.001
Near 8/26/2004 2 < 0.001 34 39.1 125 0.035 < 0.005 < 0.005 0.014 < 0.001 < 0.001
Near 8/26/2004 3 < 0.001 34 39.1 125 0.037 < 0.005 < 0.005 0.014 < 0.001 < 0.001
Mid 8/26/2004 1 < 0.001 32 39.7 117 0.018 < 0.005 < 0.005 0.007 < 0.001 < 0.001
Mid 8/26/2004 2 < 0.001 31 38.8 115 0.019 < 0.005 < 0.005 0.008 < 0.001 < 0.001
Mid 8/26/2004 3 < 0.001 32 38.8 117 0.020 < 0.005 < 0.005 0.007 < 0.001 < 0.001
Far 8/26/2004 1 < 0.001 33 38.6 119 0.118 < 0.005 0.006 0.004 < 0.001 < 0.001
Far 8/26/2004 2 < 0.001 33 38.5 117 0.127 < 0.005 < 0.005 0.004 < 0.001 < 0.001
Far 8/26/2004 3 < 0.001 34 39.6 121 0.141 < 0.005 < 0.005 0.004 < 0.001 < 0.001
DI/MQ BLANK 8/26/2004 < 0.001 < 0.05 <1 0.232 < 0.001
FIELD BLANK 8/26/2004 < 0.001 < 0.05 <1 0.018 < 0.001
FILTER BLANK 8/26/2004 0.024 <0.001
PRE-ULTRA FILTER BLANK 8/26/2004 <0.005 <0.001
POST-ULTRA FILTER BLANK 8/26/2004 <0.006 <0.001
267
Near 11/1/2004 1 < 0.001 33 34.5 125 0.010 < 0.005 < 0.005 0.002 < 0.001 0.002
Near 11/1/2004 2 < 0.001 33 35.6 126 0.010 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Near 11/1/2004 3 < 0.001 33 34.6 126 0.011 < 0.005 0.019 0.001 < 0.001 < 0.001
Mid 11/1/2004 1 < 0.001 31 36.0 119 0.018 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Mid 11/1/2004 2 < 0.001 31 36.4 117 0.018 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Mid 11/1/2004 3 < 0.001 35 35.3 132 0.017 < 0.005 0.008 0.001 < 0.001 < 0.001
Far 11/1/2004 1 < 0.001 32 34.7 120 0.163 0.005 < 0.005 0.002 < 0.001 < 0.001
Far 11/1/2004 2 < 0.001 32 35.5 121 0.178 < 0.005 < 0.005 0.002 < 0.001 < 0.001
Far 11/1/2004 3 < 0.001 32 35.4 120 0.178 < 0.005 < 0.005 0.002 < 0.001 < 0.001
DI/MQ BLANK 11/1/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 11/1/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 11/1/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 11/1/2004 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 11/1/2004 < 0.006 < 0.001
268
Mid 8/24/2004 1 0.010 41 10.3 125 0.038 < 0.005 < 0.005 0.063 0.049 0.049
Mid 8/24/2004 2 0.011 41 10.2 127 0.033 < 0.005 < 0.005 0.062 0.050 0.050
Mid 8/24/2004 3 0.011 41 10.5 126 0.033 < 0.005 < 0.005 0.062 0.051 0.045
Far 8/24/2004 1 0.013 42 10.8 128 0.040 < 0.005 < 0.005 0.075 0.060 0.055
Far 8/24/2004 2 0.013 42 10.7 126 0.039 < 0.005 0.014 0.075 0.060 0.059
Far 8/24/2004 3 0.013 42 10.9 127 0.037 < 0.005 0.021 0.072 0.061 0.057
DI/MQ BLANK 8/24/2004 < 0.005 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 8/24/2004 < 0.005 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 8/24/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 8/24/2004 <0.005 <0.001
POST-ULTRA FILTER BLANK 8/24/2004 <0.005 <0.001
269
Mid 10/21/2004 1 0.013 44 48.3 136 0.037 0.026 < 0.005 0.060 0.052 0.029
Mid 10/21/2004 2 0.013 43 46.8 134 0.038 0.029 < 0.005 0.059 0.055 0.052
Mid 10/21/2004 3 0.013 43 48.3 134 0.037 0.026 < 0.005 0.059 0.047 0.052
Far 10/21/2004 1 0.012 48 43.7 149 0.030 < 0.005 < 0.005 0.060 0.048 0.045
Far 10/21/2004 2 0.011 47 43.8 146 0.029 < 0.005 < 0.005 0.060 0.047 0.044
Far 10/21/2004 3 0.012 47 42.0 147 0.024 < 0.005 < 0.005 0.061 0.047 0.044
DI/MQ BLANK 10/21/2004 < 0.005 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 10/21/2004 < 0.005 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 10/21/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 10/21/2004 <0.005 <0.001
POST-ULTRA FILTER BLANK 10/21/2004 <0.005 <0.001
270
Mid 1/7/2005 1 0.014 46 51.8 141 0.035 * < 0.005 0.066 * 0.056
Mid 1/7/2005 2 0.014 46 53.5 139 0.039 0.033 * 0.062 0.064 *
Mid 1/7/2005 3 0.014 45 53.4 137 0.033 * < 0.005 0.067 * 0.057
Far 1/7/2005 1 0.014 46 54.8 142 0.037 0.026 0.010 0.067 0.062 0.051
Far 1/7/2005 2 0.014 45 52.6 140 0.037 * * 0.066 * *
Far 1/7/2005 3 0.014 45 52.4 140 0.040 * < 0.005 0.065 * 0.054
DI/MQ BLANK 1/7/2005 < 0.005 <1 < 10 < 0.005 < 0.001
FIELD BLANK
FILTER BLANK 1/7/2005 < 0.006 <0.001
PRE-ULTRA FILTER BLANK 1/7/2005 <0.005 <0.001
POST-ULTRA FILTER BLANK 1/7/2005 <0.005 <0.001
271
Near 6/16/2004 1 <0.001 17 10.2 59 0.018 < 0.005 < 0.005 0.010 < 0.001 < 0.001
Near 6/16/2004 2 <0.001 16 10.6 58 0.016 < 0.005 < 0.005 0.009 < 0.001 < 0.001
Near 6/16/2004 3 <0.001 18 10.0 62 0.016 < 0.005 < 0.005 0.010 < 0.001 < 0.001
Mid 6/16/2004 1 <0.001 16 10.0 57 < 0.005 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Mid 6/16/2004 2 <0.001 16 10.2 58 < 0.005 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Mid 6/16/2004 3 <0.001 16 10.0 58 < 0.006 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Far 6/16/2004 1 <0.001 25 11.6 86 0.007 < 0.005 < 0.005 0.004 < 0.001 < 0.001
Far 6/16/2004 2 <0.001 25 11.4 87 0.008 < 0.005 < 0.005 0.004 < 0.001 < 0.001
Far 6/16/2004 3 <0.001 25 12.6 86 0.008 < 0.005 < 0.005 0.003 < 0.001 < 0.001
DI/MQ BLANK 6/16/2004 < 0.001 < 0.05 < 1.66 < 0.005 < 0.001
FIELD BLANK 6/16/2004 < 0.001 < 0.05 < 1.66 < 0.005 < 0.001
FILTER BLANK 6/16/2004 < 0.006 <0.001
PRE-ULTRA FILTER BLANK 6/16/2004 <0.005 <0.001
POST-ULTRA FILTER BLANK
272
Near 8/5/2004 1 < 0.001 18 10.6 62 < 0.005 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Near 8/5/2004 2 < 0.001 17 10.9 61 < 0.005 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Near 8/5/2004 3 < 0.001 17 10.1 59 < 0.006 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Mid 8/5/2004 1 < 0.001 17 10.3 59 < 0.005 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Mid 8/5/2004 2 < 0.001 17 10.2 60 < 0.005 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Mid 8/5/2004 3 < 0.001 17 10.5 61 < 0.006 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Far 8/5/2004 1 < 0.001 20 10.8 69 0.008 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Far 8/5/2004 2 < 0.001 20 10.7 70 0.007 < 0.005 < 0.005 0.006 < 0.001 < 0.001
Far 8/5/2004 3 < 0.001 21 10.9 71 0.008 < 0.005 < 0.005 0.006 < 0.001 < 0.001
DI/MQ BLANK 8/5/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 8/5/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 8/5/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 8/5/2004 <0.005 <0.001
POST-ULTRA FILTER BLANK 8/5/2004 <0.005 <0.001
273
Near 11/23/2004 1 < 0.005 15 8.7 55 0.006 < 0.005 < 0.005 0.002 < 0.001 < 0.001
Near 11/23/2004 2 < 0.006 15 9.0 55 0.006 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Near 11/23/2004 3 < 0.005 16 8.6 55 0.008 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Mid 11/23/2004 1 < 0.005 15 9.0 54 < 0.005 < 0.005 < 0.005 0.002 < 0.001 < 0.001
Mid 11/23/2004 2 < 0.005 15 9.1 53 0.005 0.018 < 0.005 0.002 < 0.001 < 0.001
Mid 11/23/2004 3 < 0.005 15 9.1 54 < 0.006 < 0.005 < 0.005 0.002 < 0.001 < 0.001
Far 11/23/2004 1 < 0.005 24 10.6 81 0.017 < 0.005 < 0.005 0.004 < 0.001 < 0.001
Far 11/23/2004 2 < 0.005 24 10.7 80 0.017 < 0.005 < 0.005 0.004 < 0.001 < 0.001
Far 11/23/2004 3 < 0.005 24 10.3 81 0.015 < 0.005 < 0.005 0.004 < 0.001 < 0.001
DI/MQ BLANK 11/23/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 11/23/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 11/23/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 11/23/2004 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 11/23/2004 < 0.005 < 0.001
274
Near 12/22/2004 1 < 0.001 13 9.7 52 < 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Near 12/22/2004 2 < 0.001 13 9.5 52 < 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Near 12/22/2004 3 < 0.001 13 9.5 51 < 0.006 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Mid 12/22/2004 1 < 0.001 12 10.0 51 < 0.005 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Mid 12/22/2004 2 < 0.001 12 9.9 51 < 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Mid 12/22/2004 3 < 0.001 12 9.2 51 < 0.006 < 0.005 < 0.005 0.001 < 0.001 < 0.001
Far 12/22/2004 1 < 0.001 29 10.7 103 0.017 < 0.005 < 0.005 0.005 < 0.001 < 0.001
Far 12/22/2004 2 < 0.001 27 10.8 96 0.016 < 0.005 < 0.005 0.004 < 0.001 < 0.001
Far 12/22/2004 3 < 0.001 27 10.5 96 0.016 < 0.005 < 0.005 0.004 < 0.001 < 0.001
DI/MQ BLANK 12/22/2004 < 0.001 <1 < 0.005 < 0.001
FIELD BLANK 12/22/2004 < 0.001 44 < 0.005 < 0.001
FILTER BLANK 12/22/2004 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 12/22/2004 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 12/22/2004 < 0.005 < 0.001
275
Near 10/5/2004 1 < 0.001 16 9.4 58 0.008 < 0.005 < 0.005 0.004 < 0.001 < 0.001
Mid 10/5/2004 1 < 0.001 16 9.3 58 < 0.006 < 0.005 < 0.005 0.003 < 0.001 < 0.001
Far 10/5/2004 1 < 0.001 17 9.4 59 0.017 < 0.005 < 0.005 0.006 < 0.001 < 0.001
DI/MQ BLANK 10/5/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 10/5/2004 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 10/5/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 10/5/2004 <0.005 <0.001
POST-ULTRA FILTER BLANK 10/5/2004 <0.005 <0.001
276
Near 6/10/2004 1 < 0.001 21 25.9 83 < 0.005 < 0.005 < 0.005 0.009 0.007 0.005
Near 6/10/2004 2 < 0.001 21 26.0 83 < 0.005 < 0.005 < 0.005 0.009 0.007 0.005
Near 6/10/2004 3 < 0.001 22 26.1 85 < 0.006 < 0.005 < 0.005 0.009 0.006 0.005
Mid 6/10/2004 1 < 0.001 21 25.6 83 < 0.005 < 0.005 < 0.005 0.009 0.007 0.004
Mid 6/10/2004 2 < 0.001 21 25.8 82 < 0.005 < 0.005 < 0.005 0.009 0.006 0.005
Mid 6/10/2004 3 < 0.001 16 19.9 63 < 0.006 < 0.005 < 0.005 0.007 0.006 0.005
Far 6/10/2004 1 < 0.001 21 26.3 82 < 0.005 < 0.005 < 0.005 0.009 0.006 0.005
Far 6/10/2004 2 < 0.001 20 25.2 79 < 0.005 < 0.005 < 0.005 0.009 0.006 0.005
Far 6/10/2004 3 < 0.001 21 26.0 83 < 0.006 < 0.005 < 0.005 0.009 0.006 0.005
DI/MQ BLANK 6/10/2004 < 0.001 1.04 3.10 < 0.005 < 0.001
FIELD BLANK 6/10/2004 < 0.001 < 0.05 < 1.66 < 0.005 < 0.001
FILTER BLANK 6/10/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 6/10/2004 < 0.005 0.001
POST-ULTRA FILTER BLANK 6/10/2004 < 0.005 < 0.001
277
Near 12/29/2004 1 < 0.006 16 22.3 61 0.006 < 0.005 < 0.005 0.012 0.004 < 0.001
Near 12/29/2004 2 < 0.005 16 21.5 61 < 0.005 < 0.005 < 0.005 0.012 0.003 0.002
Near 12/29/2004 3 < 0.005 16 21.3 60 < 0.006 < 0.005 < 0.005 0.011 0.004 0.003
Mid 12/29/2004 1 < 0.005 17 21.7 63 < 0.005 < 0.005 < 0.005 0.011 0.002 < 0.001
Mid 12/29/2004 2 < 0.005 18 21.5 65 < 0.005 < 0.005 < 0.005 0.010 0.002 0.001
Mid 12/29/2004 3 < 0.005 18 21.4 64 < 0.006 < 0.005 < 0.005 0.010 0.002 0.001
Far 12/29/2004 1 < 0.005 18 22.1 65 < 0.005 < 0.005 < 0.005 0.010 0.002 0.001
Far 12/29/2004 2 < 0.005 18 22.1 66 < 0.005 < 0.005 < 0.005 0.010 0.002 0.002
Far 12/29/2004 3 < 0.005 18 22.2 64 < 0.006 < 0.005 < 0.005 0.009 0.002 0.002
DI/MQ BLANK 12/29/2004 < 0.001 <1 < 0.005 < 0.005 < 0.05
FIELD BLANK 12/29/2004 < 0.001 <1 < 0.005 < 0.005 < 0.05
FILTER BLANK 12/29/2004 < 0.005
PRE-ULTRA FILTER BLANK 12/29/2004 < 0.005 0.005
POST-ULTRA FILTER BLANK 12/29/2004 < 0.006 0.008
278
Near 6/9/2004 1 < 0.001 31 29.3 128 < 0.005 < 0.005 < 0.005 0.004 0.004 0.004
Near 6/9/2004 2 0.001 30 27.8 126 < 0.005 < 0.005 < 0.005 0.004 0.004 0.004
Near 6/9/2004 3 0.001 32 29.5 131 < 0.006 < 0.005 < 0.005 0.004 0.004 0.004
Mid 6/9/2004 1 0.001 30 28.4 125 < 0.005 < 0.005 < 0.005 0.005 0.005 0.005
Mid 6/9/2004 2 0.001 31 28.9 128 < 0.005 < 0.005 < 0.005 0.006 0.005 0.005
Mid 6/9/2004 3 0.001 29 27.8 120 < 0.006 < 0.005 < 0.005 0.005 0.005 0.005
Far 6/9/2004 1 0.001 32 29.4 130 < 0.005 < 0.005 < 0.005 0.009 0.006 0.006
Far 6/9/2004 2 < 0.001 28 26.6 115 < 0.005 < 0.005 < 0.005 0.008 0.005 0.006
Far 6/9/2004 3 < 0.001 31 28.2 126 < 0.006 < 0.005 < 0.005 0.009 0.006 0.005
DI/MQ BLANK 6/9/2004 < 0.001 0.06 < 1.66 < 0.005 < 0.001
FIELD BLANK 6/9/2004 < 0.001 0.06 < 1.66 < 0.005 < 0.001
FILTER BLANK 6/9/2004 < 0.005 <0.001
PRE-ULTRA FILTER BLANK 6/9/2004 < 0.005 0.001
POST-ULTRA FILTER BLANK 6/9/2004 < 0.006 < 0.001
279
Near 2/9/2005 1 < 0.001 22.8 90 < 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Near 2/9/2005 2 < 0.001 22.7 91 < 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Near 2/9/2005 3 < 0.001 22.5 90 < 0.006 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Mid 2/9/2005 1 < 0.001 23.4 89 < 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Mid 2/9/2005 2 < 0.001 23.7 90 < 0.005 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Mid 2/9/2005 3 < 0.001 23.5 87 < 0.006 < 0.005 < 0.005 < 0.001 < 0.001 < 0.001
Far 2/9/2005 1 < 0.001 24.0 89 < 0.005 < 0.006 < 0.005 0.001 < 0.001 < 0.001
Far 2/9/2005 2 < 0.001 23.3 91 < 0.005 < 0.006 < 0.005 0.001 < 0.001 < 0.001
Far 2/9/2005 3 < 0.001 22.4 88 < 0.006 < 0.005 < 0.005 0.001 < 0.001 < 0.001
DI/MQ BLANK 2/9/2005 < 0.001 < 0.05 <1 < 0.005 < 0.001
FIELD BLANK 2/9/2005 < 0.001 < 0.05 <1 < 0.005 < 0.001
FILTER BLANK 2/9/2005 < 0.005 < 0.001
PRE-ULTRA FILTER BLANK 2/9/2005 < 0.005 < 0.001
POST-ULTRA FILTER BLANK 2/9/2005 < 0.006 0.001
280
2 002-E1-1 2/26/2004 8:25 238.0 0.21 0.62 6.80 0.061 10.5 1.1 0.0165 <5 940.0 1.1 146.00 1.0 11.0 570.0
2 002-E1-2 2/26/2004 8:25 238.0 0.21 0.62 6.80 0.061 10.5 1.1 0.0165 <5 940.0 1.1 146.00 1.0 11.0 570.0
2 002-E1-3 2/26/2004 8:25 238.0 0.21 0.62 6.80 0.061 10.5 1.1 0.0165 <5 940.0 1.1 146.00 1.0 11.0 570.0
2 002-M1-1 2/26/2004 9:15 242.0 0.30 0.42 6.80 0.23 6.5 1.1 0.017 <5 930.0 1.1 144.00 0.3 10.8 572.0
2 002-M1-2 2/26/2004 9:15 242.0 0.30 0.42 6.80 0.23 6.5 1.1 0.017 <5 930.0 1.1 144.00 0.3 10.8 572.0
2 002-M1-3 2/26/2004 9:15 242.0 0.30 0.42 6.80 0.23 6.5 1.1 0.017 <5 930.0 1.1 144.00 0.3 10.8 572.0
2 002-N1-1 2/26/2004 9:55 240.0 0.30 0.42 6.50 0.074 6.0 1.1 0.0205 <5 930.0 1.0 147.00 0.3 10.8 569.0
2 002-N1-2 2/26/2004 9:55 240.0 0.30 0.42 6.50 0.074 6.0 1.1 0.0205 <5 930.0 1.0 147.00 0.3 10.8 569.0
2 002-N1-3 2/26/2004 9:55 240.0 0.30 0.42 6.50 0.074 6.0 1.1 0.0205 <5 930.0 1.0 147.00 0.3 10.8 569.0
2 002-F1-1 2/26/2004 10:30 237.0 0.22 0.35 6.70 0.478 9.5 1.2 0.014 <5 880.0 1.1 146.00 0.3 10.8 565.0
2 002-F1-2 2/26/2004 10:30 237.0 0.22 0.35 6.70 0.478 9.5 1.2 0.014 <5 880.0 1.1 146.00 0.3 10.8 565.0
2 002-F1-3 2/26/2004 10:30 237.0 0.22 0.35 6.70 0.478 9.5 1.2 0.014 <5 880.0 1.1 146.00 0.3 10.8 565.0
281
2 002-E2-1 5/20/2004 8:30 238.0 0.30 0.49 6.80 0.61 12.5 1.2 0.0215 5 <5 930.0 <1.0 142.00 1.4 9.1 652.0
2 002-E2-2 5/20/2004 8:30 238.0 0.30 0.49 6.80 0.61 12.5 1.2 0.0215 5 <5 930.0 <1.0 142.00 1.4 9.1 652.0
2 002-E2-3 5/20/2004 8:30 238.0 0.30 0.49 6.80 0.61 12.5 1.2 0.0215 5 <5 930.0 <1.0 142.00 1.4 9.1 652.0
2 002-M2-1 5/20/2004 9:15 231.0 0.21 0.25 6.80 0.659 14.0 <1.0 0.023 <5 <5 900.0 <1.0 140.00 1.8 8.5 669.0
2 002-M2-2 5/20/2004 9:15 231.0 0.21 0.25 6.80 0.659 14.0 <1.0 0.023 <5 <5 900.0 <1.0 140.00 1.8 8.5 669.0
2 002-M2-3 5/20/2004 9:15 231.0 0.21 0.25 6.80 0.659 14.0 <1.0 0.023 <5 <5 900.0 <1.0 140.00 1.8 8.5 669.0
2 002-N2-1 5/20/2004 10:30 235.0 0.30 0.40 6.80 0.622 13.0 <1.0 0.029 <5 <5 940.0 <1.0 143.00 1.1 10.3 637.0
2 002-N2-2 5/20/2004 10:30 235.0 0.30 0.40 6.80 0.622 13.0 <1.0 0.029 <5 <5 940.0 <1.0 143.00 1.1 10.3 637.0
2 002-N2-3 5/20/2004 10:30 235.0 0.30 0.40 6.80 0.622 13.0 <1.0 0.029 <5 <5 940.0 <1.0 143.00 1.1 10.3 637.0
