COMPARISON OF NATURAL ORGANIC MATTER (NOM) REMOVAL

PROCESSES ON DISINFECTION BYPRODUCT (DBP) FORMATION DURING

DRINKING WATER TREATMENT

A Thesis

Presented to

The Graduate Faculty of The University of Akron

In Partial Fulfillment

of the Requirements for the Degree

Master of Science

John Ryan Less

May, 2011
 COMPARISON OF NATURAL ORGANIC MATTER (NOM) REMOVAL

PROCESSES ON DISINFECTION BYPRODUCT (DBP) FORMATION DURING

DRINKING WATER TREATMENT

John Ryan Less

Thesis

Approved: Accepted:

_______________________________ _______________________________
Advisor Dean of the College
Dr. Stephen Duirk Dr. George K. Haritos

_______________________________ _______________________________
Faculty Reader Dean of the Graduate School
Dr. Christopher Miller Dr. George R. Newkome

_______________________________ _______________________________
Faculty Reader Date
Dr. Lan Zhang

_______________________________
Department Chair
Dr. Wieslaw Binienda

ii
 ABSTRACT

Natural aquatic organic matter (NOM) reacts with chlorinated disinfectants used

to treat public drinking water supplies resulting in the formation of toxic and

carcinogenic disinfection byproducts (DBPs). Therefore, treatment processes that reduce

the concentration of NOM prior to drinking water disinfection have been found to reduce

the formation of these unwanted DBPs. Conventional enhanced coagulation was

compared with a novel anion exchange resins for reducing DBP precursors located in the

negatively charged fraction of the NOM matrix.

Three anion exchange resins (AERs) were compared (IRA-910, IRA-958, and

MIEX) to determine which resin would not only remove NOM but DBP precursors as

well. All the AERs were found to be highly proficient at NOM reduction specifically the

moieties that absorb UV light at 254 nm and 272 nm over 75 minutes of contact time;

however, MIEX removed NOM at a faster rate than the Amberlite resins. Results show

that pH had no significant effect on the removal of chromophores and fluorophores (i.e.

EEM base pairs A and C) when treated with MIEX or enhanced coagulation.

Coagulation was effective at removing 30-45% NOM for Akron and Barberton source

waters based on peak intensity excitation-emission pairs taken from the EEM (excitation-

emission matrix). Peak intensity in the T region of the EEM for the Barberton source

iii
water, which correlates to positively charged soluble microbial, was found to be

relatively resilient to each NOM removal process.

DBP formation was determined as a function of pH for the different NOM

removal processes. MIEX resulted in significant reduction in DBP concentrations for

both source waters when compared to DBP formation in the chlorinated raw source

waters. MIEX out performed both coagulants reducing the formation of DBPs in both

source waters. At an elevated chlorine concentration in the raw samples, as pH increases

from 6.5 to 8, chloroform formation increases, TCAA concentrations decrease and

dichloroacetic acid (DCAA) is not affected. The two coagulants both reduced DBP

formation; however, alum appeared to reduce DBP concentrations more significantly

than ACH at pH 8.2.

iv
 ACKNOWLEDGEMENTS

I would like to thank my committee members: Dr. Lan Zhang, and Dr.

Christopher Miller. Your guidance throughout this experience is greatly appreciated. I

would also like to thank Andrew Skeriotis, Daniel Leslie, Danyang Wu, Elizabeth

Crafton, and Nancy Sanchez for all of their help and guidance. I would like to thank my

family and friends for their support.

Finally, I would like to express my sincere gratitude to my advisor, Dr. Stephen

Duirk for his help throughout this process. Without his encouragement and guidance as

my advisor and my friend I would not have accomplished all that I have.

v
 TABLE OF CONTENTS
Page

INTRODUCTION.................................................................................................................... 1

1.1 Perspective ............................................................................................................. 1

1.2 Research Objectives .............................................................................................. 3

1.3 Research Approach ................................................................................................ 4

LITERATURE REVIEW ........................................................................................................ 5

2.1 Chlorination, DBP formation, and NOM Characterization ................................ 5

2.2 Conventional Technologies Processes for NOM removal .................................. 7

2.3 Anion Exchange for NOM Removal .................................................................... 9

2.4 Spectroscopic Techniques used to Determine NOM Removal ........................ 10

EXPERIMENTAL PROCEDURES ..................................................................................... 13

3.1 Materials............................................................................................................... 13

3.2 Methods and Procedures ..................................................................................... 16

3.2.1Anion exchange resin (AER) preparation and

experiments ................................................................................................................ 16