2 002-F2-1 5/20/2004 11:05 234.0 0.26 0.30 7.00 0.668 13.5 <1.0 0.0205 <5 <5 880.0 <1.0 136.00 0.8 8.3 604.0
2 002-F2-2 5/20/2004 11:05 234.0 0.26 0.30 7.00 0.668 13.5 <1.0 0.0205 <5 <5 880.0 <1.0 136.00 0.8 8.3 604.0
2 002-F2-3 5/20/2004 11:05 234.0 0.26 0.30 7.00 0.668 13.5 <1.0 0.0205 <5 <5 880.0 <1.0 136.00 0.8 8.3 604.0
282
2 002-E3-1 8/31/2004 7:50 223.0 0.42 0.62 6.00 0.307 13.3 1.2 0.009 <5 <5 760.0 <1.0 143.00 0.32 7.8 550.0
2 002-E3-2 8/31/2004 7:50 223.0 0.42 0.62 6.00 0.307 13.3 1.2 0.009 <5 <5 760.0 <1.0 143.00 0.32 7.8 550.0
2 002-E3-3 8/31/2004 7:50 223.0 0.42 0.62 6.00 0.307 13.3 1.2 0.009 <5 <5 760.0 <1.0 143.00 0.32 7.8 550.0
2 002-M3-1 8/31/2004 8:25 223.0 0.24 0.37 6.60 0.497 17.6 1.5 0.013 <5 <5 750.0 <1.0 145.00 2.01 8.7 552.0
2 002-M3-2 8/31/2004 8:25 223.0 0.24 0.37 6.60 0.497 17.6 1.5 0.013 <5 <5 750.0 <1.0 145.00 2.01 8.7 552.0
2 002-M3-3 8/31/2004 8:25 223.0 0.24 0.37 6.60 0.497 17.6 1.5 0.013 <5 <5 750.0 <1.0 145.00 2.01 8.7 552.0
2 002-N3-1 8/31/2004 9:00 225.0 0.33 0.46 6.30 0.328 14.7 1.2 0.012 <5 <5 810.0 1.0 143.00 1.63 7.9 553.0
2 002-N3-2 8/31/2004 9:00 225.0 0.33 0.46 6.30 0.328 14.7 1.2 0.012 <5 <5 810.0 1.0 143.00 1.63 7.9 553.0
2 002-N3-3 8/31/2004 9:00 225.0 0.33 0.46 6.30 0.328 14.7 1.2 0.012 <5 <5 810.0 1.0 143.00 1.63 7.9 553.0
2 002-F3-1 8/31/2004 9:30 225.0 0.01 0.04 6.50 0.724 18.5 1.4 < 0.009 <5 <5 740.0 <1.0 144.00 1.41 7.2 550.0
2 002-F3-2 8/31/2004 9:30 225.0 0.01 0.04 6.50 0.724 18.5 1.4 < 0.009 <5 <5 740.0 <1.0 144.00 1.41 7.2 550.0
2 002-F3-3 8/31/2004 9:30 225.0 0.01 0.04 6.50 0.724 18.5 1.4 < 0.009 <5 <5 740.0 <1.0 144.00 1.41 7.2 550.0
283
2 002-E4-1 11/9/2004 8:30 217.0 0.58 0.64 6.60 0.491 10.5 1.12 0.024 <5 <5 810.0 3.81 210.00 2.29 8.0 648.0
2 002-E4-2 11/9/2004 8:30 217.0 0.58 0.64 6.60 0.491 10.5 1.12 0.024 <5 <5 810.0 3.81 210.00 2.29 8.0 648.0
2 002-E4-3 11/9/2004 8:30 217.0 0.58 0.64 6.60 0.491 10.5 1.12 0.024 <5 <5 810.0 3.81 210.00 2.29 8.0 648.0
2 002-M4-1 11/9/2004 9:00 228.0 0.80 0.9 6.50 0.675 14.5 0.76 0.046 <5 <5 780.0 1.22 222.00 2.27 6.9 677.0
2 002-M4-2 11/9/2004 9:00 228.0 0.80 0.9 6.50 0.675 14.5 0.76 0.046 <5 <5 780.0 1.22 222.00 2.27 6.9 677.0
2 002-M4-3 11/9/2004 9:00 228.0 0.80 0.9 6.50 0.675 14.5 0.76 0.046 <5 <5 780.0 1.22 222.00 2.27 6.9 677.0
2 002-N4-1 11/9/2004 9:35 219.0 0.15 0.25 7.00 0.552 16.5 1.13 0.032 <5 <5 770.0 3.35 211.00 2.24 7.8 651.0
2 002-N4-2 11/9/2004 9:35 219.0 0.15 0.25 7.00 0.552 16.5 1.13 0.032 <5 <5 770.0 3.35 211.00 2.24 7.8 651.0
2 002-N4-3 11/9/2004 9:35 219.0 0.15 0.25 7.00 0.552 16.5 1.13 0.032 <5 <5 770.0 3.35 211.00 2.24 7.8 651.0
2 002-F4-1 11/9/2004 10:05 226.0 0.13 0.12 7.10 0.736 16.0 0.87 0.026 <5 <5 780.0 1.27 211.00 4.11 8.0 626.0
2 002-F4-2 11/9/2004 10:05 226.0 0.13 0.12 7.10 0.736 16.0 0.87 0.026 <5 <5 780.0 1.27 211.00 4.11 8.0 626.0
2 002-F4-3 11/9/2004 10:05 226.0 0.13 0.12 7.10 0.736 16.0 0.87 0.026 <5 <5 780.0 1.27 211.00 4.11 8.0 626.0
284
7 007-E1-1 2/26/2004
7 007-E1-2 2/26/2004
7 007-E1-3 2/26/2004
7 007-N1-1 2/26/2004 9:30 155 11.0 0.40 3.5 8.89 16.0 25 84.9 42.4
7 007-N1-2 2/26/2004 9:30 155 11.0 0.40 3.5 8.89 16.0 25 84.9 42.4
7 007-N1-3 2/26/2004 9:30 155 11.0 0.40 3.5 8.89 16.0 25 84.9 42.4
7 007-M1-1 2/26/2004 10:40 4967 12.0 1.30 3.3 9.11 16.0 7 164.9 82.4
7 007-M1-2 2/26/2004 10:40 4967 12.0 1.30 3.3 9.11 16.0 7 164.9 82.4
7 007-M1-3 2/26/2004 10:40 4967 12.0 1.30 3.3 9.11 16.0 7 164.9 82.4
7 007-F1-1 2/26/2004 11:50 170 12.0 0.20 1.3 9.13 15.0 5 153.7 77.0
7 007-F1-2 2/26/2004 11:50 170 12.0 0.20 1.3 9.13 15.0 5 153.7 77.0
7 007-F1-3 2/26/2004 11:50 170 12.0 0.20 1.3 9.13 15.0 5 153.7 77.0
285
7 007-E2-1 5/4/2004 20.0 0.10 3.30 8.90 25.0 0.064 6 14 96.0 47.1
7 007-E2-2 5/4/2004 20.0 0.10 3.30 8.90 25.0 0.064 6 14 96.0 47.1
7 007-E2-3 5/4/2004 20.0 0.10 3.30 8.90 25.0 0.064 6 14 96.0 47.1
7 007-F2-1 5/4/2004 170 17.0 0.00 2.0 8.98 26.0 0.053 6 13 117.0 50.5
7 007-F2-2 5/4/2004 170 17.0 0.00 2.0 8.98 26.0 0.053 6 13 117.0 50.5
7 007-F2-3 5/4/2004 170 17.0 0.00 2.0 8.98 26.0 0.053 6 13 117.0 50.5
7 007-M2-1 5/4/2004 4967 22.0 0.00 2.5 8.98 25.0 0.055 6 8 114.0 57.3
7 007-M2-2 5/4/2004 4967 22.0 0.00 2.5 8.98 25.0 0.055 6 8 114.0 57.3
7 007-M2-3 5/4/2004 4967 22.0 0.00 2.5 8.98 25.0 0.055 6 8 114.0 57.3
7 007-N2-1 5/4/2004 155 20.0 0.10 2.7 8.84 26.0 0.063 5 14 100.0 47.9
7 007-N2-2 5/4/2004 155 20.0 0.10 2.7 8.84 26.0 0.063 5 14 100.0 47.9
7 007-N2-3 5/4/2004 155 20.0 0.10 2.7 8.84 26.0 0.063 5 14 100.0 47.9
286
7 007-N4-1 11/18/2004 10:35 155 20.0 0.00 3.2 8.22 20.6 2.3 0.073 4 100.0 50.0
7 007-N4-2 11/18/2004 10:35 155 20.0 0.00 3.2 8.22 20.6 2.3 0.073 4 100.0 50.0
7 007-N4-3 11/18/2004 10:35 155 20.0 0.00 3.2 8.22 20.6 2.3 0.073 4 100.0 50.0
7 007-F4-1 11/18/2004 13:02 170 18.0 0.00 0.0 7.49 21.4 1.6 0.057 3 120.0 60.0
7 007-F4-2 11/18/2004 13:02 170 18.0 0.00 0.0 7.49 21.4 1.6 0.057 3 120.0 60.0
7 007-F4-3 11/18/2004 13:02 170 18.0 0.00 0.0 7.49 21.4 1.6 0.057 3 120.0 60.0
7 007-M4-1 11/18/2004 14:05 4967 20.0 0.30 2.7 9.14 19.0 1.9 0.055 3 180.0 90.0
7 007-M4-2 11/18/2004 14:05 4967 20.0 0.30 2.7 9.14 19.0 1.9 0.055 3 180.0 90.0
7 007-M4-3 11/18/2004 14:05 4967 20.0 0.30 2.7 9.14 19.0 1.9 0.055 3 180.0 90.0
7 007-E4-1 11/18/2004 16:32 22.0 0.10 3.4 8.95 23.0 3.5 0.074 3 100.0 50.0
7 007-E4-2 11/18/2004 16:32 22.0 0.10 3.4 8.95 23.0 3.5 0.074 3 100.0 50.0
7 007-E4-3 11/18/2004 16:32 22.0 0.10 3.4 8.95 23.0 3.5 0.074 3 100.0 50.0
287
7 007-F5-1 1/10/2005 10:24 170 11.0 0.00 2.0 8.90 16.0 4.0 0.044 12 7 203.0 60.0
7 007-F5-2 1/10/2005 10:24 170 11.0 0.00 2.0 8.90 16.0 4.0 0.044 12 7 203.0 60.0
7 007-F5-3 1/10/2005 10:24 170 11.0 0.00 2.0 8.90 16.0 4.0 0.044 12 7 203.0 60.0
7 007-M5-1 1/10/2005 11:55 4967 13.0 0.50 3.5 8.85 13.0 4.3 0.043 8 3 127.0 100.0
7 007-M5-2 1/10/2005 11:55 4967 13.0 0.50 3.5 8.85 13.0 4.3 0.043 8 3 127.0 100.0
7 007-M5-3 1/10/2005 11:55 4967 13.0 0.50 3.5 8.85 13.0 4.3 0.043 8 3 127.0 100.0
7 007-N5-1 1/10/2005 13:17 155 13.0 1.50 3.5 8.93 14.0 3.2 0.049 11 7 90.0 50.0
7 007-N5-2 1/10/2005 13:17 155 13.0 1.50 3.5 8.93 14.0 3.2 0.049 11 7 90.0 50.0
7 007-N5-3 1/10/2005 13:17 155 13.0 1.50 3.5 8.93 14.0 3.2 0.049 11 7 90.0 50.0
7 007-E5-1 1/10/2005 14:30 14.0 1.50 3.13 9.03 13.3 4.0 0.057 7 5 80.0 50.0
7 007-E5-2 1/10/2005 14:30 14.0 1.50 3.13 9.03 13.3 4.0 0.057 7 5 80.0 50.0
7 007-E5-3 1/10/2005 14:30 14.0 1.50 3.13 9.03 13.3 4.0 0.057 7 5 80.0 50.0
288
9 009-M1-1 3/9/2004 9:05 1302 48.6 0.08 2.06 7.34 1.245 14.2 1.05 0.0216 0 0 344.0 0.092
9 009-M1-2 3/9/2004 9:05 1302 48.6 0.08 2.06 7.34 1.245 14.2 1.05 0.0216 0 0 344.0 0.092
9 009-M1-3 3/9/2004 9:05 1302 48.6 0.08 2.06 7.34 1.245 14.2 1.05 0.0216 0 0 344.0 0.092
9 009-N1-1 3/9/2004 9:43 1202 50.1 0.28 2.2 7.29 1.291 9.3 1.24 0.0215 0 0 341.0 0.088
9 009-N1-2 3/9/2004 9:43 1202 50.1 0.28 2.2 7.29 1.291 9.3 1.24 0.0215 0 0 341.0 0.088
9 009-N1-3 3/9/2004 9:43 1202 50.1 0.28 2.2 7.29 1.291 9.3 1.24 0.0215 0 0 341.0 0.088
9 009-E1-1 3/9/2004 10:30 4001 54.3 0.20 2.2 7.24 1.285 9.1 1.03 0.0212 1 0 333.0 0.099
9 009-E1-2 3/9/2004 10:30 4001 54.3 0.20 2.2 7.24 1.285 9.1 1.03 0.0212 1 0 333.0 0.099
9 009-E1-3 3/9/2004 10:30 4001 54.3 0.20 2.2 7.24 1.285 9.1 1.03 0.0212 1 0 333.0 0.099
9 009-F1-1 3/9/2004 11:10 1101 52.2 0.47 2.2 7.22 1.26 9.0 1.08 0.0206 0 0 343.0 0.081
9 009-F1-2 3/9/2004 11:10 1101 52.2 0.47 2.2 7.22 1.26 9.0 1.08 0.0206 0 0 343.0 0.081
9 009-F1-3 3/9/2004 11:10 1101 52.2 0.47 2.2 7.22 1.26 9.0 1.08 0.0206 0 0 343.0 0.081
289
9 009-M2-1 6/16/2004 8:45 1302 40.3 0.09 1.96 7.25 1.279 23.4 1.31 0.026 0 0 307.0 0.074
9 009-M2-2 6/16/2004 8:45 1302 40.3 0.09 1.96 7.25 1.279 23.4 1.31 0.026 0 0 307.0 0.074
9 009-M2-3 6/16/2004 8:45 1302 40.3 0.09 1.96 7.25 1.279 23.4 1.31 0.026 0 0 307.0 0.074
9 009-N2-1 6/16/2004 9:50 1202 40.6 0.05 1.97 7.25 1.279 21.0 1.13 0.0261 0 0 307.0 0.082
9 009-N2-2 6/16/2004 9:50 1202 40.6 0.05 1.97 7.25 1.279 21.0 1.13 0.0261 0 0 307.0 0.082
9 009-N2-3 6/16/2004 9:50 1202 40.6 0.05 1.97 7.25 1.279 21.0 1.13 0.0261 0 0 307.0 0.082
9 009-E2-1 6/16/2004 10:50 4001 40.2 0.05 2.05 7.27 1.275 23.6 1.88 0.0282 0 0 304.0 0.076
9 009-E2-2 6/16/2004 10:50 4001 40.2 0.05 2.05 7.27 1.275 23.6 1.88 0.0282 0 0 304.0 0.076
9 009-E2-3 6/16/2004 10:50 4001 40.2 0.05 2.05 7.27 1.275 23.6 1.88 0.0282 0 0 304.0 0.076
9 009-F2-1 6/16/2004 12:15 1101 41.3 0.05 1.99 7.27 1.266 22.4 1.51 0.0261 0 0 307.0 0.062
9 009-F2-2 6/16/2004 12:15 1101 41.3 0.05 1.99 7.27 1.266 22.4 1.51 0.0261 0 0 307.0 0.062
9 009-F2-3 6/16/2004 12:15 1101 41.3 0.05 1.99 7.27 1.266 22.4 1.51 0.0261 0 0 307.0 0.062
290
9 009-M3-1 9/10/2004 8:30 1302 36.1 0.04 1.91 6.98 1.165 25.3 1.62 0.0305 0 0 275.0 0.056
9 009-M3-2 9/10/2004 8:30 1302 36.1 0.04 1.91 6.98 1.165 25.3 1.62 0.0305 0 0 275.0 0.056
9 009-M3-3 9/10/2004 8:30 1302 36.1 0.04 1.91 6.98 1.165 25.3 1.62 0.0305 0 0 275.0 0.056
9 009-N3-1 9/10/2004 9:15 1202 38.7 0.04 1.96 7.05 1.156 24.3 1.96 0.031 0 0 274.0 0.081
9 009-N3-2 9/10/2004 9:15 1202 38.7 0.04 1.96 7.05 1.156 24.3 1.96 0.031 0 0 274.0 0.081
9 009-N3-3 9/10/2004 9:15 1202 38.7 0.04 1.96 7.05 1.156 24.3 1.96 0.031 0 0 274.0 0.081
9 009-E3-1 9/10/2004 9:55 4001 33.4 0.07 2.15 7.02 1.168 24.7 1.59 0.0333 0 0 266.0 0.070
9 009-E3-2 9/10/2004 9:55 4001 33.4 0.07 2.15 7.02 1.168 24.7 1.59 0.0333 0 0 266.0 0.070
9 009-E3-3 9/10/2004 9:55 4001 33.4 0.07 2.15 7.02 1.168 24.7 1.59 0.0333 0 0 266.0 0.070
9 009-F3-1 9/10/2004 10:45 1101 37.1 0.04 1.67 7.13 1.199 24.8 1.59 0.0308 0 0 275.0 0.056
9 009-F3-2 9/10/2004 10:45 1101 37.1 0.04 1.67 7.13 1.199 24.8 1.59 0.0308 0 0 275.0 0.056
9 009-F3-3 9/10/2004 10:45 1101 37.1 0.04 1.67 7.13 1.199 24.8 1.59 0.0308 0 0 275.0 0.056
291
9 009-M4-1 12/8/2004 8:45 1302 25.0 0.02 2.07 7.01 1.236 11.1 0.0259 0 0 234.0 0.051
9 009-M4-2 12/8/2004 8:45 1302 25.0 0.02 2.07 7.01 1.236 11.1 0.0259 0 0 234.0 0.051
9 009-M4-3 12/8/2004 8:45 1302 25.0 0.02 2.07 7.01 1.236 11.1 0.0259 0 0 234.0 0.051
9 009-N4-1 12/8/2004 9:50 1202 26.1 0.02 2.06 6.97 1.536 13.5 0.0259 0 0 232.0 0.056
9 009-N4-2 12/8/2004 9:50 1202 26.1 0.02 2.06 6.97 1.536 13.5 0.0259 0 0 232.0 0.056
9 009-N4-3 12/8/2004 9:50 1202 26.1 0.02 2.06 6.97 1.536 13.5 0.0259 0 0 232.0 0.056
9 009-E4-1 12/8/2004 10:35 4001 26.3 0.01 2.20 6.87 1.36 8.4 1.51 0.0262 0 0 241.0 0.049
9 009-E4-2 12/8/2004 10:35 4001 26.3 0.01 2.20 6.87 1.36 8.4 1.51 0.0262 0 0 241.0 0.049
9 009-E4-3 12/8/2004 10:35 4001 26.3 0.01 2.20 6.87 1.36 8.4 1.51 0.0262 0 0 241.0 0.049
9 009-F4-1 12/8/2004 11:50 1101 30.3 0.02 1.78 6.58 1.325 12.0 0.0256 0 0 260.0 0.065
9 009-F4-2 12/8/2004 11:50 1101 30.3 0.02 1.78 6.58 1.325 12.0 0.0256 0 0 260.0 0.065
9 009-F4-3 12/8/2004 11:50 1101 30.3 0.02 1.78 6.58 1.325 12.0 0.0256 0 0 260.0 0.065
292
293
294
295
296
22 022-E1-1 1/24/2004 9:15 HM FW 42.0 2.9 8.00 0.644 4.0 2.37 0.04 0 0 238.0 39.70 0.329 202.0
22 022-E1-2 1/24/2004 9:15 HM FW 42.0 2.9 8.00 0.644 4.0 2.37 0.04 0 0 238.0 39.70 0.329 202.0
22 022-E1-3 1/24/2004 9:15 HM FW 42.0 2.9 8.00 0.644 4.0 2.37 0.04 0 0 238.0 39.70 0.329 202.0
22 022-N1-1 1/24/2004 10:24 T05 42.0 3.5 8.30 0.675 9.0 2.36 0.042 0 0 239.0 39.80 0.254 200.0
22 022-N1-2 1/24/2004 10:24 T05 42.0 3.5 8.30 0.675 9.0 2.36 0.042 0 0 239.0 39.80 0.254 200.0
22 022-N1-3 1/24/2004 10:24 T05 42.0 3.5 8.30 0.675 9.0 2.36 0.042 0 0 239.0 39.80 0.254 200.0
22 022-M1-1 1/24/2004 11:18 T09 46.0 3.1 8.10 0.705 10.0 2.43 0.04 0 0 251.0 39.40 0.231 284.0
22 022-M1-2 1/24/2004 11:18 T09 46.0 3.1 8.10 0.705 10.0 2.43 0.04 0 0 251.0 39.40 0.231 284.0
22 022-M1-3 1/24/2004 11:18 T09 46.0 3.1 8.10 0.705 10.0 2.43 0.04 0 0 251.0 39.40 0.231 284.0
22 022-F1-1 1/24/2004 12:24 T08 46.0 0.8 8.10 0.583 7.0 2.42 0.035 0 0 243.0 39.80 0.26 180.0
22 022-F1-2 1/24/2004 12:24 T08 46.0 0.8 8.10 0.583 7.0 2.42 0.035 0 0 243.0 39.80 0.26 180.0
22 022-F1-3 1/24/2004 12:24 T08 46.0 0.8 8.10 0.583 7.0 2.42 0.035 0 0 243.0 39.80 0.26 180.0
297
22 022-E2-1 4/20/2004 8:20 HM FW 38.0 2.8 7.80 0.46 20.0 2.57 0.038 0 0 226.0 30.60 0.362 177.0
22 022-E2-2 4/20/2004 8:20 HM FW 38.0 2.8 7.80 0.46 20.0 2.57 0.038 0 0 226.0 30.60 0.362 177.0
22 022-E2-3 4/20/2004 8:20 HM FW 38.0 2.8 7.80 0.46 20.0 2.57 0.038 0 0 226.0 30.60 0.362 177.0
22 022-N2-1 4/20/2004 9:56 T05 34.0 2.8 7.50 0.491 22.5 2.34 0.039 0 0 227.0 33.50 0.39 198.0
22 022-N2-2 4/20/2004 9:56 T05 34.0 2.8 7.50 0.491 22.5 2.34 0.039 0 0 227.0 33.50 0.39 198.0
22 022-N2-3 4/20/2004 9:56 T05 34.0 2.8 7.50 0.491 22.5 2.34 0.039 0 0 227.0 33.50 0.39 198.0
22 022-M2-1 4/20/2004 10:55 T09 40.0 2.4 7.80 0.491 19.5 2.39 0.037 0 0 230.0 33.80 0.167 185.0
22 022-M2-2 4/20/2004 10:55 T09 40.0 2.4 7.80 0.491 19.5 2.39 0.037 0 0 230.0 33.80 0.167 185.0
22 022-M2-3 4/20/2004 10:55 T09 40.0 2.4 7.80 0.491 19.5 2.39 0.037 0 0 230.0 33.80 0.167 185.0
22 022-F2-1 4/20/2004 11:51 T08 44.0 0 8.30 0.552 16.5 2.00 0.029 0 0 243.0 33.10 0.165 181.0
22 022-F2-2 4/20/2004 11:51 T08 44.0 0 8.30 0.552 16.5 2.00 0.029 0 0 243.0 33.10 0.165 181.0
22 022-F2-3 4/20/2004 11:51 T08 44.0 0 8.30 0.552 16.5 2.00 0.029 0 0 243.0 33.10 0.165 181.0
298
22 022-N3-1 8/27/2004 9:50 T05 40.0 4.2 7.60 0.552 28.0 3.35 0.063 0 0 225.0 36.50 1.10 180.0
22 022-N3-2 8/27/2004 9:50 T05 40.0 4.2 7.60 0.552 28.0 3.35 0.063 0 0 225.0 36.50 1.10 180.0
22 022-N3-3 8/27/2004 9:50 T05 40.0 4.2 7.60 0.552 28.0 3.35 0.063 0 0 225.0 36.50 1.10 180.0
22 022-M3-1 8/27/2004 10:35 T09 44.0 3.1 7.70 0.613 26.0 3.44 0.055 0 0 218.0 34.60 0.53 182.0
22 022-M3-2 8/27/2004 10:35 T09 44.0 3.1 7.70 0.613 26.0 3.44 0.055 0 0 218.0 34.60 0.53 182.0
22 022-M3-3 8/27/2004 10:35 T09 44.0 3.1 7.70 0.613 26.0 3.44 0.055 0 0 218.0 34.60 0.53 182.0
22 022-E3-1 8/27/2004 11:02 HM FW 44.0 4.2 7.50 0.521 26.5 3.29 0.061 0 0 220.0 37.00 1.03 181.0
22 022-E3-2 8/27/2004 11:02 HM FW 44.0 4.2 7.50 0.521 26.5 3.29 0.061 0 0 220.0 37.00 1.03 181.0
22 022-E3-3 8/27/2004 11:02 HM FW 44.0 4.2 7.50 0.521 26.5 3.29 0.061 0 0 220.0 37.00 1.03 181.0
22 022-F3-1 8/27/2004 11:24 T08 42.0 2.5 8.10 0.583 27.0 3.39 0.050 0 0 223.0 36.00 0.37 211.0
22 022-F3-2 8/27/2004 11:24 T08 42.0 2.5 8.10 0.583 27.0 3.39 0.050 0 0 223.0 36.00 0.37 211.0
22 022-F3-3 8/27/2004 11:24 T08 42.0 2.5 8.10 0.583 27.0 3.39 0.050 0 0 223.0 36.00 0.37 211.0
299
22 022-N4-1 11/12/2004 9:23 T05 38.0 3.9 7.30 0.601 23.5 2.57 0.045 0 0 245.0 44.40 0.80 159.0
22 022-N4-2 11/12/2004 9:23 T05 38.0 3.9 7.30 0.601 23.5 2.57 0.045 0 0 245.0 44.40 0.80 159.0
22 022-N4-3 11/12/2004 9:23 T05 38.0 3.9 7.30 0.601 23.5 2.57 0.045 0 0 245.0 44.40 0.80 159.0
22 022-M4-1 11/12/2004 10:06 T09 36.0 2.4 7.10 0.589 20.0 2.53 0.040 0 0 243.0 44.50 1.14 155.0
22 022-M4-2 11/12/2004 10:06 T09 36.0 2.4 7.10 0.589 20.0 2.53 0.040 0 0 243.0 44.50 1.14 155.0
22 022-M4-3 11/12/2004 10:06 T09 36.0 2.4 7.10 0.589 20.0 2.53 0.040 0 0 243.0 44.50 1.14 155.0
22 022-F4-1 11/12/2004 10:53 T08 40.0 2.0 7.30 0.521 17.0 2.50 0.042 0 0 246.0 44.00 0.39 158.0
22 022-F4-2 11/12/2004 10:53 T08 40.0 2.0 7.30 0.521 17.0 2.50 0.042 0 0 246.0 44.00 0.39 158.0
22 022-F4-3 11/12/2004 10:53 T08 40.0 2.0 7.30 0.521 17.0 2.50 0.042 0 0 246.0 44.00 0.39 158.0
22 022-E4-1 11/12/2004 11:25 HM FW 38.0 4.6 7.50 0.662 15.0 2.54 0.069 0 0 242.0 11.40 0.41 157.0
22 022-E4-2 11/12/2004 11:25 HM FW 38.0 4.6 7.50 0.662 15.0 2.54 0.069 0 0 242.0 11.40 0.41 157.0
22 022-E4-3 11/12/2004 11:25 HM FW 38.0 4.6 7.50 0.662 15.0 2.54 0.069 0 0 242.0 11.40 0.41 157.0
300
216 216-E1-1 2/11/2004 8:20 3587 60.0 0.86 0.95 7.22 2.28 5.2 2.81 0.066 8 334.6 1.06
216 216-E1-2 2/11/2004 8:30 3588 55.2 0.92 1.08 7.13 2.23 3.6 2.97 0.067 9 330.6 0.8
216 216-E1-3 2/11/2004 8:40 3589 55.4 0.97 1.09 7.06 2.01 3.6 2.91 0.067 7 330.1 0.74
216 216-N1-1 2/11/2004 9:12 33450 54.5 0.90 1.05 7.10 2.28 5.0 2.93 0.068 7 332.1 0.74
216 216-N1-2 2/11/2004 9:22 33450 54.3 0.90 1.11 7.13 2.23 4.9 2.93 0.067 6 333.8 0.74
216 216-N1-3 2/11/2004 9:32 33450 54.8 0.87 1.02 7.13 1.99 4.8 2.84 0.065 7 332.6 1
216 216-M1-1 2/11/2004 10:05 33450 55.9 0.60 0.78 7.20 2.2 4.8 3.02 0.067 6 334.0 0.71
216 216-M1-2 2/11/2004 10:15 33450 54.8 0.61 0.8 7.12 1.87 4.4 2.88 0.067 7 332.4 0.74
216 216-M1-3 2/11/2004 10:25 33450 54.6 0.58 0.74 7.11 2.24 4.2 3 0.065 8 333.7 0.81
216 216-F1-1 2/11/2004 10:53 31550 33.4 0.41 0.52 7.21 2.2 4.5 2.29 0.052 6 201.3 0.77
216 216-F1-2 2/11/2004 11:03 31550 32.3 0.40 0.53 7.18 2.13 4.2 2.27 0.053 6 195.5 0.89
216 216-F1-3 2/11/2004 11:13 31550 32.2 0.40 0.53 7.10 2.05 4.1 2.41 0.056 6 197.4 0.89
301
216 216-E2-1 5/27/2004 9:06 BX 33 55.9 0.88 1.06 7.19 2.06 13.7 3.19 0.054 7 380.0 1.16
216 216-E2-2 5/27/2004 9:15 BX 33 55.2 0.90 1.06 7.18 2.05 13.1 2.81 0.053 7 384.0 1.15
216 216-E2-3 5/27/2004 9:23 BX 33 55.5 0.81 0.93 7.18 2.19 13.3 2.48 0.052 6 398.0 1.07
216 216-N2-1 5/27/2004 9:58 38400 54.9 0.62 0.7 7.22 2.43 13.0 2.66 0.055 6 383.0 1.22
216 216-N2-2 5/27/2004 10:06 38400 55.0 0.60 0.76 7.25 1.95 12.5 2.8 0.054 7 384.0 1.22
216 216-N2-3 5/27/2004 10:13 38400 54.7 0.58 0.79 7.25 2.06 12.5 2.55 0.055 6 389.0 1.23
216 216-M2-1 5/27/2004 11:05 33450 54.8 0.42 0.46 7.29 1.98 13.9 2.52 0.054 8 378.0 1.06
216 216-M2-2 5/27/2004 11:13 33450 55.1 0.31 0.43 7.29 2.12 13.7 2.5 0.054 7 383.0 1.15
216 216-M2-3 5/27/2004 11:21 33450 55.0 0.30 0.5 7.27 1.95 13.7 2.72 0.055 7 384.0 0.94
216 216-F2-1 5/27/2004 12:25 31550 49.0 0.07 0.13 7.27 1.92 17.2 2.43 0.05 6 339.0 0.91
216 216-F2-2 5/27/2004 12:33 31550 48.9 0.01 0.16 7.26 1.8 16.7 2.62 0.051 6 344.0 0.95
216 216-F2-3 5/27/2004 12:40 31550 51.5 0.01 0.16 7.24 1.87 16.8 2.45 0.053 7 351.0 1.13
302
216 216-E3-1 8/19/2004 8:20 BX33 56.4 0.90 1.27 6.96 1.43 13.3 2.11 0.048 7 384.1 0.58
216 216-E3-2 8/19/2004 8:30 BX33 56.2 1.08 1.16 6.95 1.49 12.5 2.08 0.049 7 384.5 0.56
216 216-E3-3 8/19/2004 8:40 BX33 56.0 1.21 1.4 6.96 1.69 12.6 2.16 0.048 7 384.4 0.58
216 216-N3-3 8/19/2004 8:40 38400 57.8 1.31 1.56 6.98 2.04 12.0 2.41 0.05 8 384.1 0.67
216 216-N3-1 8/19/2004 9:20 38400 57.6 1.23 1.62 7.00 2.2 12.9 2.06 0.051 7 382.9 0.65
216 216-N3-2 8/19/2004 9:30 38400 57.8 1.29 1.59 6.99 2.38 12.2 2.19 0.05 8 383.6 0.64
216 216-M3-1 8/19/2004 10:10 33450 57.0 0.99 1.27 7.02 2.31 13.4 2.18 0.05 8 385.3 0.66
216 216-M3-2 8/19/2004 10:20 33450 56.9 0.98 1.09 7.02 2.32 13.2 2.15 0.05 6 386.3 0.65
216 216-M3-3 8/19/2004 10:30 33450 57.0 0.96 1.12 7.02 2.33 13.1 2.20 0.05 7 385.1 0.64
216 216-F3-1 8/19/2004 11:30 31550 56.6 0.33 0.60 7.07 1.64 15.7 2.14 0.051 7 385.9 0.67
216 216-F3-2 8/19/2004 11:40 31550 56.6 0.33 0.56 7.06 1.77 14.8 2.13 0.05 7 387.4 0.67
216 216-F3-3 8/19/2004 11:50 31550 56.7 0.43 0.50 7.04 1.73 14.7 2.15 0.05 7 386.1 0.59
303
269 269-E3-1 7/22/2004 11:00 132.0 1.10 1.3 7.00 0.337 0.981 1.318 21.5 0.31 0.004 316.0 2.9 174.0
269 269-E3-2 7/22/2004 11:00 132.0 1.10 1.3 7.00 0.337 0.981 1.318 21.5 0.31 0.004 316.0 2.9 174.0
269 269-E3-3 7/22/2004 11:00 132.0 1.10 1.3 7.00 0.337 0.981 1.318 21.5 0.31 0.004 316.0 2.9 174.0
269 269-F3-1 7/23/2004 9:00 132.0 0.50 0.8 7.25 0.368 0.889 1.257 21.1 < 0.1 0.005 321.0 <0.5 194.0
269 269-F3-2 7/23/2004 9:00 132.0 0.50 0.8 7.25 0.368 0.889 1.257 21.1 < 0.1 0.005 321.0 <0.5 194.0
269 269-F3-3 7/23/2004 9:00 132.0 0.50 0.8 7.25 0.368 0.889 1.257 21.1 < 0.1 0.005 321.0 <0.5 194.0
269 269-N3-1 7/23/2004 10:00 132.0 2.00 2 7.22 0.429 0.981 1.41 21.5 <0.1 0.008 316.0 1.3 194.0
269 269-N3-2 7/23/2004 10:00 132.0 2.00 2 7.22 0.429 0.981 1.41 21.5 <0.1 0.008 316.0 1.3 194.0
269 269-N3-3 7/23/2004 10:00 132.0 2.00 2 7.22 0.429 0.981 1.41 21.5 <0.1 0.008 316.0 1.3 194.0
304
269 269-E4-1 12/20/2004 2:05 112.0 0.80 1.2 7.80 0.399 1.042 1.441 18.6 <0.10 0.004 350.0 1.7 182.0
269 269-E4-2 12/20/2004 2:05 112.0 0.80 1.2 7.80 0.399 1.042 1.441 18.6 <0.10 0.004 350.0 1.7 182.0
269 269-E4-3 12/20/2004 2:05 112.0 0.80 1.2 7.80 0.399 1.042 1.441 18.6 <0.10 0.004 350.0 1.7 182.0
269 269-N4-1 12/20/2004 3:05 109.0 0.30 0.4 7.87 0.496 0.976 1.472 17.9 <0.1 0.002 299.0 2.4 188.0
269 269-N4-2 12/20/2004 3:05 109.0 0.30 0.4 7.87 0.496 0.976 1.472 17.9 <0.1 0.002 299.0 2.4 188.0
269 269-N4-3 12/20/2004 3:05 109.0 0.30 0.4 7.87 0.496 0.976 1.472 17.9 <0.1 0.002 299.0 2.4 188.0
269 269-F4-1 1/11/2005 3:45 110.0 0.20 0.3 7.94 0.399 1.011 1.410 16.4 < 0.1 0.003 308.0 6.5 186.0
269 269-F4-2 1/11/2005 3:45 110.0 0.20 0.3 7.94 0.399 1.011 1.410 16.4 < 0.1 0.003 308.0 6.5 186.0
269 269-F4-3 1/11/2005 3:45 110.0 0.20 0.3 7.94 0.399 1.011 1.410 16.4 < 0.1 0.003 308.0 6.5 186.0
305
306
315 315-E2-1 5/26/2004 13:00 2.55 2.7 7.28 21.4 1.48 371.0
315 315-E2-2 5/26/2004 13:00 2.55 2.7 7.28 21.4 1.48 371.0
315 315-E2-3 5/26/2004 13:00 2.55 2.7 7.28 21.4 1.48 371.0
315 315-X2-1 5/27/2004 13:30 2.00 2.1 7.90 16.7 2.1 395.0
315 315-X2-2 5/27/2004 13:30 2.00 2.1 7.90 16.7 2.1 395.0
315 315-X2-3 5/27/2004 13:30 2.00 2.1 7.90 16.7 2.1 395.0
307
315 315-E3-1 8/26/2004 13:23 31.0 2.43 2.49 7.60 22.8 1.05 467.0
315 315-E3-2 8/26/2004 13:23 31.0 2.43 2.49 7.60 22.8 1.05 467.0
315 315-E3-3 8/26/2004 13:23 31.0 2.43 2.49 7.60 22.8 1.05 467.0
315 315-M3-1 8/26/2004 10:30 30.0 1.40 1.47 7.90 25.3 1.01 421.0
315 315-M3-2 8/26/2004 10:30 30.0 1.40 1.47 7.90 25.3 1.01 421.0
315 315-M3-3 8/26/2004 10:30 30.0 1.40 1.47 7.90 25.3 1.01 421.0
315 315-N3-1 8/26/2004 11:15 35.0 1.31 1.38 7.50 23.9 1.03 440.0
315 315-N3-2 8/26/2004 11:15 35.0 1.31 1.38 7.50 23.9 1.03 440.0
315 315-N3-3 8/26/2004 11:15 35.0 1.31 1.38 7.50 23.9 1.03 440.0
315 315-F3-1 8/26/2004 9:30 30.0 1.30 1.38 8.00 23.9 1.01 420.0
315 315-F3-2 8/26/2004 9:30 30.0 1.30 1.38 8.00 23.9 1.01 420.0
315 315-F3-3 8/26/2004 9:30 30.0 1.30 1.38 8.00 23.9 1.01 420.0
308
315 315-E4-1 11/1/2004 14:00 61.0 2.44 2.50 7.23 1.334 20.0 0.98 421.0 0.070
315 315-E4-2 11/1/2004 14:00 61.0 2.44 2.50 7.23 1.334 20.0 0.98 421.0 0.070
315 315-E4-3 11/1/2004 14:00 61.0 2.44 2.50 7.23 1.334 20.0 0.98 421.0 0.070
309
318 318-E3-1 8/24/2004 10:40 180.0 0.80 0.86 7.90 0.83 0 0.797 20.0 <1.0 0.012 0 510.0 49.00 .14
318 318-E3-2 8/24/2004 10:40 180.0 0.80 0.86 7.90 0.83 0 0.797 20.0 <1.0 0.012 0 510.0 49.00 .14
318 318-E3-3 8/24/2004 10:40 180.0 0.80 0.86 7.90 0.83 0 0.797 20.0 <1.0 0.012 0 510.0 49.00 .14
318 318-M3-1 8/24/2004 13:00 20503 180.0 0.90 0.92 7.90 0.59 0.054 0.644 21.7 <1.0 0.012 0 510.0 48.00 .27
318 318-M3-2 8/24/2004 13:00 20503 180.0 0.90 0.92 7.90 0.59 0.054 0.644 21.7 <1.0 0.012 0 510.0 48.00 .27
318 318-M3-3 8/24/2004 13:00 20503 180.0 0.90 0.92 7.90 0.59 0.054 0.644 21.7 <1.0 0.012 0 510.0 48.00 .27
318 318-F3-1 8/24/2004 13:15 20326 180.0 0.74 1.07 7.90 0.52 0.185 0.705 23.3 <1.0 0.015 0 520.0 46.00 .63
318 318-F3-2 8/24/2004 13:15 20326 180.0 0.74 1.07 7.90 0.52 0.185 0.705 23.3 <1.0 0.015 0 520.0 46.00 .63
318 318-F3-3 8/24/2004 13:15 20326 180.0 0.74 1.07 7.90 0.52 0.185 0.705 23.3 <1.0 0.015 0 520.0 46.00 .63
310
318 318-E4-1 10/21/2004 11:59 170.0 0.83 0.89 7.90 0.66 0.996 1.656 15.0 13 0.011 <1 500.0 47.00 <0.10
318 318-E4-2 10/21/2004 11:59 170.0 0.83 0.89 7.90 0.66 0.996 1.656 15.0 13 0.011 <1 500.0 47.00 <0.10
318 318-E4-3 10/21/2004 11:59 170.0 0.83 0.89 7.90 0.66 0.996 1.656 15.0 13 0.011 <1 500.0 47.00 <0.10
318 318-M4-1 10/21/2004 12:14 20503 170.0 0.86 0.87 7.60 0.66 0.781 1.441 16.7 9.5 0.014 <1 510.0 47.00 <0.10
318 318-M4-2 10/21/2004 12:14 20503 170.0 0.86 0.87 7.60 0.66 0.781 1.441 16.7 9.5 0.014 <1 510.0 47.00 <0.10
318 318-M4-3 10/21/2004 12:14 20503 170.0 0.86 0.87 7.60 0.66 0.781 1.441 16.7 9.5 0.014 <1 510.0 47.00 <0.10
318 318-F4-1 10/21/2004 12:29 20326 150.0 0.93 0.98 7.60 < 0.50 > 0.54 1.042 17.8 11 0.012 <1 520.0 48.00 <0.10
318 318-F4-2 10/21/2004 12:29 20326 150.0 0.93 0.98 7.60 < 0.50 > 0.54 1.042 17.8 11 0.012 <1 520.0 48.00 <0.10
318 318-F4-3 10/21/2004 12:29 20326 150.0 0.93 0.98 7.60 < 0.50 > 0.54 1.042 17.8 11 0.012 <1 520.0 48.00 <0.10
311
318 318-E5-1 1/7/2005 12:20 170.0 0.38 1.04 8.00 < 1.0 > 0.318 1.318 0.23 0.014 < 1.0 480.0 49.00 <
318 318-E5-2 1/7/2005 12:20 170.0 0.38 1.04 8.00 < 1.0 > 0.318 1.318 0.23 0.014 < 1.0 480.0 49.00 <
318 318-E5-3 1/7/2005 12:20 170.0 0.38 1.04 8.00 < 1.0 > 0.318 1.318 0.23 0.014 < 1.0 480.0 49.00 <
318 318-M5-1 1/7/2005 12:40 20503 180.0 0.88 1.08 7.90 < 1.0 >0.68 1.686 0.23 0.016 < 1.0 480.0 55.00 <
318 318-M5-2 1/7/2005 12:40 20503 180.0 0.88 1.08 7.90 < 1.0 >0.68 1.686 0.23 0.016 < 1.0 480.0 55.00 <
318 318-M5-3 1/7/2005 12:40 20503 180.0 0.88 1.08 7.90 < 1.0 >0.68 1.686 0.23 0.016 < 1.0 480.0 55.00 <
318 318-F5-1 1/7/2005 12:54 20326 180.0 0.99 1.12 7.90 < 1.0 >0.50 1.502 0.21 0.015 < 1.0 480.0 50.00 <
318 318-F5-2 1/7/2005 12:54 20326 180.0 0.99 1.12 7.90 < 1.0 >0.50 1.502 0.21 0.015 < 1.0 480.0 50.00 <
318 318-F5-3 1/7/2005 12:54 20326 180.0 0.99 1.12 7.90 < 1.0 >0.50 1.502 0.21 0.015 < 1.0 480.0 50.00 <
312
336 336-E2-1 6/16/2004 12:20 E2-WQP 36.0 1.14 1.26 7.50 0.121 23.8 0.061 0 178.6 0.2 228.0
336 336-E2-2 6/16/2004 12:20 E2-WQP 36.0 1.14 1.26 7.50 0.121 23.8 0.061 0 178.6 0.2 228.0
336 336-E2-3 6/16/2004 12:20 E2-WQP 36.0 1.14 1.26 7.50 0.121 23.8 0.061 0 178.6 0.2 228.0
336 336-N2-1 6/16/2004 13:30 N2-WQP 42.0 0.91 1.04 7.50 0.351 22.9 0.0468 5 177.6 0.3 228.0
336 336-N2-2 6/16/2004 13:30 N2-WQP 42.0 0.91 1.04 7.50 0.351 22.9 0.0468 5 177.6 0.3 228.0
336 336-N2-3 6/16/2004 13:30 N2-WQP 42.0 0.91 1.04 7.50 0.351 22.9 0.0468 5 177.6 0.3 228.0
336 336-M2-1 6/16/2004 14:20 M2- 46.0 0.97 1.14 7.50 0.165 23.2 0.0451 0 177.4 0.1 216.0
336 336-M2-2 6/16/2004 14:20 M2- 46.0 0.97 1.14 7.50 0.165 23.2 0.0451 0 177.4 0.1 216.0
336 336-M2-3 6/16/2004 14:20 M2- 46.0 0.97 1.14 7.50 0.165 23.2 0.0451 0 177.4 0.1 216.0
336 336-F2-1 6/16/2004 15:10 F2-WQP 60.0 0.67 0.86 7.70 0.875 23.9 0.0554 0 238.0 0.1 236.0
336 336-F2-2 6/16/2004 15:10 F2-WQP 60.0 0.67 0.86 7.70 0.875 23.9 0.0554 0 238.0 0.1 236.0
336 336-F2-3 6/16/2004 15:10 F2-WQP 60.0 0.67 0.86 7.70 0.875 23.9 0.0554 0 238.0 0.1 236.0
313
336 336-E3-1 8/5/2004 10:00 E3 40.0 1.10 1.44 7.25 1.14 25.7 1.58 .0327 5 163.7 1.86 0.05 172.0
336 336-E3-2 8/5/2004 10:00 E3 40.0 1.10 1.44 7.25 1.14 25.7 1.58 .0327 5 163.7 1.86 0.05 172.0
336 336-E3-3 8/5/2004 10:00 E3 40.0 1.10 1.44 7.25 1.14 25.7 1.58 .0327 5 163.7 1.86 0.05 172.0
336 336-N3-1 8/5/2004 11:25 N3 40.0 0.98 1.10 7.31 1.13 25.5 1.44 0.0342 0 160.5 1.78 0.3 136.0
336 336-N3-2 8/5/2004 11:25 N3 40.0 0.98 1.10 7.31 1.13 25.5 1.44 0.0342 0 160.5 1.78 0.3 136.0
336 336-N3-3 8/5/2004 11:25 N3 40.0 0.98 1.10 7.31 1.13 25.5 1.44 0.0342 0 160.5 1.78 0.3 136.0
336 336-M3-1 8/5/2004 13:20 M3 42.0 1.11 1.30 7.39 1.04 25.0 1.44 0.032 0 160.5 1.85 0.3 116.0
336 336-M3-2 8/5/2004 13:20 M3 42.0 1.11 1.30 7.39 1.04 25.0 1.44 0.032 0 160.5 1.85 0.3 116.0
336 336-M3-3 8/5/2004 13:20 M3 42.0 1.11 1.30 7.39 1.04 25.0 1.44 0.032 0 160.5 1.85 0.3 116.0
336 336-F3-1 8/5/2004 14:05 F3 48.0 0.80 0.96 7.65 0.79 25.5 1.61 0.0353 5 181.2 2.17 0.7 148.0
336 336-F3-2 8/5/2004 14:05 F3 48.0 0.80 0.96 7.65 0.79 25.5 1.61 0.0353 5 181.2 2.17 0.7 148.0
336 336-F3-3 8/5/2004 14:05 F3 48.0 0.80 0.96 7.65 0.79 25.5 1.61 0.0353 5 181.2 2.17 0.7 148.0
314
336 336-E9-1 10/5/2004 9:20 Ee 38.0 1.16 1.32 7.60 1.31 23.0 1.42 0.0649 0 169.8 2.02 0.2 140.0
336 336-N9-1 10/5/2004 10:58 Ne 44.0 0.99 1.16 7.80 0.53 23.2 1.47 0.0511 0 165.0 1.80 0.3 132.0
336 336-M9-1 10/5/2004 11:35 Me 42.0 1.13 1.33 7.70 0.86 22.2 1.39 0.0638 0 163.3 1.77 0.2 152.0
336 336-F9-1 10/5/2004 12:02 Fe 52.0 0.93 1.09 7.90 1.03 21.8 1.37 0.0546 0 167.8 1.70 0.3 136.0
315
336 336-E4-1 11/23/2004 9:35 E4 48.0 1.50 1.65 7.57 0.135 15.5 1.61 0.058 0 163.7 2.01 0.2 116.0
336 336-E4-2 11/23/2004 9:35 E4 48.0 1.50 1.65 7.57 0.135 15.5 1.61 0.058 0 163.7 2.01 0.2 116.0
336 336-E4-3 11/23/2004 9:35 E4 48.0 1.50 1.65 7.57 0.135 15.5 1.61 0.058 0 163.7 2.01 0.2 116.0
336 336-N4-1 11/23/2004 10:53 N4 52.0 0.83 1.06 7.82 0.046 15.5 1.65 0.0511 0 159.6 2.13 0.3 104.0
336 336-N4-2 11/23/2004 10:53 N4 52.0 0.83 1.06 7.82 0.046 15.5 1.65 0.0511 0 159.6 2.13 0.3 104.0
336 336-N4-3 11/23/2004 10:53 N4 52.0 0.83 1.06 7.82 0.046 15.5 1.65 0.0511 0 159.6 2.13 0.3 104.0
336 336-M4-1 11/23/2004 11:40 M4 48.0 1.11 1.83 7.73 0.028 13.8 1.65 0.0516 0 157.2 2.08 0.3 100.0
336 336-M4-2 11/23/2004 11:40 M4 48.0 1.11 1.83 7.73 0.028 13.8 1.65 0.0516 0 157.2 2.08 0.3 100.0
336 336-M4-3 11/23/2004 11:40 M4 48.0 1.11 1.83 7.73 0.028 13.8 1.65 0.0516 0 157.2 2.08 0.3 100.0
336 336-F4-1 11/23/2004 12:20 F4 70.0 1.21 1.43 7.93 0.136 16.2 1.66 0.0489 0 208.0 2.11 0.3 172.0
336 336-F4-2 11/23/2004 12:20 F4 70.0 1.21 1.43 7.93 0.136 16.2 1.66 0.0489 0 208.0 2.11 0.3 172.0
336 336-F4-3 11/23/2004 12:20 F4 70.0 1.21 1.43 7.93 0.136 16.2 1.66 0.0489 0 208.0 2.11 0.3 172.0
316
336 336-E5-1 12/22/2004 8:50 E1 23.0 1.65 1.80 8.21 0.436 13.2 1.47 0.0488 0 136.6 1.85 0.11
336 336-E5-2 12/22/2004 8:50 E1 23.0 1.65 1.80 8.21 0.436 13.2 1.47 0.0488 0 136.6 1.85 0.11
336 336-E5-3 12/22/2004 8:50 E1 23.0 1.65 1.80 8.21 0.436 13.2 1.47 0.0488 0 136.6 1.85 0.11
336 336-N5-1 12/22/2004 10:20 N1 29.0 0.74 0.88 7.79 0.410 24.7 1.23 0.0440 0 144.6 1.93 0.12
336 336-N5-2 12/22/2004 10:20 N1 29.0 0.74 0.88 7.79 0.410 24.7 1.23 0.0440 0 144.6 1.93 0.12
336 336-N5-3 12/22/2004 10:20 N1 29.0 0.74 0.88 7.79 0.410 24.7 1.23 0.0440 0 144.6 1.93 0.12
336 336-M5-1 12/22/2004 11:00 M1 29.0 1.30 1.47 7.84 0.682 11.2 1.24 0.0532 0 143.4 1.78 0.11
336 336-M5-2 12/22/2004 11:00 M1 29.0 1.30 1.47 7.84 0.682 11.2 1.24 0.0532 0 143.4 1.78 0.11
336 336-M5-3 12/22/2004 11:00 M1 29.0 1.30 1.47 7.84 0.682 11.2 1.24 0.0532 0 143.4 1.78 0.11
336 336-F5-1 12/22/2004 11:45 F1 60.0 1.85 2.06 7.84 0.834 11.8 1.25 0.0492 0 222.0 1.77 0.18
336 336-F5-2 12/22/2004 11:45 F1 60.0 1.85 2.06 7.84 0.834 11.8 1.25 0.0492 0 222.0 1.77 0.18
336 336-F5-3 12/22/2004 11:45 F1 60.0 1.85 2.06 7.84 0.834 11.8 1.25 0.0492 0 222.0 1.77 0.18
317
318
Geo.: Midwest; Source: Groundwater; Treatment: Parallel Conventional Gravity Settling & Mn Greensand
0.060
Manganese (mg/L) .