3.2.2 Coagulation Experiments ......................................................................... 18

3.2.3 Chlorine Experiments ............................................................................... 19

3.2.4 DBP Analysis ............................................................................................ 19

vi
 3.2.5 Fluorescence and UV Spectroscopy ........................................................ 21

3.2.6 Ion Analysis ................................................................................................. 21

RESULTS AND DISCUSSION ........................................................................................... 23

4.1 Kinetic Removal of NOM with selected AERs ................................................. 23

4.2 Comparison of NOM Removal Processes ......................................................... 30

4.2.1 MIEX removal of NOM as a function of pH ........................................... 30

4.2.2 MIEX and Enhanced Coagulation Treatment Processes

for NOM Removal ..................................................................................................... 36

4.3 DBP Formation .................................................................................................... 43

4.3.1 DBP Formation after Coagulation/MIEX Treatment

During Simulated Drinking Water Treatment Conditions ...................................... 43

4.3.2 DBP Formation after Coagulation/MIEX Treatment at

Elevated Chlorine Concentrations ............................................................................ 47

SUMMARY AND RECOMMENDATIONS ...................................................................... 57

5.1 Summary .............................................................................................................. 57

5.2 Recommendations ............................................................................................... 59

BIBLIOGRAPHY .................................................................................................................. 60

Appendix A………………………………………………………………………………64

vii
 LIST OF TABLES

Table Page

3.1 NOM and source water characteristics for the Akron/Barberton

raw waters .………………………………………………………………………15

3.2 Anion exchange resin structural characteristics and

capacities ………………...………………………………………………………17

4.1 Spectral Characteristics of Akron/Barberton prior to

Chlorination …………………………………………………………………......37

4.2 Spectral characteristics of Akron/Barberton prior to

Chlorination ……………………………………………………………………..37

4.3 Average DBP concentrations for treated Akron/Barberton water

after 24 hours in the presence of aqueous chlorine ……………………………...46

4.4 Average DBP concentrations for treated Akron/Barberton water

after 24 hours in the presence of aqueous chlorine ……………………………...46

4.5 DBP- Carbon ratio in final DBP formation for pH 6.5 ………………………....56

4.6 DBP- Carbon ratio in final DBP formation for pH 8.2 ………………………....56

viii
 LIST OF FIGURES

Figure Page

Figure 4.1 Monitoring DOC removal as a function of time in the presence of AERs
[AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C. ..................................................................... 25

Figure 4.2 Monitoring UV254 reduction as a function of time in the presence of AERs
[AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C. ..................................................................... 26

Figure 4.3 Monitoring UV272 reduction as a function of time in the presence of AERs
[AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C. ..................................................................... 27

Figure 4.4 Monitoring EEM base pair A reduction as a function of time in the presence of
AERs [AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C. .......................................................... 28

Figure 4.5 Monitoring EEM base pair C reduction as a function of time in the presence of
AERs [AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C. .......................................................... 29

Figure 4.6 Monitoring UV254 removal as a function of time in the presence of MIEX
[MIEX] = 3.2 g/L and [DOC] o = 6.43 mg/L-C. ................................................................... 32

Figure 4.7 Monitoring UV272 removal as a function of time in the presence of MIEX
[MIEX] = 3.2 g/L and [DOC] o = 6.43 mg/L-C. ................................................................... 33

Figure 4.8 Monitoring EEM base pair A removal as a function of time in the presence of
MIEX. [MIEX] = 3.2 g/L and [DOC]o = 6.43 mg/L-C. .................................................... 34

Figure 4.9 Monitoring EEM base pair C removal as a function of time in the presence of
MIEX. [MIEX] = 3.2 g/L and [DOC]o = 6.43 mg/L-C. .................................................... 35

Figure 4. 10 EEM spectra for (a) Akron Raw, (b) MIEX, (c) ACH, and (d) Alum ([DOC]
Raw = 6.43 mg/L, [DOC] MIEX = 1.52 mg/L, [MIEX]Dose= 3.2 g/L, [DOC]ACH = 4.20
mg/L, [ACH]Dose= 10 mg/L, [DOC]Alum= 4.08, [Alum]Dose= 40 mg/L). ............................ 41

Figure 4. 11 Fluorescence intensity: (a) Barberton Raw and (b) MIEX treated water
([TOC]Raw = 4.15 mg/L, [TOC]MIEX = 1.51 mg/L, and [MIEX]Dose= 3.2 g/L). ................ 42

ix
Figure 4. 12 TCAA formations at pH 6.5 for Akron source water as a function of NOM
removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC] MIEX =1.52 mg/L-
C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C). .................... 49