0.045
0.030
0.015
0.000
3.00 600
Eh (mV)
2.50 500
2.00 400
1.50 300
1.00 200
0.50 100
0.00 0
Alkalinity & Hardness (mg/L as CaCO3) .
6.8 6.8 6.0 6.6 6.50 6.80 6.30 7.00 6.80 6.80 6.60 6.50 6.70 7.00 6.50 7.10
2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04
Figure D.13: Utility 002 - Distribution water quality & manganese data as a function of
location
319
0.060
Manganese (mg/L) .
0.045
0.030
0.015
0.000
TOC Turbidity
4.50 4.50
4.00 4.00
3.50 3.50
Turbidity (NTU)
TOC (mg/L)
3.00 3.00
2.50 2.50
2.00 2.00
1.50 1.50
1.00 1.00
0.50 0.50
0.00 0.00
700 700
TDS (mg/L)
600 600
500 500
400 400
300 300
200 200
100 100
0 0
10.5 12.5 13.3 10.5 6.0 13.0 14.7 16.5 6.5 14.0 17.6 14.5 9.5 13.5 18.5 16.0
6.8 6.8 6.0 6.6 6.50 6.80 6.30 7.00 6.80 6.80 6.60 6.50 6.70 7.00 6.50 7.10
2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.14: Utility 002 - Distribution water quality & manganese data as a function of
location
320
0.060
Manganese (mg/L) .
0.045
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
140.0 18.0
16.0
120.0
Sodium (mg/L)
14.0
Calcium (mg/L)
100.0 12.0
80.0 10.0
60.0 8.0
6.0
40.0
4.0
20.0 2.0
0.0 0.0
10.5 12.5 13.3 10.5 6.0 13.0 14.7 16.5 6.5 14.0 17.6 14.5 9.5 13.5 18.5 16.0
6.8 6.8 6.0 6.6 6.50 6.80 6.30 7.00 6.80 6.80 6.60 6.50 6.70 7.00 6.50 7.10
2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.15: Utility 002 - Distribution water quality & manganese data as a function of
location
321
0.060
Manganese (mg/L) .
0.045
0.030
0.015
0.000
0.0050 Arsenic
0.0040
Arsenic (mg/L)
0.0030
0.0020
0.0010
0.0000
0.8 Orthophosphate
0.7
Phosphate (mg/L as PO4)
0.6
0.5
0.4
0.3
0.2
0.1
0.0
10.5 12.5 13.3 10.5 6.0 13.0 14.7 16.5 6.5 14.0 17.6 14.5 9.5 13.5 18.5 16.0
6.8 6.8 6.0 6.6 6.50 6.80 6.30 7.00 6.80 6.80 6.60 6.50 6.70 7.00 6.50 7.10
2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04 2/26/04 5/20/04 8/31/04 11/9/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.16: Utility 002 - Distribution water quality & manganese data as a function of
location
322
0.120
Manganese (mg/L) .
0.105
0.090
0.075
0.060
0.045
0.030
0.015
0.000
3.50 800
Eh (mV)
3.00 700
2.50 600
2.00 500
1.50 400
1.00 300
0.50 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
80.0
60.0
40.0
20.0
0.0
25.0 23.0 13.3 16.0 26.0 20.6 14.0 16.0 25.0 19.0 13.0 15.0 26.0 21.4 16.0
8.9 9.0 9.0 8.89 8.84 8.22 8.93 9.11 8.98 9.14 8.85 9.13 8.98 4.49 8.90
2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05
Figure D.17: Utility 007 - Distribution water quality & manganese data as a function of
location
323
0.120
Manganese (mg/L) .
0.105
0.090
0.075
0.060
0.045
0.030
0.015
0.000
5.00
TOC Turbidity 1.00
4.50 0.90
4.00 0.80
Turbidity (NTU)
TOC (mg/L)
3.50 0.70
3.00 0.60
2.50 0.50
2.00 0.40
1.50 0.30
1.00 0.20
0.50 0.10
0.00 0.00
250 250
Conductivity (mhos)
200 200
TDS (mg/L)
150 150
100 100
50 50
0 0
25.0 23.0 13.3 16.0 26.0 20.6 14.0 16.0 25.0 19.0 13.0 15.0 26.0 21.4 16.0
8.9 9.0 9.0 8.89 8.84 8.22 8.93 9.11 8.98 9.14 8.85 9.13 8.98 4.49 8.90
2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.18: Utility 007 - Distribution water quality & manganese data as a function of
location
324
0.120
Manganese (mg/L) .
0.105
0.090
0.075
0.060
0.045
0.030
0.015
0.000
0.090
0.075
0.060
0.045
0.030
0.015
0.000
25.0 25.0
Sodium (mg/L)
Calcium (mg/L)
20.0 20.0
15.0 15.0
10.0 10.0
5.0 5.0
0.0 0.0
25.0 23.0 13.3 16.0 26.0 20.6 14.0 16.0 25.0 19.0 13.0 15.0 26.0 21.4 16.0
8.9 9.0 9.0 8.89 8.84 8.22 8.93 9.11 8.98 9.14 8.85 9.13 8.98 4.49 8.90
2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05 2/26/04 5/4/04 11/18/041/10/05
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.19: Utility 007 - Distribution water quality & manganese data as a function of
location
325
0.120
Manganese (mg/L) .
0.105
0.090
0.075
0.060
0.045
0.030
0.015
0.000
0.0070 Arsenic
0.0060
Arsenic (mg/L)
0.0050
0.0040
0.0030
0.0020
0.0010
0.0000
1.0 Orthophosphate
0.9
Phosphate (mg/L as PO4)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
25.0 23.0 13.3 16.0 26.0 20.6 14.0 16.0 25.0 19.0 13.0 15.0 26.0 21.4 16.0
8.9 9.0 9.0 8.89 8.84 8.22 8.93 9.11 8.98 9.14 8.85 9.13 8.98 4.49 8.90
2/26/04 5/4/04 11/18/04 1/10/05 2/26/04 5/4/04 11/18/04 1/10/05 2/26/04 5/4/04 11/18/04 1/10/05 2/26/04 5/4/04 11/18/04 1/10/05
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.20: Utility 007 - Distribution water quality & manganese data as a function of
location
326
0.008
Manganese (mg/L) .
0.007
0.006
0.005
0.004
0.003
0.002
0.001
0.000
3.50 800
Eh (mV)
3.00 700
2.50 600
2.00 500
1.50 400
1.00 300
0.50 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
125.0
100.0
75.0
50.0
25.0
0.0
9.1 23.6 24.7 8.4 9.3 21.0 24.3 13.5 14.2 23.4 25.3 11.1 9.0 22.4 24.8 12.0
7.24 7.27 7.02 6.87 7.29 7.25 7.05 6.97 7.34 7.25 6.98 7.01 7.22 7.27 7.13 6.58
3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04
Figure D.21: Utility 009 - Distribution water quality & manganese data as a function of
location
327
0.008
Manganese (mg/L) .
0.007
0.006
0.005
0.004
0.003
0.002
0.001
0.000
TOC Turbidity
3.50 0.14
3.00 0.12
Turbidity (NTU)
2.50 0.10
TOC (mg/L)
2.00 0.08
1.50 0.06
1.00 0.04
0.50 0.02
0.00 0.00
200
250
TDS (mg/L)
200 150
150
100
100
50
50
0 0
9.1 23.6 24.7 8.4 9.3 21.0 24.3 13.5 14.2 23.4 25.3 11.1 9.0 22.4 24.8 12.0
7.24 7.27 7.02 6.87 7.29 7.25 7.05 6.97 7.34 7.25 6.98 7.01 7.22 7.27 7.13 6.58
3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.22: Utility 009 - Distribution water quality & manganese data as a function of
location
328
0.008
Manganese (mg/L) .
0.007
0.006
0.005
0.004
0.003
0.002
0.001
0.000
0.030
Iron (mg/L)
0.015
0.000
35.0 35.0
30.0 30.0
Sodium (mg/L)
Calcium (mg/L)
25.0 25.0
20.0 20.0
15.0 15.0
10.0 10.0
5.0 5.0
0.0 0.0
9.1 23.6 24.7 8.4 9.3 21.0 24.3 13.5 14.2 23.4 25.3 11.1 9.0 22.4 24.8 12.0
7.24 7.27 7.02 6.87 7.29 7.25 7.05 6.97 7.34 7.25 6.98 7.01 7.22 7.27 7.13 6.58
3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04
Notes:
-- Hatch-marked bars represent all data below MDL.
-- Dissolved iron data is not available for 3/9/04 samples.
Figure D.23: Utility 009 - Distribution water quality & manganese data as a function of
location
329
0.008
Manganese (mg/L) .
0.007
0.006
0.005
0.004
0.003
0.002
0.001
0.000
0.010 Arsenic
0.009
0.008
Arsenic (mg/L)
0.007
0.006
0.005
0.004
0.003
0.002
0.001
0.000
1.8 Orthophosphate
1.6
Phosphate (mg/L as PO4)
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
9.1 23.6 24.7 8.4 9.3 21.0 24.3 13.5 14.2 23.4 25.3 11.1 9.0 22.4 24.8 12.0
7.24 7.27 7.02 6.87 7.29 7.25 7.05 6.97 7.34 7.25 6.98 7.01 7.22 7.27 7.13 6.58
3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04 3/9/04 6/16/04 9/10/04 12/8/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.24: Utility 009 - Distribution water quality & manganese data as a function of
location
330
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
3.50 800
Eh (mV)
3.00 700
2.50 600
2.00 500
1.50 400
1.00 300
0.50 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
80.0
60.0
40.0
20.0
0.0
19.0 18.0 12.0 12.0 16.0 18.8 12.0 7.0 17.0 19.1 13.0 9.0 15.0 19.0 12.0 12.0
8.0 8.0 7.7 8.0 8.00 7.90 7.90 7.90 8.00 8.00 7.80 8.00 8.00 8.00 7.70 8.10
4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05
Figure D.25: Utility 021 - Distribution water quality & manganese data as a function of
location
331
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
TOC Turbidity
3.50 1.00
0.90
3.00
0.80
Turbidity (NTU)
2.50
TOC (mg/L)
0.70
2.00 0.60
0.50
1.50 0.40
1.00 0.30
0.20
0.50
0.10
0.00 0.00
250 250
Conductivity (mhos)
200 200
TDS (mg/L)
150 150
100 100
50 50
0 0
19.0 18.0 12.0 12.0 16.0 18.8 12.0 7.0 17.0 19.1 13.0 9.0 15.0 19.0 12.0 12.0
8.0 8.0 7.7 8.0 8.00 7.90 7.90 7.90 8.00 8.00 7.80 8.00 8.00 8.00 7.70 8.10
4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.26: Utility 021 - Distribution water quality & manganese data as a function of
location
332
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
25.0 25.0
Sodium (mg/L)
Calcium (mg/L)
20.0 20.0
15.0 15.0
10.0 10.0
5.0 5.0
0.0 0.0
19.0 18.0 12.0 12.0 16.0 18.8 12.0 7.0 17.0 19.1 13.0 9.0 15.0 19.0 12.0 12.0
8.0 8.0 7.7 8.0 8.00 7.90 7.90 7.90 8.00 8.00 7.80 8.00 8.00 8.00 7.70 8.10
4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.27: Utility 021 - Distribution water quality & manganese data as a function of
location
333
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.0050 Arsenic
0.0040
Arsenic (mg/L)
0.0030
0.0020
0.0010
0.0000
1.0 Orthophosphate
0.9
Phosphate (mg/L as PO4)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
19.0 18.0 12.0 12.0 16.0 18.8 12.0 7.0 17.0 19.1 13.0 9.0 15.0 19.0 12.0 12.0
8.0 8.0 7.7 8.0 8.00 7.90 7.90 7.90 8.00 8.00 7.80 8.00 8.00 8.00 7.70 8.10
4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05 4/29/04 7/15/04 11/3/04 1/4/05
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.28: Utility 021 - Distribution water quality & manganese data as a function of
location
334
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
3.50 800
ORP (mV)
3.00 700
2.50 600
2.00 500
1.50 400
1.00 300
0.50 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
125.0
100.0
75.0
50.0
25.0
0.0
4.0 20.0 26.5 15.0 9.0 22.5 28.0 23.5 10.0 19.5 26.0 20.0 7.0 16.5 27.0 17.0
8.0 7.8 7.5 7.5 8.30 7.50 7.60 7.30 8.10 7.80 7.70 7.10 8.10 8.30 8.10 7.30
1/24/04 4/20/04 8/27/0411/12/04 1/24/04 4/20/04 8/27/0411/12/04 1/24/04 4/20/04 8/27/04 11/12/04 1/24/04 4/20/04 8/27/0411/12/04
Figure D.29: Utility 022 - Distribution water quality & manganese data as a function of
location
335
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
3.50
TOC Turbidity 1.40
3.00 1.20
Turbidity (NTU)
2.50 1.00
TOC (mg/L)
2.00 0.80
1.50 0.60
1.00 0.40
0.50 0.20
0.00 0.00
250 250
Conductivity (mhos)
200 200
TDS (mg/L)
150 150
100 100
50 50
0 0
4.0 20.0 26.5 15.0 9.0 22.5 28.0 23.5 10.0 19.5 26.0 20.0 7.0 16.5 27.0 17.0
8.0 7.8 7.5 7.5 8.30 7.50 7.60 7.30 8.10 7.80 7.70 7.10 8.10 8.30 8.10 7.30
1/24/04 4/20/04 8/27/04 11/12/04 1/24/04 4/20/04 8/27/04 11/12/04 1/24/04 4/20/04 8/27/04 11/12/04 1/24/04 4/20/04 8/27/04 11/12/04
Figure D.30: Utility 022 - Distribution water quality & manganese data as a function of
location
336
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
35.0 18.0
16.0
30.0
Sodium (mg/L)
14.0
Calcium (mg/L)
25.0 12.0
20.0 10.0
15.0 8.0
6.0
10.0
4.0
5.0 2.0
0.0 0.0
4.0 20.0 26.5 15.0 9.0 22.5 28.0 23.5 10.0 19.5 26.0 20.0 7.0 16.5 27.0 17.0
8.0 7.8 7.5 7.5 8.30 7.50 7.60 7.30 8.10 7.80 7.70 7.10 8.10 8.30 8.10 7.30
1/24/04 4/20/04 8/27/0411/12/04 1/24/04 4/20/04 8/27/04 11/12/04 1/24/04 4/20/04 8/27/0411/12/04 1/24/04 4/20/04 8/27/0411/12/04
Notes:
-- Hatch-marked bars represent all data below MDL.
-- Dissolved iron data is not available for the 1/24/04 samples.
Figure D.31: Utility 022 - Distribution water quality & manganese data as a function of
location
337
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.0050 Arsenic
0.0040
Arsenic (mg/L)
0.0030
0.0020
0.0010
0.0000
0.8 Orthophosphate
0.7
Phosphate (mg/L as PO4)
0.6
0.5
0.4
0.3
0.2
0.1
0.0
4.0 20.0 26.5 15.0 9.0 22.5 28.0 23.5 10.0 19.5 26.0 20.0 7.0 16.5 27.0 17.0
8.0 7.8 7.5 7.5 8.30 7.50 7.60 7.30 8.10 7.80 7.70 7.10 8.10 8.30 8.10 7.30
1/24/04 4/20/04 8/27/04 11/12/04 1/24/04 4/20/04 8/27/04 11/12/04 1/24/04 4/20/04 8/27/04 11/12/04 1/24/04 4/20/04 8/27/04 11/12/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.32: Utility 022 - Distribution water quality & manganese data as a function of
location
338
0.045
Manganese (mg/L) .
0.030
0.015
0.000
3.00
800
Eh (mV)
2.50 700
2.00 600
1.50 500
400
1.00
300
0.50 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
125.0
100.0
75.0
50.0
25.0
0.0
4.1 13.4 12.8 4.9 12.7 12.4 4.5 13.8 13.2 4.3 16.9 15.1
7.14 7.18 6.96 7.12 7.24 6.99 7.14 7.28 7.02 7.16 7.26 7.06
2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04
Figure D.33: Utility 216 - Distribution water quality & manganese data as a function of
location
339
0.045
Manganese (mg/L) .
0.030
0.015
0.000
3.50
TOC Turbidity 1.40
3.00 1.20
Turbidity (NTU)
2.50 1.00
TOC (mg/L)
2.00 0.80
1.50 0.60
1.00 0.40
0.50 0.20
0.00 0.00
300 200
TDS (mg/L)
250
150
200
150 100
100
50
50
0 0
4.1 13.4 12.8 4.9 12.7 12.4 4.5 13.8 13.2 4.3 16.9 15.1
7.14 7.18 6.96 7.12 7.24 6.99 7.14 7.28 7.02 7.16 7.26 7.06
2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04
Figure D.34: Utility 216 - Distribution water quality & manganese data as a function of
location
340
0.045
Manganese (mg/L) .
0.030
0.015
0.000
3.00
800
Eh (mV)
2.50 700
2.00 600
1.50 500
400
1.00
300
0.50 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
125.0
100.0
75.0
50.0
25.0
0.0
4.1 13.4 12.8 4.9 12.7 12.4 4.5 13.8 13.2 4.3 16.9 15.1
7.14 7.18 6.96 7.12 7.24 6.99 7.14 7.28 7.02 7.16 7.26 7.06
2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04
Figure D.35: Utility 216 - Distribution water quality & manganese data as a function of
location
341
0.045
Manganese (mg/L) .
0.030
0.015
0.000
3.50
TOC Turbidity 1.40
3.00 1.20
Turbidity (NTU)
2.50 1.00
TOC (mg/L)
2.00 0.80
1.50 0.60
1.00 0.40
0.50 0.20
0.00 0.00
300 200
TDS (mg/L)
250
150
200
150 100
100
50
50
0 0
4.1 13.4 12.8 4.9 12.7 12.4 4.5 13.8 13.2 4.3 16.9 15.1
7.14 7.18 6.96 7.12 7.24 6.99 7.14 7.28 7.02 7.16 7.26 7.06
2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04
Figure D.36: Utility 216 - Distribution water quality & manganese data as a function of
location
342
0.045
Manganese (mg/L) .
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
35.0 35.0
30.0 30.0
Sodium (mg/L)
Calcium (mg/L)
25.0 25.0
20.0 20.0
15.0 15.0
10.0 10.0
5.0 5.0
0.0 0.0
4.1 13.4 12.8 4.9 12.7 12.4 4.5 13.8 13.2 4.3 16.9 15.1
7.14 7.18 6.96 7.12 7.24 6.99 7.14 7.28 7.02 7.16 7.26 7.06
2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04
Figure D.37: Utility 269 - Distribution water quality & manganese data as a function of
location
343
0.045
Manganese (mg/L) .
0.030
0.015
0.000
0.0050 Arsenic
0.0040
Arsenic (mg/L)
0.0030
0.0020
0.0010
0.0000
2.5 Orthophosphate
Phosphate (mg/L as PO4)
2.0
1.5
1.0
0.5
0.0
4.1 13.4 12.8 4.9 12.7 12.4 4.5 13.8 13.2 4.3 16.9 15.1
7.14 7.18 6.96 7.12 7.24 6.99 7.14 7.28 7.02 7.16 7.26 7.06
2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04 2/11/04 5/27/04 8/19/04
Figure D.38: Utility 269 - Distribution water quality & manganese data as a function of
location
344
0.150
0.135
0.120
0.105
0.090
0.075
0.060
0.045
0.030
0.015
0.000
0.030
Iron (mg/L)
0.015
0.000
35.0 35.0
30.0 30.0
Sodium (mg/L)
Calcium (mg/L)
25.0 25.0
20.0 20.0
15.0 15.0
10.0 10.0
5.0 5.0
0.0 0.0
21.5 18.6 21.5 17.9 21.1 16.4
Notes:
-- Hatch-marked bars represent all data below MDL.
-- Samples for the mid location were not collected for this utility.
Figure D.39: Utility 269 - Distribution water quality & manganese data as a function of
location
345
0.150
0.135
0.120
0.105
0.090
0.075
0.060
0.045
0.030
0.015
0.000
0.0050 Arsenic
0.0040
Arsenic (mg/L)
0.0030
0.0020
0.0010
0.0000
1.60
1.40
1.20
1.00
0.80
0.60
0.40
0.20
0.00
21.5 18.6 21.5 17.9 21.1 16.4
Notes:
-- Hatch-marked bars represent all data below MDL.
-- Samples for the mid location were not collected for this utility.
Figure D.40: Utility 269 - Distribution water quality & manganese data as a function of
location
346
0.030
0.015
0.000
3.00
800
Eh (mV)
2.50 700
2.00 600
1.50 500
400
1.00
300
0.50 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
125.0
100.0
75.0
50.0
25.0
0.0
5.0 21.4 22.8 20.0 5.0 16.6 23.9 20.0 5.0 16.7 27.4 25.3 18.3 5.0 17.0 23.9 19.3
7.3 7.3 7.6 7.2 7.40 7.90 7.50 7.60 7.20 7.90 7.5 7.90 7.90 7.30 7.70 8.00 7.90
Figure D.41: Utility 315 - Distribution water quality & manganese data as a function of
location
347
0.030
0.015
0.000
3.50
TOC Turbidity 0.08
3.00 0.07
0.06
Turbidity (NTU)
2.50
TOC (mg/L)
0.05
2.00
0.04
1.50
0.03
1.00
0.02
0.50 0.01
0.00 0.00
350
200
TDS (mg/L)
300
250 150
200
100
150
100
50
50
0 0
5.0 21.4 22.8 20.0 5.0 16.6 23.9 20.0 5.0 16.7 27.4 25.3 18.3 5.0 17.0 23.9 19.3
7.3 7.3 7.6 7.2 7.40 7.90 7.50 7.60 7.20 7.90 7.5 7.90 7.90 7.30 7.70 8.00 7.90
2/24/04 5/26/04 8/26/04 11/1/04 2/25/04 5/27/04 8/26/04 11/1/04 2/26/04 5/27/04 6/2/04 8/26/04 11/1/04 2/27/04 5/27/04 8/26/04 11/1/04
Notes:
-- Mid 2 sample on 5/27/04 was an episodic sample taken at a different location than the other mid samples.
-- Hatch-marked bars represent all data below MDL.
Figure D.42: Utility 315 - Distribution water quality & manganese data as a function of
location
348
0.030
0.015
0.000
0.120
0.105
0.090
0.075
0.060
0.045
0.030
0.015
0.000
Sodium (mg/L)
35.0 35.0
Calcium (mg/L)
30.0 30.0
25.0 25.0
20.0 20.0
15.0 15.0
10.0 10.0
5.0 5.0
0.0 0.0
5.0 21.4 22.8 20.0 5.0 16.6 23.9 20.0 5.0 16.7 27.4 25.3 18.3 5.0 17.0 23.9 19.3
7.3 7.3 7.6 7.2 7.40 7.90 7.50 7.60 7.20 7.90 7.5 7.90 7.90 7.30 7.70 8.00 7.90
Notes:
-- Mid 2 sample on 5/27/04 was an episodic sample taken at a different location than the other mid samples.
-- Hatch-marked bars represent all data below MDL.
Figure D.43: Utility 315 - Distribution water quality & manganese data as a function of
location
349
0.030
0.015
0.000
0.0050 Arsenic
0.0040
Arsenic (mg/L)
0.0030
0.0020
0.0010
0.0000
1.6 Orthophosphate
1.4
Phosphate (mg/L as PO4)
1.2
1.0
0.8
0.6
0.4
0.2
0.0
5.0 21.4 22.8 20.0 5.0 16.6 23.9 20.0 5.0 16.7 27.4 25.3 18.3 5.0 17.0 23.9 19.3
7.3 7.3 7.6 7.2 7.40 7.90 7.50 7.60 7.20 7.90 7.5 7.90 7.90 7.30 7.70 8.00 7.90
2/24/04 5/26/04 8/26/04 11/1/04 2/25/04 5/27/04 8/26/04 11/1/04 2/26/04 5/27/04 6/2/04 8/26/04 11/1/04 2/27/04 5/27/04 8/26/04 11/1/04
Notes:
-- Mid 2 sample on 5/27/04 was an episodic sample taken at a different location than the other mid samples.
-- Hatch-marked bars represent all data below MDL.
Figure D.44: Utility 315 - Distribution water quality & manganese data as a function of
location
350
0.075
Manganese (mg/L) .
0.060
0.045
0.030
0.015
0.000
1.75 1000
900
Chlorine (mg/L)
1.50
800
Eh (mV)
1.25 700
1.00 600
0.75 500
400
0.50
300
0.25 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
175.0
150.0
125.0
100.0
75.0
50.0
25.0
0.0
20.00 15.00 21.70 16.70 23.3 17.8
Figure D.45: Utility 318 - Distribution water quality & manganese data as a function of
location
351
0.075
Manganese (mg/L) .
0.060
0.045
0.030
0.015
0.000
16.00
TOC Turbidity 0.80
14.00 0.70
12.00 0.60
Turbidity (NTU)
TOC (mg/L)
10.00 0.50
8.00 0.40
6.00 0.30
4.00 0.20
2.00 0.10
0.00 0.00
500 250
Conductivity (mhos)
400 200
TDS (mg/L)
300 150
200 100
100 50
0 0
20.00 15.00 21.70 16.70 23.3 17.8
Notes:
-- Samples for the near location were not collected for this utility.
-- Hatch-marked bars represent all data below MDL.
Figure D.46: Utility 318 - Distribution water quality & manganese data as a function of
location
352
0.075
Manganese (mg/L) .
0.060
0.045
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
50.0 50.0
Sodium (mg/L)
Calcium (mg/L)
40.0 40.0
30.0 30.0
20.0 20.0
10.0 10.0
0.0 0.0
20.00 15.00 21.70 16.70 23.3 17.8
Notes:
-- Samples for the near location were not collected for this utility.
-- Hatch-marked bars represent all data below MDL.
Figure D.47: Utility 318 - Distribution water quality & manganese data as a function of
location
353
0.075
Manganese (mg/L) .
0.060
0.045
0.030
0.015
0.000
0.0150 Arsenic
0.0120
Arsenic (mg/L)
0.0090
0.0060
0.0030
0.0000
1.60
1.40
1.20
1.00
0.80
0.60
0.40
0.20
0.00
20.00 15.00 21.70 16.70 23.3 17.8
Notes:
-- Samples for the near location were not collected for this utility.
-- Hatch-marked bars represent all data below MDL.
Figure D.48: Utility 318 - Distribution water quality & manganese data as a function of
location
354
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
3.00
800
Eh (mV)
2.50 700
2.00 600
1.50 500
400
1.00
300
0.50 200
0.00 100
Alkalinity & Hardness (mg/L as CaCO3) .
80.0
60.0
40.0
20.0
0.0
23.8 25.7 15.5 13.2 22.9 25.5 15.5 24.7 23.2 25.0 13.8 11.2 23.9 25.5 16.2 11.8
7.50 7.25 7.57 8.21 7.50 7.31 7.82 7.79 7.50 7.39 7.73 7.84 7.70 7.65 7.93 7.84
6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.49: Utility 336 - Distribution water quality & manganese data as a function of
location
355
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
TOC Turbidity
2.50 1.00
2.00 0.80
Turbidity (NTU)
TOC (mg/L)
1.50 0.60
1.00 0.40
0.50 0.20
0.00 0.00
250 250
Conductivity (mhos)
200 200
TDS (mg/L)
150 150
100 100
50 50
0 0
23.8 25.7 15.5 13.2 22.9 25.5 15.5 24.7 23.2 25.0 13.8 11.2 23.9 25.5 16.2 11.8
7.50 7.25 7.57 8.21 7.50 7.31 7.82 7.79 7.50 7.39 7.73 7.84 7.70 7.65 7.93 7.84
6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.50: Utility 336 - Distribution water quality & manganese data as a function of
location
356
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
Sodium (mg/L)
14.0
Calcium (mg/L)
20.0
12.0
15.0 10.0
8.0
10.0
6.0
4.0
5.0
2.0
0.0 0.0
23.8 25.7 15.5 13.2 22.9 25.5 15.5 24.7 23.2 25.0 13.8 11.2 23.9 25.5 16.2 11.8
7.50 7.25 7.57 8.21 7.50 7.31 7.82 7.79 7.50 7.39 7.73 7.84 7.70 7.65 7.93 7.84
6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.51: Utility 336 - Distribution water quality & manganese data as a function of
location
357
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.0070 Arsenic
0.0060
Arsenic (mg/L)
0.0050
0.0040
0.0030
0.0020
0.0010
0.0000
1.2 Orthophosphate
Phosphate (mg/L as PO4)
1.0
0.8
0.6
0.4
0.2
0.0
23.8 25.7 15.5 13.2 22.9 25.5 15.5 24.7 23.2 25.0 13.8 11.2 23.9 25.5 16.2 11.8
7.50 7.25 7.57 8.21 7.50 7.31 7.82 7.79 7.50 7.39 7.73 7.84 7.70 7.65 7.93 7.84
6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04 6/16/04 8/5/04 11/23/0412/22/04
Notes:
-- Hatch-marked bars represent all data below MDL.
Figure D.52: Utility 336 - Distribution water quality & manganese data as a function of
location
358
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
3.50 800
Eh (mV)
3.00 700
2.50 600
2.00 500
1.50 400
1.00 300
0.50 200
0.00 100
125.0
100.0
75.0
50.0
25.0
0.0
6/10/04 12/29/04 6/10/04 12/29/04 6/10/04 12/29/04 6/10/04 12/29/04
Figure D.53: Utility 400 - Distribution water quality & manganese data as a function of
location
359
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
3.50
TOC Turbidity 1.00
0.90
3.00
0.80
Turbidity (NTU)
2.50
TOC (mg/L)
0.70
2.00 0.60
0.50
1.50 0.40
1.00 0.30
0.20
0.50
0.10
0.00 0.00
1
250
1
1
Conductivity (mhos)
200
1
TDS (mg/L)
1 150
0
100
0
0
50
0
0 0
6/10/04 12/29/04 6/10/04 12/29/04 6/10/04 12/29/04 6/10/04 12/29/04
Notes:
-- TOC, turbidity, conductivity and TDS data was not available.
-- Only two sets of samples were collected for this utility.
Figure D.54: Utility 400 - Distribution water quality & manganese data as a function of
location
360
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
25.0 25.0
Sodium (mg/L)
20.0 20.0
Calcium (mg/L)
15.0 15.0
10.0 10.0
5.0 5.0
0.0 0.0
6/10/04 12/29/04 6/10/04 12/29/04 6/10/04 12/29/04 6/10/04 12/29/04
Notes:
-- Hatch-marked bars represent all data below MDL.
-- Only two sets of samples were collected for this utility.
Figure D.55: Utility 400 - Distribution water quality & manganese data as a function of
location
361
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.0060 Arsenic
0.0050
Arsenic (mg/L)
0.0040
0.0030
0.0020
0.0010
0.0000
1.2 Orthophosphate
1.0
Phosphate (mg/L as PO4)
0.8
0.6
0.4
0.2
0.0
6/10/04 12/29/04 6/10/04 12/29/04 6/10/04 12/29/04 6/10/04 12/29/04
Notes:
-- Hatch-marked bars represent all data below MDL.
-- Only two sets of samples were collected for this utility.
-- Orthophosphate data was not available.
Figure D.56: Utility 400 - Distribution water quality & manganese data as a function of
location
362
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
3.50 800
Eh (mV)
3.00 700
2.50 600
2.00 500
1.50 400
1.00 300
0.50 200
0.00 100
125.0
100.0
75.0
50.0
25.0
0.0
6/9/04 6/9/04 1/0/00 1/0/00
Figure D.57: Utility 401 - Distribution water quality & manganese data as a function of
location
363
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
3.50
TOC Turbidity 1.00
0.90
3.00
0.80
Turbidity (NTU)
2.50
TOC (mg/L)
0.70
2.00 0.60
0.50
1.50 0.40
1.00 0.30
0.20
0.50
0.10
0.00 0.00
250 250
Conductivity (mhos)
200 200
TDS (mg/L)
150 150
100 100
50 50
0 0
6/9/04 6/9/04 1/0/00 1/0/00
Notes:
-- TOC, turbidity, conductivity and TDS data was not available.
-- Only one set of samples were collected for this utility.
Figure D.58: Utility 401 - Distribution water quality & manganese data as a function of
location
364
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.075
0.060
Iron (mg/L)
0.045
0.030
0.015
0.000
30.0 30.0
25.0 25.0
Sodium (mg/L)
Calcium (mg/L)
20.0 20.0
15.0 15.0
10.0 10.0
5.0 5.0
0.0 0.0
6/9/04 6/9/04 1/0/00 1/0/00
Notes:
-- Hatch-marked bars represent all data below MDL.
-- Only one set of samples were collected for this utility.
Figure D.59: Utility 401 - Distribution water quality & manganese data as a function of
location
365
Manganese (mg/L) . 0.045 Dissolved Manganese (<0.22 m) Total Manganese (entire bar height)
0.030
0.015
0.000
0.0050 Arsenic
0.0040
Arsenic (mg/L)
0.0030
0.0020
0.0010
0.0000
1.2 Orthophosphate
1.0
Phosphate (mg/L as PO4)
0.8
0.6
0.4
0.2
0.0
6/9/04 6/9/04 1/0/00 1/0/00
Notes:
-- Hatch-marked bars represent all data below MDL.
-- Only one set of samples were collected for this utility.
-- Orthophosphate data was not available.
Figure D.60: Utility 401 - Distribution water quality & manganese data as a function of
location
366
Dissolved Mn (mg/L)
269 269 269 269
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315 315 315 315
0.10 318 0.10 318 0.10 318 0.10 318
336 336 336 336
400 400 400 400
401 401 401 401
0.05 0.05 0.05 0.05
2 2 7 2
Particulate Manganese vs Total Iron Particulate Manganese vs. Total Manganese Total Manganese vs Total Calcium Total Manganese vs Total Arsenic
0.20 7 7 9 0.20 7
0.20 0.20
9 9 21 9
21 21 Utility 2 data omitted 22 21
22 22 216 22
0.15 0.15 0.15 216
216 0.15 216 269
Particulate Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315
315 315 318
0.10
318
0.10 318 0.10 318 0.10 336
336
336 336 400
400
400 400 401
401
401 401 0.05
0.05 0.05 0.05
0.00
0.00 0.00 0.00
0.00 0.05 0.10 0.15 0.20
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0 10 20 30 40 50
Total Fe (mg/L) Total Mn (mg/L) Total Ca (mg/L) Total Arsenic (mg/L)
2 2 2
Dissolved Manganese vs Total Iron Particulate Manganese vs Particulatel Iron Total Manganese vs Hardness
0.20 7 7 7
0.20
9 9 0.20
9
21 21
21
22 22
0.15 0.15 216 22
216 0.15
Particulate Mn (mg/L)
216
Dissolved Mn (mg/L)
269 269
Total Mn (mg/L)
315 269
315
318 315
0.10 318 0.10 336 0.10
336 318
400
400 336
401
401 400
0.05 0.05 0.05
401
2
Manganese < 0.22m vs. Manganese < 30kDa 2 Dissolved Manganese vs Dissolved Iron Total Manganese vs Hardness
7 7
7 0.20 0.20
0.20 9 9
9
21 21 Utility 2 data omitted 21
2 22
R = 0.9304 22
Manganese < 0.22 m (mg/L)
22
0.15 216 0.15 216 0.15 216
Dissolved Mn (mg/L)
Total Mn (mg/L)
315 315 315
318 318 318
0.10 0.10 0.10
336 336 336
400 400 400
401 401 401
0.05 0.05 0.05
Figure D.42 Correlations of distribution system water metals to total, particulate and dissolved manganese.
367
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315 315 318
318 318 318 336
0.10 336 0.10 0.10 0.10
336 336
2 2
Total Manganese vs Total Chlorine Total Manganese vs Orthophosphate Total Manganese vs Oxidation Reduction Potential 2 Total Manganese vs Sulfate
0.20 7 0.20 0.20 0.20 22
2 9
9 318
9
21
22
22
0.15 0.15 216 0.15 0.15
216
269
269
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315
315
318
0.10 318 0.10 0.10 0.10
336
336
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315 315
318 318
0.10 0.10 0.10 0.10
336 336
2 2
Total Manganese vs pH Total Manganese vs Total Phosphate Total Manganese vs Apparent Color Total Manganese vs Temperature
0.20 7 0.20 0.20 2 0.20 7
9 7 9
21 9 21
22 22 22
0.15 0.15 269 0.15 0.15
216 216 269
318
269 216
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
Total Mn (mg/L)
315 315
0.10 318 0.10 0.10 0.10 318
336 336
Figure D.43 Correlations of distribution system water manganese to single water quality parameters.
368
Far Mn (mg/L)
Far Mn (mg/L)
R2 = 0.64
0.05 R2 = 0.81
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
2 PLOT #4 2
PLOT #3
7 Far Mn (Total & Diss.) vs Entry Mn (Total) 7
Far Mn (Total & Diss.) vs Entry Mn (Total)
0.20 9 9
0.100
21 One sequestration facility omitted 21
22 22
Far Total Mn (mg/L)
0.00 0.000
0.00 0.05 0.10 0.15 0.20 0.000 0.025 0.050 0.075 0.100
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
Figure D.45 Correlations of seasonal testing distribution system manganese: entry point and far point of system
369
22 22
0.15
216
Far Dissolved Mn
216
0.04
269 315
(mg/L)
0.10 315 336
318
0.02
0.05 336
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.02 0.04 0.06
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
PLOT #6 2
Far Mn (Total & Diss.) vs Entry Mn (Total) 7
9
0.100
21
Far Dissolved Mn (mg/L)
22
0.075
216
315
0.050 318
336
0.025
0.000
0.000 0.025 0.050 0.075 0.100
Entry Total Mn (mg/L)
Figure D.46 Correlations of seasonal testing distribution system manganese: entry point and far point of system
370
0.050 0.050
R2 = 0.74 315
318
336
0.025 R2 = 0.63 0.025
0.000 0.000
0.000 0.025 0.050 0.075 0.000 0.025 0.050 0.075
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
2 2
PLOT #10 PLOT #11
7 7
Mid Mn (Diss.) vs Entry Mn (Total) Mid Mn (Diss.) vs Entry Mn (Total)
9 9
0.075 0.06
21 21
Sequestration facilities omitted
Mid Dissolved Mn (mg/L)
22 22
216
Mid Dissolved Mn
0.050 216
0.04
315 315
(mg/L)
318 336
336
0.025 0.02
0.000 0.00
0.000 0.025 0.050 0.075 0.00 0.02 0.04 0.06
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
Figure D.47 Correlations of seasonal testing distribution system manganese: entry point and mid point of system
371
21
0.10 22
0.10
216
2
R = 0.97 269
0.05 0.05
315
336
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
0.04 216
315
(mg/L)
315
336
336
0.02 0.02
0.00 0.00
0.00 0.02 0.04 0.06 0.00 0.02 0.04 0.06
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
Figure D.48 Correlations of seasonal testing distribution system manganese: entry point and near point of system
372
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.02 0.04 0.06
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
Figure D.49 Correlations of seasonal testing distribution system manganese: entry point and near point of system
373
269
0.10 0.10
315
R2 = 0.66
336
0.05 0.05
R2 = 0.43
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Near Total Mn (mg/L) Near Total Mn (mg/L)
Figure D.50 Correlations of seasonal testing distribution system manganese: far point and near point of system
374
2
R = 0.77 216
269
0.05 0.05 315
R2 = 0.58 318
0.03 0.03 336
0.00
0.00
0.00 0.05 0.10 0.15 0.20
0.00 0.05 0.10 0.15 0.20
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
Figure D.51 Correlations of seasonal testing distribution system manganese: change in manganese from entry point to far
point in the distribution system
375
0.02 2
0.02 216
R = 0.35
315
R2 = 0.22
0.00 0.00 318
0.000 0.025 0.050 0.075 0.100 0.000 0.025 0.050 0.075 0.100 336
-0.02 -0.02
-0.04 -0.04
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
Figure D.52 Correlations of seasonal testing distribution system manganese: change in manganese from entry point to mid
point in the distribution system
376
-0.10 -0.10
-0.20 -0.15
Entry Total Mn (mg/L) Entry Total Mn (mg/L)
Change in Mn (mg/L)
0.00 21
2
0.00 0.05 0.10 0.15 0.20 22 7
216 0.00
9
269 0.00 0.05 0.10 0.15 0.20
21
-0.02 315
22
336 -0.01
216
269
-0.04 -0.02 315
Entry Total Mn(mg/L) Entry Total Mn (mg/L) 336
Figure D.53 Correlations of seasonal testing distribution system manganese: change in manganese from entry point to near
point in the distribution system
377
-0.01 -0.01
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Near Total Mn (mg/L) Near Total Mn (mg/L)
0.03 R2 = 0.57
216 216
0.01
0.00
0.00 0.02 0.04 0.06
0.00 0.02 0.04 0.06 -0.01
-0.01
Near Total Mn (mg/L) Near Total Mn (mg/L)
Figure D.54 Correlations of seasonal testing distribution system manganese: change in manganese from near point to far point
in the distribution system
378
Groundwater Facilities
Number of
facilities Total < 0.22m < 30 kDa Particulate Colloidal
providing Manganese Manganese Manganese Manganese Manganese
WQ parameter data 'n' value R R R R R
Total Manganese 4 47
< 0.22 m Manganese 4 47 0.8634
< 30 kDa Manganese 4 47 0.6383 0.9135
Particulate Manganese 4 47 0.3940 0.0874 0.0027
Colloidal Manganese 4 47 0.6868 0.4119 0.1504 0.6247
379
380
Particulate Mn (mg/L)
0.15
Colloidal Mn (mg/L)
0.10 0.10 0.10 0.10
0.20 Total Manganese vs. 30 kDa Filtered Manganese 0.20 0.22 m Filtered Manganese vs. Particulate Manganese 0.20 30 kDa Filtered Manganese vs. Colloidal Manganese
0.15
0.15 0.15
Colloidal Mn (mg/L)
Particulate Mn (mg/L)
0.10
0.10 0.10
0.05
0.05 0.05
0.00
0.00 0.05 0.10 0.15 0.20
0.00 0.00
0.00 0.05 0.10 0.15 0.20 -0.05 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L)
0.20 Total Manganese vs. Particulate Manganese 0.20 0.22 m Filtered Manganese vs. Colloidal Manganese
Colloidal Mn (mg/L)
0.10 0.10
0.05 0.05
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L)
y = 0.2155x - 0.0021
2
0.15 R = 0.6868
Colloidal Mn (mg/L)
0.10
0.05
0.00
0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L)
Figure D.55 Correlations of speciated manganese to speciated manganese of seasonal testing distribution system manganese: groundwater facilities only.