Figure 4. 13 TCAA formation at pH 8.2 for Akron source water as a function of NOM
removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC] MIEX =1.52 mg/L-
C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C). .................... 50

Figure 4. 14 DCAA formation at pH 6.5 for Akron source water as a function of NOM
removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC] MIEX =1.52 mg/L-
C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C). .................... 51

Figure 4. 15 DCAA formation at pH 8.2 for Akron source water as a function of NOM
removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC] MIEX =1.52 mg/L-
C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C). .................... 52

Figure 4. 16 Chloroform formation at pH 6.5 for Akron source water as a function of

NOM removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC]MIEX =1.52
mg/L-C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C). .......... 53

Figure 4. 17 Chloroform formation at pH 8.2 for Akron source water as a function of

NOM removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC]MIEX =1.52
mg/L-C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C). .......... 54

x
 CHAPTER I

INTRODUCTION

1.1 Perspective

Chlorination has been a well established method for disinfecting public drinking

water supplies in order to minimize outbreaks of waterborne pathogens protecting

communities from diseases like cholera and typhoid fever. However, the reaction of

aqueous chlorine with natural organic matter (NOM) results in the formation of unwanted

disinfection byproducts (DBPs). Trihalomethanes (THMs) and haloacetic acids (HAAs)

are the two most prevalent DBPs classes resulting from chlorination of drinking water

supplies (Liang & Singer, 2003). These DBPs and have been found to be carcinogenic,

genotoxic, cytotoxic, and hepatotoxic (Muellner et al., 2007; Plewa et al, 2008).

Therefore, the drinking water disinfection process must not only maintain the microbial

integrity of a community water system but minimize exposure to toxic carcinogens.

To minimize human health effects from consuming DBPs formed in chlorinated

drinking water, the Disinfectants/Disinfection Byproducts (D/DBP) rule established

maximum contaminant levels (MCLs) for these two classes of DBPs (USEPA, 1998 and

USEPA, 2006), which is 60µg/L and 80µg/L for the sum of regulated HAAs and THMs

respectively. For the HAAs, 60µg/L represents the sum of the 5 regulated HAAs

1
including trichloroacetic acid (TCAA), dichloroacetic acid (DCAA), monochloroacetic

acid (MCAA), monobromoacetic acid (MBAA), and dibromoacetic acid (DBAA) on a

total mass per volume basis. The sum of the concentrations of chloroform,

bromodichloromethane, dibromochloromethane, and bromoform are regulated on at a

total of 80µg/L.

One strategy to reduce the DBP formation is to reduce the concentration of NOM

prior to chlorination. Stage 1 of the D/DBP rule defines the amount of NOM to be

removed through enhanced coagulation as a function of source water alkalinity (Bell-

Ajay et al., 2000). Stage 2 of the D/DBP rule mandates that there must be a minimum

disinfectant residual detected throughout the entire drinking water distribution system.

Therefore, reducing DBP formation is highly dependent on treatment processes that not

only reduce the concentration of NOM but the specific components that contribute to

DBP formation (i.e., DBP precursors).

Anion exchange resins are an efficient and emerging treatment process for

removing NOM from public drinking water supplies. Anion exchange resins are highly

complex polymeric surfaces designed for trapping and exchanging ions (Croue et al.,

1999; Singer, 2002; Tan et al., 2005). Anion exchange occurs when the resin exchanges

the negatively charged exchangeable ion bound to the resin surface with negatively

charged NOM components resulting in NOM being absorbed to the resin surface. Some

AERS have been found to reduce NOM concentrations by approximately 90% and DBP

formation by 70% (Boyer & Singer, 2005 and Wert et al, 2005).

2
 Fluorescence spectroscopy is a technique used to characterize NOM based on

composition of the organic matrix. NOM fluorescence occurs when an electron in the

NOM structure absorbs energy from light which excites an electron and promotes it into

an unoccupied orbital. The energy difference between the ground state and the exited

singlet state determines the wavelengths at which light will be emitted as the electron

returns to the ground state (Stedmon et al., 2003). NOM profiling has been achieved

through the use of fluorescence excitation-emission matrices (EEM), which captures the

fluorescence spectra across a wide range of excitation and emission wavelengths

(Christensen et al., 2005). NOM can then be characterized by peak intensity excitation-

emission pairs taken from the EEM (Marhaba and Kochar, 2000). These EEM spectra

peaks can represent DBP precursors in source waters. Monitoring the removal of these

peaks during the conventional surface water treatment process could indicate the

effectiveness of these processes to reduce DBP precursor concentrations prior to

chlorination.