381
0.15
Particulate Fe (mg/L)
0.15 0.15
Colloidal Fe (mg/L)
0.10 0.10 0.10
0.10
Total Iron vs. 30 kDa Filtered Iron 0.20 0.22 m Filtered Iron vs. Particulate Iron 0.20 30 kDa Filtered Iron vs. Colloidal Iron
0.20
y = -0.198x + 0.0091 y = -0.3604x + 0.0064
y = 0.0766x + 0.0012
R2 = 0.0281 R2 = 0.0304
R2 = 0.0534
30 kDa Filtered Fe (mg/L)
Particulate Fe (mg/L)
Colloidal Fe (mg/L)
0.10 0.10 0.10
Total Iron vs. Particulate Iron 0.20 0.22 m Filtered Iron vs. Colloidal Iron
0.20
y = 0.5987x - 0.0017 y = 0.8596x - 0.0013
R2 = 0.5137 R2 = 0.7871
0.15 0.15
Particulate Fe (mg/L)
Colloidal Fe (mg/L)
0.10 0.10
0.05 0.05
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Fe (mg/L) 0.22 m Filtered Fe (mg/L)
y = 0.3248x + 0.0005
R2 = 0.2245
0.15
Colloidal Fe (mg/L)
0.10
0.05
0.00
0.00 0.05 0.10 0.15 0.20
Total Fe (mg/L)
Figure D.56 Correlations of speciated iron to speciated iron of seasonal testing distribution system manganese: groundwater facilities only
382
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. Sodium 0.22 m Filtered Manganese vs. Sodium 30 kDa Filtered Manganese vs. Sodium Particulate Manganese vs. Sodium Colloidal Manganese vs. Sodium
70 70 70 70 70
y = 168.31x + 17.414 y = 305.52x + 17.249 y = 319.84x + 21.891
60 60 y = 244.06x + 17.063 60 60 y = 41.85x + 23.446 60
R2 = 0.3327 R2 = 0.5039 R2 = 0.0812
R2 = 0.4645 R2 = 0.0031
50 50 50 50 50
Sodium (mg/L)
Sodium (mg/L)
Sodium (mg/L)
Sodium (mg/L)
Sodium (mg/L)
40 40 40 40 40
30 30 30 30 30
20 20 20 20 20
10 10 10 10 10
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. Calcium 0.22 m Filtered Manganese vs. Calcium 30 kDa Filtered Manganese vs. Calcium Particulate Manganese vs. Calcium Colloidal Manganese vs. Calcium
160 160 160 160 160
140 y = -212.25x + 69.636 y = -328.69x + 70.663 140 140 y = 39.979x + 61.056 140 y = -557.76x + 64.952
140 y = -557.76x + 64.952
R2 = 0.0426 R2 = 0.0678 R2 = 0.0002 R2 = 0.0199
120 120 120 R2 = 0.0199 120 120
Calcium (mg/L)
Calcium (mg/L)
Calcium (mg/L)
Calcium (mg/L)
Calcium (mg/L)
80 80 80 80 80
60 60 60 60 60
40 40 40 40 40
20 20 20 20 20
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Filtered Mn (mg/L) Colloidal Filtered Mn (mg/L)
Figure D.57 Correlations of speciated manganese to water quality parameters of seasonal testing distribution system manganese: groundwater facilities only
383
50 50 50 50 50
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. Turbidity 0.22 m Filtered Manganese vs. Turbidity 30 kDa Filtered Manganese vs. Turbidity Particulate Manganese vs. Turbidity Colloidal Manganese vs. Turbidity
7 7
7 7 7
6 6 6
6 6
y = 9.1712x + 1.3844
5 y = 7.0389x + 1.3821 5 2 5 y = -5.373x + 1.7158 5
5 R = 0.0587
Turbidity (NTU)
Turbidity (NTU)
Turbidity (NTU)
Turbidity (NTU)
Turbidity (NTU)
y = 3.6708x + 1.4421 2
R = 0.0495 2
4 R = 0.0076
4
2
R = 0.0206 4 4 4
y = 5.1545x + 1.5865
3 3 3 3 3 R2 = 0.0032
2 2 2 2 2
1 1 1 1 1
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. UV254 Absorbance 0.22 m Filtered Manganese vs. UV254 Absorbance 30 kDa Filtered Manganese vs. UV254 Absorbance Particulate Manganese vs. UV254 Absorbance Colloidal Manganese vs. UV254 Absorbance
0.080 0.080 0.080 0.080
0.080
y = -0.124x + 0.0175 y = -0.2562x + 0.0181
0.070 0.070 0.070 0.070 0.070 2
y = -0.1318x + 0.0231 y = -0.1601x + 0.0225 y = -0.1802x + 0.0216 2
R = 0.0798 R = 0.15
0.060 2 0.060 2
R = 0.4827 0.060 2
R = 0.438 0.060 0.060
R = 0.4822
0.050 0.050 0.050 0.050 0.050
Total Manganese vs. TOC 0.22 m Filtered Manganese vs. TOC 30 kDa Filtered Manganese vs. TOC Particulate Manganese vs. TOC Colloidal Manganese vs. TOC
14 14 14 14 14
TOC (mg/L)
TOC (mg/L)
TOC (mg/L)
TOC (mg/L)
TOC (mg/L)
8 8 8 8 8
6 6 6 6 6
4 4 4 4 4
2 2 2 2 2
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Filtered Mn (mg/L) Colloidal Filtered Mn (mg/L)
Figure D.58 Correlations of speciated manganese to water quality parameters of seasonal testing distribution system manganese: groundwater facilities only
384
Conductivity (mho/cm)
Conductivity (mho/cm)
Conductivity (mho/cm)
Conductivity (mho/cm)
Conductivity (mho/cm)
700 700 700 700 700
600 600 600 600 600
500 500 500 500 500
400 400 400 400 400
300 300 300 300 300
200 200 200 200 200
100 100 100 100 100
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Filtered Mn (mg/L) Colloidal Filtered Mn (mg/L)
Total Manganese vs. Orthophosphate 0.22 m Filtered Manganese vs. Orthophosphate 30 kDa Filtered Manganese vs. Orthophosphate Particulate Manganese vs. Orthophosphate Colloidal Manganese vs. Orthophosphate
1.0 1.0 1.0 1.0 1.0
0.9 0.9 0.9 0.9 y = -1.3323x + 0.5171 0.9 y = -1.4692x + 0.5098
y = -0.4237x + 0.5191 y = -0.2867x + 0.5072 y = -0.1536x + 0.5007
0.8 0.8 0.8 R2 = 0.0237 0.8 R2 = 0.0134
R2 = 0.0137 0.8 R2 = 0.0042 R2 = 0.0008
Orthophosphate (mg/L)
Orthophosphate (mg/L)
Orthophosphate (mg/L)
Orthophosphate (mg/L)
Orthophosphate (mg/L)
0.7 0.7 0.7 0.7 0.7
0.6 0.6 0.6 0.6 0.6
0.5 0.5 0.5 0.5 0.5
0.4 0.4 0.4 0.4 0.4
0.3 0.3 0.3 0.3 0.3
0.2 0.2 0.2 0.2 0.2
0.1 0.1 0.1 0.1 0.1
0.0 0.0 0.0 0.0 0.0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Filtered Mn (mg/L) Colloidal Filtered Mn (mg/L)
Total Manganese vs. Sulfate 0.22 m Filtered Manganese vs. Sulfate 30 kDa Filtered Manganese vs. Sulfate Particulate Manganese vs. Sulfate Colloidal Manganese vs. Sulfate
250 250 250 250 250
Sulfate (mg/L)
Sulfate (mg/L)
Sulfate (mg/L)
Sulfate (mg/L)
Sulfate (mg/L)
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. Total Dissolved Solids 0.22 m Filtered Manganese vs. Total Dissolved Solids 30 kDa Filtered Manganese vs. Total Dissolved Solids Particulate Manganese vs. Total Dissolved Solids Colloidal Manganese vs. Total Dissolved Solids
800 800 800 800 800
y = -7436.5x + 562.69
700 y = -2894.4x + 635.35 700 y = -3603.3x + 610.05 700 y = -4034.6x + 584.65 700 700
y = -3429.5x + 547.37 R2 = 0.4089
2
R = 0.769 R2 = 0.7603 R2 = 0.6294
600 600 600 600 R2 = 0.1876 600
TDS (mg/L)
TDS (mg/L)
TDS (mg/L)
TDS (mg/L)
TDS (mg/L)
Figure D.59 Correlations of speciated manganese to water quality parameters of seasonal testing distribution system manganese: groundwater facilities only
385
Particulate Mn (mg/L)
Colloidal Mn (mg/L)
R2 = 0.1253 2 2
R = 0.025
R = 0.9257 y = 0.0016x + 0.0003
2
R = 0.0007
0.10 0.10 0.10 0.10
Total Manganese vs. 30 kDa Filtered Manganese 0.22 m Filtered Manganese vs. Particulate Manganese 30 kDa Filtered Manganese vs. Colloidal Manganese
0.20 0.20 0.20
30 kDa Filtered Mn (mg/L)
Particulate Mn (mg/L)
Colloidal Mn (mg/L)
2
R = 0.1263 2
R = 0.0219 y = 0.0811x + 6E-05
R2 = 0.0655
0.10 0.10 0.10
Total Manganese vs. Particulate Manganese 0.22 m Filtered Manganese vs. Colloidal Manganese
0.20 0.20
0.15 0.15
Particulate Mn (mg/L)
Colloidal Mn (mg/L)
y = 0.1438x - 0.0002
y = 0.9239x - 0.0023 2
R = 0.2599
0.10 R2 = 0.9551 0.10
0.05 0.05
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L)
y = 0.0081x + 0.0002
0.15
Colloidal Mn (mg/L)
2
R = 0.0179
0.10
0.05
0.00
0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L)
Figure D.60 Correlations of speciated manganese to speciated manganese of seasonal testing distribution system manganese: surface water facilities only.
386
0.15 0.15
Particulate Fe (mg/L)
2
R = 0.0016
Colloidal Fe (mg/L)
0.10 0.10
0.10 0.10
0.05 0.05
0.05 0.05
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
0.00 0.00
-0.05 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 -0.05
Total Fe (mg/L) 0.22 m Filtered Fe (mg/L) 30 kDa Filtered Fe (mg/L) Particulate Fe (mg/L)
Total Iron vs. 30 kDa Filtered Iron 0.22 m Filtered Iron vs. Particulate Iron 30 kDa Filtered Iron vs. Colloidal Iron
0.20 0.20 0.20
y = 0.0056x + 0.0014 y = 0.3593x + 0.0255 y = -0.6886x + 0.0022
R2 = 0.0035 2
R = 0.0007 2
30 kDa Filtered Fe (mg/L)
R = 0.0427
0.15 0.15 0.15
Particulate Fe (mg/L)
Colloidal Fe (mg/L)
0.10 0.10 0.10
Total Iron vs. Particulate Iron 0.22 m Filtered Iron vs. Colloidal Iron
0.20 0.20
y = 0.8262x + 0.0003
2
R = 0.9106 y = 0.971x - 0.0014
2
0.15 0.15 R = 0.9107
Particulate Fe (mg/L)
Colloidal Fe (mg/L)
0.10 0.10
0.05 0.05
0.00 0.00
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Fe (mg/L) 0.22 m Filtered Fe (mg/L)
R2 = 0.2762
0.10
0.05
0.00
0.00 0.05 0.10 0.15 0.20
Total Fe (mg/L)
Figure D.61 Correlations of speciated iron to speciated iron of seasonal testing distribution system manganese: surface water facilities only.
387
80 80 80 80 80
60 60 60 60 60
40 40 40 40 40
20 20 20 20 20
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. Sodium 0.22 m Filtered Manganese vs. Sodium 30 kDa Filtered Manganese vs. Sodium Particulate Manganese vs. Sodium Colloidal Manganese vs. Sodium
50 50 50 50 50
45 y = 11.122x + 16.286 45 y = -310.07x + 17.427 45 y = -364.74x + 17.49 45 y = 28.212x + 16.169 45 y = -259.25x + 16.502
40 R2 = 0.0004 40 R2 = 0.0146 40 R2 = 0.0161 40 R2 = 0.0024 40 R2 = 0.0008
35 35 35 35 35
Sodium (mg/L)
Sodium (mg/L)
Sodium (mg/L)
Sodium (mg/L)
Sodium (mg/L)
30 30 30 30 30
25 25 25 25 25
20 20 20 20 20
15 15 15 15 15
10 10 10 10 10
5 5 5 5 5
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. Calcium 0.22 m Filtered Manganese vs. Calcium 30 kDa Filtered Manganese vs. Calcium Particulate Manganese vs. Calcium Colloidal Manganese vs. Calcium
50 50 50 50 50
45 y = -75.755x + 24.641 45 45 y = -2664.9x + 24.524 45 y = -79.234x + 24.421 45 y = -2664.9x + 24.524
y = -97.702x + 24.029
40 R2 = 0.0251 40 R2 = 0.1146 40 R2 = 0.0247 40 R2 = 0.1146
40 R2 = 0.0019
35 35 35 35 35
Calcium (mg/L)
Calcium (mg/L)
Calcium (mg/L)
Calcium (mg/L)
Calcium (mg/L)
30 30 30 30 30
25 25 25 25 25
20 20 20 20 20
15 15 15 15 15
10 10 10 10 10
5 5 5 5 5
0 0 0 0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Filtered Mn (mg/L) Colloidal Filtered Mn (mg/L)
Figure D.62 Correlations of speciated manganese to water quality parameters of seasonal testing distribution system manganese: surface water facilities only
388
Alkalinity (mg/L)
50
Alkalinity (mg/L)
Alkalinity (mg/L)
Alkalinity (mg/L)
40 40 40 40 40
30 30 30 30 30
20 20 20 20 20
10 10 10 10 10
0 0 0 0 0
0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.000 0.010 0.020 0.030 0.040 0.050
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. Turbidity 0.22 m Filtered Manganese vs. Turbidity 30 kDa Filtered Manganese vs. Turbidity Particulate Manganese vs. Turbidity Colloidal Manganese vs. Turbidity
2.0 2.0
2.0 2.0 2.0
1.8 y = 25.899x + 0.2186 1.8 y = 173.94x + 0.3906
1.8 1.8 y = 49.71x + 0.2304 1.8 y = 54.117x + 0.2177
y = 20.571x + 0.1864 1.6 R2 = 0.3588 1.6 R2 = 0.0776
1.6 1.6 R2 = 0.2763 1.6 R2 = 0.2766
R2 = 0.3993
1.4 1.4 1.4
Turbidity (NTU)
1.4
Turbidity (NTU)
1.4
Turbidity (NTU)
Turbidity (NTU)
Turbidity (NTU)
1.2 1.2 1.2 1.2 1.2
1.0 1.0 1.0 1.0 1.0
0.8 0.8 0.8 0.8 0.8
0.6 0.6 0.6 0.6 0.6
0.4 0.4 0.4 0.4 0.4
0.2 0.2 0.2 0.2 0.2
0.0 0.0 0.0 0.0 0.0
0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.000 0.010 0.020 0.030 0.040 0.050
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. UV254 Absorbance 0.22 m Filtered Manganese vs. UV254 Absorbance 30 kDa Filtered Manganese vs. UV254 Absorbance Particulate Manganese vs. UV254 Absorbance Colloidal Manganese vs. UV254 Absorbance
0.080 0.080 0.080 0.080
0.080
y = 2.2614x + 0.0358 y = 2.2938x + 0.0361 y = 0.9815x + 0.036 y = 6.0298x + 0.0429
0.070 0.070 0.070 0.070
0.070 R2 = 0.2801
2
R = 0.3328 R2 = 0.1448
R2 = 0.3304
Total Manganese vs. TOC 0.22 m Filtered Manganese vs. TOC 30 kDa Filtered Manganese vs. TOC Particulate Manganese vs. TOC Colloidal Manganese vs. TOC
5.0 5.0 5.0 5.0 5.0
4.5 y = 37.105x + 1.7 4.5 y = 123.25x + 1.6898 4.5 y = 35.456x + 1.8547 4.5 y = 539.89x + 2.0546
4.5 y = 122.37x + 1.6749
4.0 R2 = 0.2472 R2 = 0.3412 4.0 R2 = 0.1191 4.0 R2 = 0.2891
4.0 R2 = 0.4043 4.0
3.5 3.5 3.5 3.5 3.5
TOC (mg/L)
TOC (mg/L)
TOC (mg/L)
TOC (mg/L)
TOC (mg/L)
Figure D.63 Correlations of speciated manganese to water quality parameters of seasonal testing distribution system manganese: surface water facilities only
389
Conductivity (mho/cm)
Conductivity (mho/cm)
Conductivity (mho/cm)
Conductivity (mho/cm)
Conductivity (mho/cm)
350 350 350 350 350
300 300 300 300 300
250 250 250 250 250
200 200 200 200 200
150 150 150 150 150
100 100 100 100 100
50 50 50 50 50
0 0 0 0 0
0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Filtered Mn (mg/L) Colloidal Filtered Mn (mg/L)
Total Manganese vs. Orthophosphate 0.22 m Filtered Manganese vs. Orthophosphate 30 kDa Filtered Manganese vs. Orthophosphate Particulate Manganese vs.Orthophosphate Colloidal Manganese vs. Orthophosphate
2.5 2.5 2.5 2.5
2.5
y = 23.303x + 1.0711 y = 30.561x + 1.0475
y = -105.48x + 1.1547
2.0 2.0 R2 = 0.023 2.0 R2 = 0.0333 2.0 2.0
R2 = 0.011
Orthophosphate (mg/L)
Orthophosphate (mg/L)
Orthophosphate (mg/L)
Orthophosphate (mg/L)
y = 35.202x + 0.9036
Orthophosphate (mg/L)
R2 = 0.2513
1.5 1.5 1.5 1.5 1.5
Total Manganese vs. Sulfate 0.22 m Filtered Manganese vs. Sulfate 30 kDa Filtered Manganese vs. Sulfate Particulate Manganese vs. Sulfate Colloidal Manganese vs. Sulfate
50 50 50 50
50
y = -8.1456x + 36.229 45 y = -568.08x + 39.587 45 y = -463.58x + 38.787 45 y = 481.91x + 33.28 45
45 2 y = -7402.4x + 38.753
2
40
2
R = 6E-05 40 R2 = 0.0833 40 R = 0.041 40 R = 0.0673 40
R2 = 0.4308
35 35 35 35 35
Sulfate (mg/L)
Sulfate (mg/L)
Sulfate (mg/L)
Sulfate (mg/L)
Sulfate (mg/L)
30 30 30 30 30
25 25 25 25 25
20 20 20 20 20
15 15 15 15 15
10 10 10 10 10
5 5 5 5 5
0 0 0 0 0
0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Total Manganese vs. Total Dissolved Solids 0.22 m Filtered Manganese vs. Total Dissolved Solids 30 kDa Filtered Manganese vs. Total Dissolved Solids Particulate Manganese vs. Total Dissolved Solids Colloidal Manganese vs. Total Dissolved Solids
300 300 300 300
300
y = -2000.4x + 155.33 y = -1042.6x + 150.67 y = -6638.8x + 206.82 y = -15686x + 152.39
y = -4124x + 203.86 2
250 2 250 R = 0.0158 250 2
R = 0.0037 250 2
R = 0.4221 250 2
R = 0.0678
R = 0.3069
TDS (mg/L)
TDS (mg/L)
TDS (mg/L)
TDS (mg/L)
50 50 50 50 50
0 0 0 0 0
0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05 0.00 0.01 0.02 0.03 0.04 0.05
Total Mn (mg/L) 0.22 m Filtered Mn (mg/L) 30 kDa Filtered Mn (mg/L) Particulate Mn (mg/L) Colloidal Mn (mg/L)
Figure D.64 Correlations of speciated manganese to water quality parameters of seasonal testing distribution system manganese: surface water facilities only
390
FREE CHLORINE 0.40 mg/L AND FREE CHLORINE < 0.40 mg/L
391
Filter pH 6.5
Total Manganese (mg/L) .
0.045
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
0.060
Filter pH 7.0
Total Manganese (mg/L) .
0.045
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
Figure E.1 and E.2 Manganese as a function of temperature, at 0.040 mg/L free chlorine
392
0.045
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
0.060
Filter pH 8.0 and 8.5
Total Manganese (mg/L) .
0.045
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
Figure E.3 and E.4 Manganese as a function of temperature, at 0.040 mg/L free chlorine
393
Filter pH 6.5
Filter pH 7.0
0.045
Total Manganese (mg/L) .
Filter pH 7.5
Filter pH 8.0 and 8.5
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
Figure E.5 Manganese as a function of temperature, at 0.040 mg/L free chlorine combined data
394
2006 AwwaRF. All Rights Reserved.
0.090
0.075
Total Manganese (mg/L
0.030
0.015
0.000
0 5 10 15 20 25 30
0.090
Filter pH 7.0 < 0.40 mg/L Free Chlorine
0.075
Total Manganese (mg/L)
0.060
0.045
0.030
0.015
0.000
0 5 10 15 20 25 30
Figure E.6 and E.7 Manganese as a function of temperature, at < 0.040 mg/L free chlorine
395
2006 AwwaRF. All Rights Reserved.
0.060
0.045
Manganese - Total (mg/L)
Filter pH 6.5
Filter pH 7.0
Filter pH 7.5
0.030
0.015
0.000
0 5 10 15 20 25 30
Temperature (C)
Figure E.8 Manganese as a function of temperature, at < 0.040 mg/L free chlorine
396
2006 AwwaRF. All Rights Reserved.
e 0.090
Temperature > 8C
0.075
Total Manganese (mg/L) .
Filter pH 6.5
0.060
0.045
0.030
0.015
0.000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Free Chlorine (mg/L)
0.060
Temperature > 4C
Total Manganese (mg/L) .
0.045
Filter pH 7.0
0.030
0.015
0.000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Free Chlorine (mg/L)
397
0.045
Filter pH 7.5
0.030
0.015
0.000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Free Chlorine (mg/L)
0.060
Temperature > 3C
Total Manganese (mg/L) .
0.045
0.030
0.015
0.000
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Free Chlorine (mg/L)
398
Dual - no chlorine
pH 6.0 0.25 6.5 0.25 7.0 0.25 7.5 0.25 8.0 0.25 8.5 0.25 9.0 0.25
Baxter -9% -4% 9% 9% 71% 95%
n 2 23 31 10 1 1 0
Belmont 0% 6% 17% 31%
n 0 49 30 18 2 0 0
GAC - no chlorine
pH 6.0 0.25 6.5 0.25 7.0 0.25 7.5 0.25 8.0 0.25 8.5 0.25 9.0 0.25
Baxter 8% 10% 13%
n 0 21 6 7 0 0 0
Belmont 8% 10% 10% 40% 24%
n 1 25 17 8 2 0 0
Dual - chlorine
pH 6.0 0.25 6.5 0.25 7.0 0.25 7.5 0.25 8.0 0.25 8.5 0.25 9.0 0.25
Baxter 83% 70% 96% 86% 98% 97%
n 1 24 21 16 3 3 0
Belmont 90% 89% 90% 94% 99% 99%
n 1 47 30 20 4 2 0
399
400
Filter 1
-21.2 -11.2Inflow EH -1.2 Outflow8.8
EH 18.8 28.8
Dissolved Manganese 38.8 48.8
Total Manganese 58.8 PWD Mn Goal 68.8
900 0.090
700 0.060
Mn (mg/L)
Starting Run 040510
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/10/04 05/10/04 05/11/04 05/11/04 05/11/04 05/11/04 05/12/04 05/12/04 05/12/04 05/12/04 05/13/04 05/13/04 05/13/04 05/13/04 05/14/04 05/14/04
Date & Time
04:44 PM 10:44 PM 04:44 AM 10:44 AM 04:44 PM 10:44 PM 04:44 AM 10:44 AM 04:44 PM 10:44 PM 04:44 AM 10:44 AM 04:44 PM 10:44 PM 04:44 AM 10:44 AM
47.5
-0.5
0.5
27.5
2.0
21.3
23.7
1.0
71.3
Shutoff (hours)
48.8
42.5
45.0
20.7
22.3
21.8
1.5
0.0
0.0
23.3
25.3
Run Time (hours)
900
Filter 3 0.090
700 0.060
Starting Run 040510
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/10/04 05/10/04 05/11/04 05/11/04 05/11/04 05/11/04 05/12/04 05/12/04 05/12/04 05/12/04 05/13/04 05/13/04 05/13/04 05/13/04 05/14/04 05/14/04
Date & Time
04:44 PM 10:44 PM 04:44 AM 10:44 AM 04:44 PM 10:44 PM 04:44 AM 10:44 AM 04:44 PM 10:44 PM 04:44 AM 10:44 AM 04:44 PM 10:44 PM 04:44 AM 10:44 AM
Elapsed Time Since Chlorine
21.3
71.3
47.5
23.7
27.5
-0.5
2.0
0.5
1.0
Shutoff (hours)
48.8
25.3
0.0
1.5
20.7
42.5
45.0
21.8
22.3
23.3
0.0
Run Time (hours)
h Run 040510 terminated due to equipment failure. Filters 1 and 3 reached terminal head loss because the sodium hydroxide feed at the rapid mix was lost for approximately 6-hours due to the carboy running dry.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001 mg/L) for Mn data.
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.13: Baxter pilot plant runs; manganese and EH as a function of time, May 10-14, 2004. Effect of chlorine loss and pH on manganese control.
401
Filter 1
-18.2 -8.2 1.8 11.8 21.8 31.8 41.8 51.8
Inflow EH Outflow EH Dissolved Manganese Total Manganese PWD Mn Goal
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/17/04 05/17/04 05/18/04 05/18/04 05/18/04 05/18/04 05/19/04 05/19/04 05/19/04 05/19/04 05/20/04 05/20/04 05/20/04
4:00 PM 10:00 PM 4:00 AM 10:00 AM 4:00 PM 10:00 PM 4:00 AM 10:00 AM 4:00 PM 10:00 PM 4:00 AM 10:00 AM 4:00 PM Date & Time
49.3
51.8
-0.2
47.3
0.6
1.1
23.1
27.3
3.1
Shutoff (hours)
0.0
18.0
21.3
41.3
70.0
45.5
67.5
18.8
19.3
65.5
Run Time (hours)
700 0.060
Starting Run 040517
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/17/04 05/17/04 05/18/04 05/18/04 05/18/04 05/18/04 05/19/04 05/19/04 05/19/04 05/19/04 05/20/04 05/20/04 05/20/04
4:00 PM 10:00 PM 4:00 AM 10:00 AM 4:00 PM 10:00 PM 4:00 AM 10:00 AM 4:00 PM 10:00 PM 4:00 AM 10:00 AM 4:00 PM Date & Time
0.6
27.3
1.1
3.1
23.1
49.3
-0.2
47.3
51.8
Elapsed Time Since Chlorine
Shutoff (hours)
0.0
18.0
18.8
65.5
45.5
19.3
21.3
41.3
67.5
70.0
Run Time (hours)
Figure E.14: Baxter pilot plant runs; manganese and EH as a function of time, May 17-20, 2004. Effect of chlorine loss and pH on manganese control.
402
Filter 1
-19.2 -9.2 0.8 10.8 20.8 30.8 40.8 50.8 60.8 70.8
Inflow EH Outflow EH Dissolved Manganese Total Manganese PWD Mn Goal
1000 0.090
800 0.060
Mn (mg/L)
EH (mV)
700 0.045
600 0.030
500 0.015
400 0.000
05/24/04 05/24/04 05/25/04 05/25/04 05/25/04 05/25/04 05/26/04 05/26/04 05/26/04 05/26/04 05/27/04 05/27/04 05/27/04 05/27/04 05/28/04 05/28/04
Date & Time
03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM
49.6
50.1
51.6
3.0
4.0
5.0
53.1
1.0
2.0
-0.2
71.6
Shutoff (hours)
0.0
0.9
22.2
23.2
19.0
2.4
20.2
21.2
24.2
0.0
22.4
0.4
3.8
Run Time (hours)
-19.2 -9.2 0.8 10.8 20.8 30.8Filter 3 40.8 50.8 60.8 70.8
1000 0.090
800 0.060
Mn (mg/L)
EH (mV)
700 0.045
600 0.030
500 0.015
400 0.000
05/24/04 05/24/04 05/25/04 05/25/04 05/25/04 05/25/04 05/26/04 05/26/04 05/26/04 05/26/04 05/27/04 05/27/04 05/27/04 05/27/04 05/28/04 05/28/04
Date & Time
03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM 03:02 PM 09:02 PM 03:02 AM 09:02 AM
49.3
49.8
-0.2
1.0
2.0
3.0
23.8
27.8
4.0
51.3
52.7
5.0
71.3
Shutoff (hours)
22.4
0.0
0.0
19.0
20.2
21.2
22.2
23.2
24.2
43.0
47.0
0.9
2.4
3.8
0.4
Run Time (hours)
h Run 040524 was terminated due to HL - headloss. Run 040527 was terminated due to TM - Time Constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001 mg/L) for Mn data.
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.15: Baxter pilot plant runs; manganese and EH as a function of time, May 24-28, 2004. Effect of chlorine loss and pH on manganese control.
403
Filter 1
-18.1 -8.1 1.9 11.9 21.9 31.9 41.9 51.9 61.9 71.9
Inflow EH Outflow EH Dissolved Manganese Total Manganese PWD Mn Goal
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/10/04 05/10/04 05/11/04 05/11/04 05/11/04 05/11/04 05/12/04 05/12/04 05/12/04 05/12/04 05/13/04 05/13/04 05/13/04 05/13/04 05/14/04 05/14/04
Date & Time
04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM
Elapsed Time Since Chlorine
3.5
4.5
24.0
25.0
27.0
29.0
2.5
5.5
23.5
26.0
1.5
48.5
50.5
52.5
47.5
70.8
72.5
0.0
0.5
Shutoff (hours)
0.0
1.0
3.0
4.0
6.0
18.1
18.6
19.6
20.6
21.6
22.6
23.6
0.0
2.0
24.5
25.5
27.5
29.5
47.8
49.5
0.5
Filter 6
-18.1 -8.1 1.9 11.9 21.9 31.9 41.9 51.9 61.9 71.9
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/10/04 05/10/04 05/11/04 05/11/04 05/11/04 05/11/04 05/12/04 05/12/04 05/12/04 05/12/04 05/13/04 05/13/04 05/13/04 05/13/04 05/14/04 05/14/04
Date & Time
04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM 04:22 PM 10:22 PM 04:22 AM 10:22 AM
27.0
3.5
4.5
26.0
29.0
2.5
5.5
23.5
48.5
50.5
52.5
1.5
47.5
70.8
72.5
0.0
0.5
Shutoff (hours)
0.5
1.0
2.0
6.0
3.0
4.0
24.5
27.5
18.1
25.5
0.0
18.6
0.0
29.5
47.8
49.5
20.6
23.6
19.6
21.6
22.6
h Both Run 040510 and Run 040512 were terminated due to TM - time constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.16: Belmont pilot plant runs; manganese and EH as a function of time, May 10-14, 2004. Effect of chlorine loss and pH on manganese control.
404
Filter 1
-18.6 -8.6 Inflow EH 1.4 11.4
Outflow EH 21.4
Dissolved 31.4
Manganese (mg/L) 41.4 51.4
Total Manganese (mg/L) 61.4
PWD Mn Goal 71.4
900 0.090
700 0.060
Starting Run 040517
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/17/04 05/17/04 05/18/04 05/18/04 05/18/04 05/18/04 05/19/04 05/19/04 05/19/04 05/19/04 05/20/04 05/20/04 05/20/04 05/20/04 05/21/04 05/21/04
Date & Time
03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM
29.7
49.5
51.5
24.0
47.5
73.5
71.5
0.0
0.5
1.0
2.0
3.0
4.0
5.0
30.2
53.5
Shutoff (hours)
0.0
42.6
18.0
20.0
22.0
24.0
42.0
44.0
0.3
0.8
0.0
900
Filter 6 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
05/17/04 05/17/04 05/18/04 05/18/04 05/18/04 05/18/04 05/19/04 05/19/04 05/19/04 05/19/04 05/20/04 05/20/04 05/20/04 05/20/04 05/21/04 05/21/04
Date & Time
03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM 03:24 PM 09:24 PM 03:24 AM 09:24 AM
Elapsed Time Since Chlorine
1.0
47.5
0.0
0.5
2.0
3.0
4.0
5.0
29.7
73.5
24.0
30.2
49.5
51.5
53.5
71.5
Shutoff (hours)
0.0
42.6
18.0
20.0
22.0
24.0
42.0
44.0
0.8
0.3
0.0
h High headloss rates were observed during Run 040517. Further investigation determined that the high headloss rate was a function of a slight coagulant overdose. The ferric dose was decreased and the headloss rates dropped to a range considered "normal".
h Run 040519 terminated due to TM - Time constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.17: Belmont pilot plant runs; manganese and EH as a function of time, May 17-21, 2004. Effect of chlorine loss and pH on manganese control.
405
Filter 1
-17.5 -7.5 2.5 12.5 22.5 32.5
Inflow EH Outflow EH Dissolved Managanese Total Manganese PWD Mn Goal
1000 0.090
900 0.075
End Reason - TB
Mn (mg/L)
Starting Run 040524
EH (mV)
700 0.045
600 0.030
500 0.015
400 0.000
05/24/04 03:28 PM 05/24/04 09:28 PM 05/25/04 03:28 AM 05/25/04 09:28 AM 05/25/04 03:28 PM 05/25/04 09:28 PM 05/26/04 03:28 AM 05/26/04 09:28 AM 05/26/04 03:28 PM
Date & Time
2.0
2.7
5.0
7.0
0.0
0.5
1.0
Elapsed Time Since Chlorine
Shutoff (hours)
17.5
22.5
18.0
18.5
19.5
20.2
24.5
0.0
Filter 6
-17.5 -7.5 2.5 12.5 22.5 32.5
1000 0.090
900 0.075
Mn (mg/L)
Starting Run 040524
EH (mV)
700 0.045
600 0.030
500 0.015
400 0.000
05/24/04 03:28 PM 05/24/04 09:28 PM 05/25/04 03:28 AM 05/25/04 09:28 AM 05/25/04 03:28 PM 05/25/04 09:28 PM 05/26/04 03:28 AM 05/26/04 09:28 AM 05/26/04 03:28 PM
Date & Time
0.0
0.5
1.0
2.0
2.7
5.0
7.0
27
29
31
25
Elapsed Time Since Chlorine
Shutoff (hours)
42.5
44.5
46.5
48.5
17.5
19.5
22.5
18.0
18.5
20.2
24.5
0.0
[1]
Filter 1, Run 040524 was terminated due to turbidity breakthrough which was unusual for a filter being operated at this temperature. Its turbidity trending statistics become erratic after a spike at 25.5 hours of run time. The headloss profile changes shows up approximately 30 minutes after the spike. This
phenomenon was only witnessed on Filter 1.
h Filter 6, Run 040524 was terminated due to TB - turbidity breakthrough. It ran for 52 hours which precluded the option of a second filter run for this investigation.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.18: Belmont pilot plant runs; manganese and EH as a function of time, May 24-26, 2004. Effect of chlorine loss and pH on manganese control.
406
Filter 1
-16.8 -6.8 3.2 13.2 23.2 33.2 43.2 53.2 63.2
Inflow EH Outflow EH Dissolved Manganese Total Manganese PWD Mn Goal
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
12/06/04 12/07/04 12/07/04 12/07/04 12/07/04 12/08/04 12/08/04 12/08/04 12/08/04 12/09/04 12/09/04 12/09/04 12/09/04 12/10/04 12/10/04
Date & Time
06:18 PM 12:18 AM 06:18 AM 12:18 PM 06:18 PM 12:18 AM 06:18 AM 12:18 PM 06:18 PM 12:18 AM 06:18 AM 12:18 PM 06:18 PM 12:18 AM 06:18 AM
20.2
24.2
53.9
43.9
57.9
10.0
22.2
29.6
31.6
33.6
45.9
49.9
55.9
48.4
51.9
-0.8
2.0
1.0
3.0
4.0
6.0
8.0
0.5
Shutoff (hours)
26.5
15.7
18.5
19.5
20.5
22.5
38.7
40.7
30.3
17.0
17.5
16.3
18.3
20.8
22.3
24.3
26.3
28.3
1.9
3.9
5.9
24.5
36.7
0.0
0.0
Run Time (hours)
-16.8 -6.8 3.2 13.2 23.2 Filter 333.2 43.2 53.2 63.2
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
12/06/04 12/07/04 12/07/04 12/07/04 12/07/04 12/08/04 12/08/04 12/08/04 12/08/04 12/09/04 12/09/04 12/09/04 12/09/04 12/10/04 12/10/04
Date & Time
06:18 PM 12:18 AM 06:18 AM 12:18 PM 06:18 PM 12:18 AM 06:18 AM 12:18 PM 06:18 PM 12:18 AM 06:18 AM 12:18 PM 06:18 PM 12:18 AM 06:18 AM
43.9
53.9
10.0
33.6
45.9
-0.8
0.5
2.0
4.0
6.0
8.0
29.6
3.0
31.6
48.4
49.9
51.9
57.9
55.9
Shutoff (hours)
19.5
20.5
26.5
26.3
16.3
18.3
17.0
17.5
18.5
22.5
24.5
20.8
22.3
24.3
15.7
1.9
3.9
5.9
28.3
30.3
0.0
0.0
h During Run 041206 and 041208, both filters terminated due to TB - turbidity breakthrough.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001 mg/L) for Mn data.
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.19: Baxter pilot plant runs; manganese and EH as a function of time, December 6-10, 2004. Effect of chlorine loss and pH on manganese control.
407
Filter 1
-16.4 -6.4 3.6 13.6 23.6 33.6 43.6 53.6 63.6
Inflow EH Outflow EH Dissolved Manganese Total Manganese PWD Mn Goal
900 0.090
End Reason - TM
800 0.075
Starting Run 041213
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
12/13/04 12/14/04 12/14/04 12/14/04 12/14/04 12/15/04 12/15/04 12/15/04 12/15/04 12/16/04 12/16/04 12/16/04 12/16/04 12/17/04 12/17/04
Date & Time
06:04 PM 12:04 AM 06:04 AM 12:04 PM 06:04 PM 12:04 AM 06:04 AM 12:04 PM 06:04 PM 12:04 AM 06:04 AM 12:04 PM 06:04 PM 12:04 AM 06:04 AM
54.5
52.5
56.5
58.3
22.5
24.5
26.5
32.5
50.5
68.5
0.0
48.5
1.3
70.5
0.8
2.3
3.2
4.3
6.2
8.3
10.3
20.5
28.5
30.5
34.5
Shutoff (hours)
3.1
11.1
17.7
18.7
20.7
22.7
36.9
38.9
46.9
23.1
5.1
7.1
25.1
16.4
17.2
19.7
24.7
26.7
40.9
42.9
44.9
48.9
50.9
12.8
9.1
0.0
0.0
Run Time (hours)
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
12/13/04 12/14/04 12/14/04 12/14/04 12/14/04 12/15/04 12/15/04 12/15/04 12/15/04 12/16/04 12/16/04 12/16/04 12/16/04 12/17/04 12/17/04
Date & Time
06:04 PM 12:04 AM 06:04 AM 12:04 PM 06:04 PM 12:04 AM 06:04 AM 12:04 PM 06:04 PM 12:04 AM 06:04 AM 12:04 PM 06:04 PM 12:04 AM 06:04 AM
48.5
20.5
22.5
24.5
28.5
1.3
58.3
70.5
26.5
30.5
32.5
68.5
34.5
52.5
54.5
56.5
0.0
50.5
0.8
2.3
3.2
4.3
6.2
8.3
Shutoff (hours)
9.1
20.7
22.7
42.9
50.9
38.9
12.8
17.2
36.9
44.9
46.9
48.9
3.1
5.1
16.4
17.7
18.7
19.7
24.7
26.7
11.1
23.1
40.9
7.1
25.1
0.0
0.0
h During Run 041213 both filters terminated due to TB - turbidity breakthrough. During Run 041216 both filters terminated due to TM - time constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001 mg/L) for Mn data.
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.20: Baxter pilot plant runs; manganese and EH as a function of time, December 13-17, 2004. Effect of chlorine loss and pH on manganese control.
408
Filter 1
-19.4 -14.4 Inflow EH -9.4 -4.4
Outflow EH 0.6 5.6
Dissolved Manganese 10.6 Total Manganese 15.6 20.6Mn Goal
PWD 25.6
900 0.090
End Filter Run 041220;
800 0.075 End Reason - TB
700 0.060
Starting Run 041220
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
12/20/04 03:04 PM 12/20/04 09:04 PM 12/21/04 03:04 AM 12/21/04 09:04 AM 12/21/04 03:04 PM 12/21/04 09:04 PM 12/22/04 03:04 AM 12/22/04 09:04 AM Date & Time
10.3
1.3
22.5
20.5
24.5
6.2
26.5
0.0
4.3
2.3
3.2
0.8
8.3
Elapsed Time Since Chlorine
Shutoff (hours)
22.7
19.4
20.7
20.2
21.7
23.7
27.7
25.7
41.9
45.9
39.9
43.9
29.7
0.0
-19.4 -14.4 -9.4 -4.4 0.6 5.6 Filter 3 10.6 15.6 20.6 25.6
900 0.090
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
12/20/04 03:04 PM 12/20/04 09:04 PM 12/21/04 03:04 AM 12/21/04 09:04 AM 12/21/04 03:04 PM 12/21/04 09:04 PM 12/22/04 03:04 AM 12/22/04 09:04 AM Date & Time
10.3
20.5
24.5
1.3
22.5
6.2
0.8
3.2
2.3
4.3
8.3
0.0
Shutoff (hours)
19.4
20.2
20.7
21.7
22.7
23.7
25.7
27.7
29.7
39.9
41.9
43.9
0.0
Figure E.21: Baxter pilot plant runs; manganese and EH as a function of time, December 20-22, 2004. Effect of chlorine loss and pH on manganese control.
409
Filter 1
-22.9 -12.9Inflow EH -2.9 Outflow EH 7.1 Dissolved17.1
Manganese 27.1 Total Manganese 37.1 PWD47.1
Mn Goal 57.1
900 0.090
700 0.060
Starting Run 041025
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
10/25/04 10/25/04 10/26/04 10/26/04 10/26/04 10/26/04 10/27/04 10/27/04 10/27/04 10/27/04 10/28/04 10/28/04 10/28/04 10/28/04
03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM Date & Time
49.0
26.5
28.5
45.0
47.0
25.5
26.0
27.5
30.5
39.0
41.0
43.0
51.0
54.5
53.0
0.0
2.0
3.0
0.5
1.0
Elapsed Time Since Chlorine
Shutoff (hours)
14.6
16.6
18.6
20.6
26.6
28.6
30.1
1.1
6.1
22.6
1.6
2.1
3.1
4.1
24.6
22.9
23.4
24.9
25.9
23.9
0.0
0.0
-22.9 -12.9 -2.9 7.1 17.1
Filter 6 27.1 37.1 47.1 57.1
900 0.090
End Filter Run 041025; End Reason - TB
700 0.060
Starting Run 041025
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
10/25/04 10/25/04 10/26/04 10/26/04 10/26/04 10/26/04 10/27/04 10/27/04 10/27/04 10/27/04 10/28/04 10/28/04 10/28/04 10/28/04
Date & Time
03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM 03:36 AM 09:36 AM 03:36 PM 09:36 PM
49.0
54.5
27.5
30.5
39.0
41.0
47.0
53.0
0.0
43.0
45.0
0.5
25.5
26.5
28.5
51.0
26.0
2.0
4.0
1.0
3.0
22.6
6.1
3.1
4.1
22.6
30.1
Run Time (hours)
2.1
1.1
1.6
14.6
22.9
23.4
23.9
24.9
25.9
16.6
18.6
20.6
24.6
26.6
28.6
0.0
h Both Run 041025 and Run 041027 were terminated due to TB - turbidity breakthrough.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.22: Belmont pilot plant runs; manganese and EH as a function of time, October 25-28, 2004. Effect of chlorine loss and pH on manganese control.
410
Filter 1
-3.6 6.4
Inflow EH 16.4Outflow EH 26.4 Dissolved Manganese36.4 46.4
Total Manganese 56.4PWD Mn Goal 66.4
900 0.090
End Reason - TM
700 0.060
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
11/02/04 11/02/04 11/02/04 11/03/04 11/03/04 11/03/04 11/03/04 11/04/04 11/04/04 11/04/04 11/04/04 11/05/04
11:24 AM 05:24 PM 11:24 PM 05:24 AM 11:24 AM 05:24 PM 11:24 PM 05:24 AM 11:24 AM 05:24 PM 11:24 PM 05:24 AM Date & Time
48.5
0.5
18.5
22.5
52.5
14.5
16.5
24.5
26.5
28.5
30.0
46.5
50.5
66.5
2.0
20.5
54.5
64.5
0.0
3.0
5.0
1.0
Shutoff (hours)
30.1
18.1
20.1
26.1
32.1
19.9
3.6
24.1
33.6
3.9
5.9
9.9
21.9
4.1
4.6
5.6
6.6
8.6
21.1
28.1
1.9
7.9
0.0
Run Time (hours)
0.0
Filter 6
-3.6 6.4 16.4 26.4 36.4 46.4 56.4 66.4
900 0.090
Mn (mg/L)
EH (mV)
600 0.045
500 0.030
400 0.015
300 0.000
11/02/04 11/02/04 11/02/04 11/03/04 11/03/04 11/03/04 11/03/04 11/04/04 11/04/04 11/04/04 11/04/04 11/05/04
Date & Time
11:24 AM 05:24 PM 11:24 PM 05:24 AM 11:24 AM 05:24 PM 11:24 PM 05:24 AM 11:24 AM 05:24 PM 11:24 PM 05:24 AM
24.5
50.5
20.5
26.5
0.0
3.0
16.5
30.0
38.5
42.5
48.5
52.5
54.5
66.5
0.5
2.0
5.0
14.5
18.5
22.5
28.5
40.5
46.5
64.5
Shutoff (hours)
0.0
5.9
8.6
18.1
20.1
32.1
46.1
19.9
21.9
3.6
4.6
24.1
26.1
28.1
30.1
33.6
0.0
4.1
5.6
6.6
22.1
42.1
44.1
9.9
1.9
3.9
7.9
Run Time (hours)
h Run 041102 terminated due to TB - turbidity breakthrough, and Run 041104 terminated due to TM - time constraints.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.23: Belmont pilot plant runs; manganese and EH as a function of time, November 2-5, 2004. Effect of chlorine loss and pH on manganese control.
411
Filter 1
-19.0 -14.0 Inflow EH -9.0 Outflow EH -4.0 1.0
Dissolved Manganese 6.0 11.0
Total Manganese 16.0 PWD Mn Goal 21.0
1000 0.090
800 0.060
Starting Run 041108
Mn (mg/L)
EH (mV)
700 0.045
600 0.030
500 0.015
400 0.000
11/08/04 03:00 PM 11/08/04 09:00 PM 11/09/04 03:00 AM 11/09/04 09:00 AM 11/09/04 03:00 PM 11/09/04 09:00 PM 11/10/04 03:00 AM 11/10/04 09:00 AM Date & Time
1.0
3.0
0.0
2.0
0.5
4.0
6.0
Shutoff (hours)
19.0
19.5
20.0
21.0
22.0
23.0
25.0
0.0
Filter 6
-19.0 -14.0 -9.0 -4.0 1.0 6.0 11.0 16.0 21.0
1000 0.090
800 0.060
Mn (mg/L)
Starting Run 041108
EH (mV)
700 0.045
600 0.030
500 0.015
400 0.000
11/08/04 03:00 PM 11/08/04 09:00 PM 11/09/04 03:00 AM 11/09/04 09:00 AM 11/09/04 03:00 PM 11/09/04 09:00 PM 11/10/04 03:00 AM 11/10/04 09:00 AM Date & Time
40.8 21.8
1.0
42.8 23.8
4.0
0.0
3.0
2.0
6.0
Shutoff (hours)
19.0
19.5
20.0
21.0
22.0
23.0
25.0
0.0
Figure E.24: Belmont pilot plant runs; manganese and EH as a function of time, November 8-10, 2004. Effect of chlorine loss and pH on manganese control.
412
Filter 1
-18.1 -8.1 Inflow EH 1.9 Outflow11.9
EH 21.9 31.9
Dissolved Manganese 41.9 Manganese
Total 51.9 PWD Mn61.9
Goal 71.9
1000 0.120
Mn (mg/L)
700 0.075
EH (mV)
600 0.060
500 0.045
400 0.030
300 0.015
200 0.000
11/15/04 11/15/04 11/16/04 11/16/04 11/16/04 11/16/04 11/17/04 11/17/04 11/17/04 11/17/04 11/18/04 11/18/04 11/18/04 11/18/04 11/19/04 11/19/04
Date & Time
03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM
Elapsed Time Since Chlorine
2.0
6.3
32.8
58.3
4.0
26.8
28.8
0.0
8.3
24.8
1.0
34.8
36.5
45.3
47.3
49.3
70.3
3.0
30.8
51.3
60.3
0.5
Shutoff (hours)
24.3
26.3
11.5
13.3
22.0
24.0
26.0
28.0
13.1
3.5
1.1
3.1
0.0
0.0
5.5
7.5
0.0
1.5
9.5
Filter 6
-18.1 -8.1 1.9 11.9 21.9 31.9 41.9 51.9 61.9 71.9
1000 0.120
Mn (mg/L)
Starting Run 041115
700 0.075
EH (mV)
600 0.060
500 0.045
400 0.030
300 0.015
200 0.000
11/15/04 11/15/04 11/16/04 11/16/04 11/16/04 11/16/04 11/17/04 11/17/04 11/17/04 11/17/04 11/18/04 11/18/04 11/18/04 11/18/04 11/19/04 11/19/04
Date & Time
03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM 03:10 PM 09:10 PM 03:10 AM 09:10 AM
70.3
72.3
26.8
32.8
34.8
36.5
58.3
30.8
28.8
47.3
49.3
0.0
4.0
6.3
10.3
45.3
1.0
8.3
24.8
55.3
60.3
3.0
2.0
12.3
0.5
51.3
53.3
13.3 Shutoff (hours)
1.1
19.1
21.1
18.1
30.4
3.5
26.0
32.0
13.1
28.4
30.0
18.6
24.3
1.5
5.5
22.0
3.1
15.1
20.1
22.1
26.3
11.5
24.0
28.0
7.5
9.5
0.0
0.
0.0
h Runs 041115 and 041117 terminated due to TB - turbidity breakthrough; run 040518 terminated due to TM - time constraint.
h For graphical continuity, a zero (0.0) was substituted for a reported value of "non-detect" (<0.001-mg/L).
h EH value is assumed to be in steady state before chlorine shutoff.
Figure E.25: Belmont pilot plant runs; manganese and EH as a function of time, November 15-19, 2004. Effect of chlorine loss and pH on manganese control.
413
Table F.1 Case Study (II) data collection sheet for September 14-16, 2004 sample event
Treated Combined
Source Water Water Sed Basin Eff Filter Influent Anthracite Filter Eff GAC Filter Eff Filter Eff Clearwell Influent Mid Clearwell Finished
On-Line 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 24hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr
Mn 0.011 0.011 0.011 0.050 0.051 0.011 0.052 0.053 0.050
Percent Eff Valve % 30.6 40.0 29.4 12.9 21.8 19.9
Turbidity (NTU) 171 98 1.20 0.67 1.20 0.137 0.051 0.060 0.131 0.041 0.085 0.090 0.13 0.21
P-Counts (#/ml) 1635 2348 2770
pH 7.20 7.10 6.02 7.91 6.78 9.46 7.63 7.73 8.03
Chlorine 3.48 3.17 4.48 1.79 1.81 2.49 4.30 2.43
Grab 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr
Mn PAN - Dissolved 0.340 0.200 0.110 0.054 0.058 0.032 0.025 0.030 0.038 0.026 0.012 0.014 0.024 0.007 0.016 0.020 0.018
Mn PAN - Total 0.649 0.490 0.315 0.049 0.059 0.048 0.050 0.096 0.063 0.053 0.015 0.016 0.017 0.011 0.018 0.016 0.019
Alkalinity 55 55 50 24 16 18 52 22 45 38 30 53 49 36 45 40 53 55
pH 7.22 7.23 7.38 6.06 6.19 6.15 7.10 6.35 7.10 7.00 6.50 7.41 7.04 6.61 7.18 6.76 7.40 7.21
Chlorine - Free 0.01 0.00 0.00 2.96 2.77 3.50 1.13 1.80 1.95 0.03 0.09 0.07 2.58 2.17 2.45
Chlorine - Total 0.05 0.00 0.00 3.04 2.80 3.60 1.23 1.83 2.05 0.09 0.15 0.12 2.58 2.34 2.49
KMnO4
Conductivity 260 260 220 300 300 340 360 290 260 340 280 270 360 280 270 250
415
Treated Combined
Source Water Water Sed Basin Eff Filter Influent Anthracite Filter Eff GAC Filter Eff Filter Eff Clearwell Influent Mid Clearwell Finished
On-Line 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2hr 2 hr 24 hr 48 hr 2 hr 24 hr 48 hr 2 hr 24 hr 48 hr
Mn X X X x X X X 0.048 0.049 0.048 0.049 0.054 0.049 0.055 0.049 0.055 0.048 x x x x x x x x x
Percent Eff Valve % x x x x x x x x x x 32.6 27.4 33.9 12.6 12.6 13.4 x x x x x x x x x x
Turbidity (NTU) 16 13 18 x X X X 0.73 0.74 0.96 0.114 0.077 0.073 0.052 0.034 0.033 0.068 x x x 0.11 x x 0.13 x x
P-Counts (#/ml) x x x x X X X 267 253 262 x x x x x x x x x x
pH 7.48 7.59 7.57 6.38 X X X 7.32 7.89 7.78 x x x x x x x 7.89 x x 7.65 x x 7.30 x x
Chlorine x x x x X X X 2.32 1.90 1.66 1.93 1.52 1.38 x x x x 4.65 x x 4.55 x x 2.55 x x
Grab 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2hr 2 hr 24 hr 48 hr 2 hr 24 hr 48 hr 2 hr 24 hr 48 hr
Mn PAN - Dissolved 0.099 0.045 0.065 0.033 0.029 0.032 0.040 0.039 0.047 0.027 0.013 0.010 0.025 0.014 0.027 x 0.020 0.014 0.015 x 0.012 0.015 0.017 0.015 0.018
Mn PAN - Total 0.114 0.074 0.098 0.032 0.027 0.029 0.050 0.043 0.046 0.044 0.048 0.019 0.041 0.021 0.051 x 0.030 0.022 0.034 x 0.020 0.031 0.026 0.030 0.038
Alkalinity 68 66 66 x 38 43 45 58 56 59 58 55 58 59 57 60 x 67 72 64 70 63 65 67 65 67
pH 7.32 7.4 7.56 x 6.5 6.51 6.63 6.98 7.01 7.12 7.00 7.08 7.17 7.01 7.17 7.22 x 7.29 7.28 7.25 7.45 7.5 7.45 7.36 7.35 7.32
Chlorine - Free x x x x 0.03 - - 2.09 1.60 1.47 1.49 1.30 1.21 0.03 0.15 0.03 x 3.98 2.91 3.87 2.48 2.28 2.55 2.31 2.43 2.42
Chlorine - Total x x x x 0.03 - - 2.16 1.7 1.49 1.52 1.31 1.21 0.04 0.21 0.06 x 3.97 2.91 3.97 2.57 2.28 2.55 2.35 2.46 2.5
KMnO4 x x x x x x x x x x x x x x x x x x x x x x x x x x
Conductivity 400 390 380 x 360 390 388 390 420 390 400 422 400 400 422 400 x 430 450 410 435 445 422 422 442 440
416
Treated Combined
Source Water Water Sed Basin Eff Filter Influent Anthracite Filter Eff GAC Filter Eff Filter Eff Clearwell Influent Mid Clearwell Finished
On-Line 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2hr 2 hr 24 hr 48 hr 2 hr 24 hr 48 hr 2 hr 24 hr 48 hr
Mn x x x x x x x 0.048 0.048 0.047 0.048 0.054 0.049 0.054 0.054 0.045 0.048 x x x
Percent Eff Valve % x x x x x x x x x x 23.4 29.5 10.3 11.3 10.9 10.3 x x x x
Turbidity (NTU) 62 51 36 x x x x 2.90 2.19 2.06 0.081 0.061 0.039 0.049 0.031 0.039 0.054 x 0.08 0.08
P-Counts (#/ml) x x x x x x x 2255 2418 447 54 x x 68 19 18 x x x x
pH 7.65 7.67 7.87 6.60 x x x 6.70 6.60 6.50 x x x x x x x 7.11 7.30 7.30
Chlorine x x x x x x x 2.09 2.12 1.84 1.12 1.46 1.47 x x x x 4.48 4.44 2.3/2.3
Grab 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2 hr 24 hr 46 hr 2hr 2 hr 24 hr 48 hr 2 hr 24 hr 48 hr 2 hr 24 hr 48 hr
Mn PAN - Dissolved 0.115 0.098 0.076 0.092 0.041 0.034 0.029 0.032 0.031 0.028 0.014 0.017 0.016 0.015 0.017 0.014 x 0.018 0.021 0.021 0.020 0.020 0.021 0.019 0.019 0.018
Mn PAN - Total 0.158 0.143 0.102 0.118 0.042 0.031 0.029 0.036 0.029 0.030 0.021 0.027 0.022 0.022 0.026 0.021 x 0.022 0.026 0.023 0.023 0.026 0.022 0.023 0.024 0.021
Alkalinity 58 53 55 x 36 33 41 37 34 31 32 34 31 33 30 31 x 50 60 46 50 55 51 52 55 50
pH 7.32 7.6 7.52 x 6.53 6.72 6.55 6.46 6.56 6.51 6.56 6.54 6.51 6.53 6.53 6.55 x 6.83 7.11 7.11 7.22 7.41 7.3 7.16 7.26 7.19
Chlorine - Free x x x x 0.00 0.00 0.00 1.59 1.45 1.55 1.43 1.48 1.35 0.12 0.18 0.22 x 3.34 3.71 3.60 2.38 2.56 2.50 2.20 2.41 2.30
Chlorine - Total x x x x 0.00 0.00 0.00 1.71 1.60 1.68 1.50 1.49 1.42 0.16 0.27 0.27 x 3.66 3.79 3.60 2.49 2.60 2.60 2.33 2.47 2.40
KMnO4 x x x x x x x x x x x x x x x x x x x x x x x x x x
Conductivity 250 280 285 x 260 270 285 260 280 285 260 240 280 260 260 280 x 290 315 320 275 320 295 280 320 275
417
0.500
0.400
0.300
0.200
0.100
0.000
2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 2 24 46 2 24 46
hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr
Source Sed Basin Filter Anthracite GAC Clearwell Mid- Clearwell
Water Effluent Influent Filter Eff Filter Eff Influent Clearwell Effluent
Figure F.1 Case Study (II) manganese concentration through plant process September 14-16, 2004; comparison of ICP-MS,
PAN, and online (colorimetric) sample Mn concentration
419
0.100
0.080
0.060
0.040
0.020
0.000
2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 2 24 46 2 24 46
hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr
Source Sed Basin Filter Anthracite GAC Clearwell Mid- Clearwell
Water Effluent Influent Filter Eff Filter Eff Influent Clearwell Effluent
Figure F.2 Case Study (II) manganese concentration through plant process September 14-16, 2004; comparison of ICP-MS,
PAN, and online (colorimetric) sample Mn concentration
420
0.100
0.080
0.060
0.040
0.020
0.000
2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 . 2 24 46 2 24 46 2 24 46
hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr
Source Sed Basin Filter Anthracite GAC Clearwell Mid- Clearwell
Water Effluent Influent Filter Eff Filter Eff Influent Clearwell Effluent
Figure F.3 Case Study (II) manganese concentration through plant process November 2-4, 2004; comparison of ICP-MS, PAN,
and online (colorimetric) sample Mn concentration
421
On-Line
0.120 Grab - PAN
Grab - ICP-MS
Total Manganese (mg/L)
0.100
0.080
0.060
0.040
0.020
0.000
2 24 48 . 2 24 48 . 2 24 48 . 2 24 48 . 2 24 48 . 2 24 48 2 24 48 2 24 48
hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr hr
Source Sed Basin Filter Anthracite GAC Clearwell Mid- Clearwell
Water Effluent Influent Filter Eff Filter Eff Influent Clearwell Effluent
Figure F.4 Case Study (II) manganese concentration through plant process December 28-30, 2004; comparison of ICP-MS,
PAN, and online (colorimetric) sample Mn concentration
422
423
Raw Water Mn Conc. Raw Water Mn Conc. Raw Water Mn Conc. Raw Water Mn Conc.
= 0.5 mg/L = 0.5 mg/L = 0.5 mg/L = 0.5 mg/L
Plant Size Finished Water Mn Finished Water Mn Finished Water Mn Finished Water Mn
(MGD) Conc. = 0.05 mg/L Conc. = 0.02 mg/L Conc. = 0.015 mg/L Conc. = 0.01 mg/L
1 $14,200 $20,200 $22,200 $22,200
CGS
10 $49,000 $103,000 $129,000 $129,000
(Conventional)
100 $356,000 $870,000 $1,120,000 $1,120,000
1 $9,400 $15,400 $17,400 $17,400
Direct Filtration 10 $43,000 $97,000 $123,000 $123,000
Technology 100 $342,000 $850,000 $1,110,000 $1,110,000
for 1 $0 $9,000 $11,000 $11,000
Manganese Lime Softening 10 $0 $80,000 $102,000 $102,000
Incidental to 100 $0 $730,000 $910,000 $910,000
Process 1 $15,200 $21,200 $22,200 $22,200
Advanced
10 $56,000 $92,000 $114,000 $114,000
Clarification
100 $392,000 $760,000 $900,000 $900,000
Membranes - 1 $6,000 $11,000 $13,000 $13,000
Mn as 10 $50,000 $100,000 $120,000 $120,000
Incidental 100 $400,000 $900,000 $1,100,000 $1,100,000
1 $100,000 $107,000 $118,000 $133,000
Mn Greensand 10 $870,000 $940,000 $1,030,000 $1,180,000
100 N/A N/A N/A N/A
1 $204,000 $209,000 $209,000 $209,000
Technology Membranes 10 $1,830,000 $1,860,000 $1,860,000 $1,860,000
for
100 $17,300,000 $17,600,000 $17,600,000 $17,600,000
Manganese
Removal 1 $157,000 $169,000 $171,000 $175,000
Diatomaceous
Only 10 $1,380,000 $1,490,000 $1,510,000 $1,540,000
Earth
100 N/A N/A N/A N/A
1 $133,000 $137,000 $141,000 $141,000
Ion Exchange 10 $1,240,000 $1,280,000 $1,310,000 $1,310,000
100 $11,800,000 $12,200,000 $12,600,000 $12,600,000
425
0
CGS Direct Filtration Lime Softening Advanced Membranes -
(Conventional) Clarification Mn as Incidental
Figure G.1 Cost to benefit comparison of technologies for manganese removal only
15
Cost to Benefit Ratio
10
0
Mn Greensand Membranes Diatomaceous Earth Ion Exchange
Figure G.2 Cost to benefit comparison of technologies for manganese removal only
426
Assumptions
1. At 0.05 mg/L approximately percentage of the utility's customers get affected = 1%
2. Per capita water consumption = 378 L/day
100 gal/day
3. Unaccounted percentage of water = 15%
4. Of the supplied water, percentage of water for residential use = 90%
Impact Analysis
Plant Total Residential Per Capita Water Population Annual Annual
Capacity Water Usage Consumption Population Affected by Per Capita Impact (0.05 Impact (0.02
(MGD) (MGD) (gal/day) Served 0.05 mg/L Mn Annual Impact mg/L of Mn) mg/L of Mn)
Plant #1 1 0.765 100 7,650 77 $150 $11,600 0
Plant #2 10 7.650 100 76,500 765 $150 $115,000 0
Plant #3 100 76.500 100 765,000 7,650 $150 $1,150,000 0
427
Legend
shaded cells are for data entry
Assumptions
Capital cost for UPGRADES if manganese is present with the following processes:
Typical Capital Modifications Capital Cost for Capital Cost for Capital Cost for
Contaminant Required for Increased 1 MGD Plant 10 MGD Plant 100 MGD Plant
Process Reduced Manganese Control (Upgrading cost only) (Upgrading cost only) (Upgrading cost only)
Turbidity - Addition of Chlorine prior NaOCl: $ 55,000 NaOCl: $ 70,000 NaOCl: $ 160,000
Organics to filtration* KMnO4: $ 60,000 KMnO4: $ 85,000 KMnO4: $ 180,000
CGS
(conventional) Taste and Odor - Addition to KMnO4 feed Total $ 115,000 Total $ 155,000 Total $ 340,000
Precursors system - raw water
Disinfection
Turbidity - Addition of Chlorine prior NaOCl: $ 55,000 NaOCl: $ 70,000 NaOCl: $ 160,000
Organics to filtration*
Direct
Taste and Odor Total $ 55,000 Total $ 70,000 Total $ 160,000
Filtration
Precursors
Disinfection
Turbidity - Addition of Chlorine prior NaOCl: $ 55,000 NaOCl: $ 70,000 NaOCl: $ 160,000
Advanced Organics to filtration* KMnO4: $ 60,000 KMnO4: $ 85,000 KMnO4: $ 180,000
Clarification Precursors - Addition to KMnO4 feed Total $ 115,000 Total $ 155,000 Total $ 340,000
system - raw water
Hardness - Addition of Chlorine prior Not Applicable Not Applicable Not Applicable
Lime
Barium to filtration*
Softening
- Addition of Chlorine prior NaOCl: $ 55,000 NaOCl: $ 70,000 Not Applicable
to filtration*
Direct
Total $ 55,000 Total $ 70,000
Filtration
* Chlorine would be available for disinfection (primary or system residual). Capital for adding feed capability and additional Chlorinator.
Comments: (1) Assume equipment life is 20 years; (2) Chlorine: Sodium Hypochlorite; (3) Capital cost includes installation, piping,
pumps, feeders, electrical, controls, Cl2 analyzer, storage (4) Capital cost does not include superstructure
428
Comments
1. Raw water manganese is assumed to be 0.5 mg/L.
2. KMnO4 dose is 1.0 to 1.5 mg/L.
3. Chlorine added prior to filtration at dose of 1.0 mg/L for catalytic oxidation
4. Capital cost include equipment, electrical, instrumentation, chemical feed system , superstructure.
5. Capital costs do not include wells, raw water pumps, high service pumps, waste disposal fees, intake, source development
6. Operating costs include labor, analysis, chemicals (chlorine and KMnO4), monitoring, plant power (excluding pumping)
Capital Cost
Effective Interest rate = 5%
Equipment life (compounding period) = 20 years
Capital Cost
Associated with Annual Capital
Capital Cost Mn Removal Recovery
Plant #1 = 1 MGD $2,000,000 $115,000 $9,200
Plant #2 = 10 MGD $15,000,000 $155,000 $12,000
Plant #3 = 100 MGD $120,000,000 $340,000 $27,000
429
Comments
1. Raw water manganese is assumed to be 0.5 mg/L.
2. Chlorine fed prior to filtration for catalytic oxidation. Applied dose 1 mg/L.
Capital Cost
Effective Interest rate = 5%
Equipment life (compounding period) = 20 years
Capital Cost
Associated with Annual Capital
Capital Cost Mn Removal Recovery
Plant #1 = 1 MGD $1,500,000 $55,000 $4,400
Plant #2 = 10 MGD $12,000,000 $70,000 $6,000
Plant #3 = 100 MGD $95,000,000 $160,000 $13,000
430
Comments
1. Raw water manganese is assumed to be 0.5 mg/L.
2. KMnO4 dose is 1.0 to 1.5 mg/L.
3. Example of advanced clarification processes include dissolved air flotation, ballasted flocculation,
tube/plate assisted devices, solid contact clarifiers.
4. Capital cost is for clarification alone
5. Chemical feed prior to both clarification and filtration (polymer, chlorine, KMnO4)
Capital Cost
Effective Interest rate = 5%
Equipment life (compounding period) = 20 years
Capital Cost
Associated with Annual Capital
Capital Cost Mn Removal Recovery
Plant #1 = 1 MGD $400,000 $115,000 $9,200
Plant #2 = 10 MGD $3,500,000 $155,000 $12,000
Plant #3 = 100 MGD $30,000,000 $340,000 $27,000
431
Comments
1. Raw water manganese is assumed to be 0.5 mg/L.
2. No bypass
3. Life of membranes is 10 years.
4. The membrane costs are based on ultrafiltration or nanofiltration
Capital Cost
Effective Interest rate = 5%
Equipment life (compounding period) = 10 years
432
Comments
1. Raw water manganese is assumed to be 0.5 mg/L.
2. No bypass
3. Life of membranes is 10 years.
4. The membrane costs are based on ultrafiltration or nanofiltration
Capital Cost
Effective Interest rate = 5%
Equipment life (compounding period) = 20 years
However, membranes are assumed to be replaced once, as a whole, in the fixed 20 year life cycle
Capital Cost of Capital Cost Annual Capital
2 Membrane Associated with Recovery in 20
Systems Mn Removal Year Period
Plant #1 = 1 MGD $1,700,000 $1,700,000 $136,000
Plant #2 = 10 MGD $16,000,000 $16,000,000 $1,280,000
Plant #3 = 100 MGD $156,000,000 $156,000,000 $12,500,000
433
Comments
1. Raw water manganese is assumed to be 0.5 mg/L.
2. KMnO4 for Mn Greensand regeneration daily
3. Chlorine feed if iron is present
4. 100 MGD is not a practical size
Capital Cost
Effective Interest rate = 5%
Equipment life (compounding period) = 20 years
Capital Cost
Associated with Annual Capital
Capital Cost Mn Removal Recovery
Plant #1 = 1 MGD $750,000 $750,000 $60,200
Plant #2 = 10 MGD $6,500,000 $6,500,000 $522,000
Plant #3 = 100 MGD N/A N/A N/A
434
Comments
1. Raw water manganese is assumed to be 0.5 mg/L.
2. Single pass
3. No bypass
4. Vacuum or pressure system
5. Capital cost is same as direct filtration
6. Chlorine fed prior to filtration for catalytic oxidation. Applied dose 1 mg/L.
Capital Cost
Effective Interest rate = 5%
Equipment life (compounding period) = 20 years
Capital Cost
Associated with Annual Capital
Capital Cost Mn Removal Recovery
Plant #1 = 1 MGD $1,000,000 $1,000,000 $80,200
Plant #2 = 10 MGD $9,000,000 $9,000,000 $722,000
Plant #3 = 100 MGD N/A N/A N/A
435
Comments
1. Raw water manganese is assumed to be 0.5 mg/L.
2. Ion exchange for manganese removal only
Capital Cost
Effective Interest rate = 5%
Equipment life (compounding period) = 20 years
Capital Cost
Associated with Annual Capital
Capital Cost Mn Removal Recovery
Plant #1 = 1 MGD $800,000 $800,000 $64,000
Plant #2 = 10 MGD $7,500,000 $7,500,000 $600,000
Plant #3 = 100 MGD $70,000,000 $70,000,000 $5,620,000
436
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