1.2 Research Objectives

Objective 1: Compare the performance of three strong anion exchange resins (AERs)

(MIEX, IRA-910, and IRA-958) for their application in drinking water treatment (i.e.

NOM removal). NOM removal was assessed by measuring total organic carbon (DOC),

reduction UV absorbance at 254nm (UV254) and 272nm (UV272), and reduction in

fluorescence EEM base pair intensities.

3
 Objective 2: The effect of pH on each NOM removal processes. MIEX and two

coagulants (ACH and alum) were used to treat two surface water sources with

significantly different fluorescence spectral characteristics. NOM/DBP precursor

removal was determined by reduction in spectral characteristics of the NOM remaining.

Objective 3: Determine DBP formation as a function of pH for the three NOM

removal treatment processes. DBP formation was then evaluated under simulated

drinking water treatment conditions in order to determine which NOM removal treatment

process was the most effect as pH of the source water was varied from 6.5-9.

1.3 Research Approach

A thorough literature review was conducted to understand human health effects and

the regulations implemented by U.S. EPA to minimizing exposure to toxic and

carcinogenic DBPs. Then, novel and conventional technologies for NOM removal were

evaluated in order to determine the correlation to NOM removal and DBP precursor

reduction. Source waters with different NOM characteristics were collected during the

months of August – November and used to examine the impact of AERs and enhanced

coagulation on NOM removal. DBP precursor reduction was then evaluated by the

kinetic formation of DBPs in the presence of aqueous chlorine. Results will be analyzed

for statistical variation of NOM properties, and their correlation to DBP formation.

4
 CHAPTER II

LITERATURE REVIEW

2.1 Chlorination, DBP formation, and NOM Characterization

Aqueous chlorine has been used in the United States to disinfect drinking water

preventing outbreaks of waterborne pathogens for over 100 years. Chlorine, either as gas

or concentrated aqueous hypochlorite solution, is the predominant choice for primary and

secondary disinfection for 90% of drinking water systems in the US (AWWA, 2000).

However, aqueous chlorine has been found to react with natural organic matter (NOM)

and other anthropogenic chemicals not removed through conventional drinking water

treatment (i.e., coagulation, flocculation, sedimentation, and filtration) (Bell-Ajy et al.,

2000). Public health concerns exist due to the formation of disinfection byproducts

(DBPs), particularly trihalomethanes (THM) and haloacetic acids (HAA), which are the

two most prevalent DBPs classes resulting from chlorination (Liang & Singer, 2003).

THMs and HAAs are carcinogenic, genotoxic, cytotoxic, and hepatotoxic (Muellner et

al., 2007; Plewa et al, 2008). Toxicological studies have shown that exposure to THMs

and HAAs can elicit reproductive and developmental effects in laboratory animals as well

as human health effects such as blood and kidney damage (USEPA, 2006). Based on the

potential for human health effects from consuming DBPs formed in chlorinated drinking

5
water, the Disinfectants/Disinfection Byproducts (D/DBP) rule established the maximum

contaminant levels (MCLs) for a few classes of these byproducts in finished drinking

water and determined specific NOM removal requirements through enhanced coagulation

(USEPA, 1998; USEPA, 2006). The MCLs for HAAs and THMs are 60µg/L and

80µg/L respectively. For HAAs, 60µg/l represents the sum of the 5 regulated HAAs

including trichloroacetic acid (TCAA), dichloroacetic acid (DCAA), monochloroacetic

acid (MCAA), monobromoacetic acid (MBAA), and dibromoacetic acid (DBAA) on a

total mass per volume basis. The sum of the concentrations of chloroform,

bromodichloromethane, dibromochloromethane, and bromoform are regulated on at

80µg/l for THMs.

NOM removal prior to chlorination is one strategy to reduce the DBP formation.

Stage 1 of the D/DBP rule established guidelines for the amount of NOM to be removed

through enhanced coagulation as a function of source water alkalinity (Bell-Ajay et al.,

2000). Stage 2 of the D/DBP rule mandated that there must be a minimum disinfectant

residual detected throughout the entire drinking water distribution system. Therefore,

reducing DBP formation is highly dependent on treatment processes to reduce the

concentration of NOM but also the components that specifically result in DBP formation

(i.e., DBP precursors). However, NOM is a complex mixture of soluble organic

components that are operationally divided into two fractions: hydrophobic and

hydrophilic (Marhaba & Yong Pu, 2003). Hydrophobic fractions primarily consist of

humic and fulvic acids (Kanokkantapong et al., 2006). Humic acid is described as being

soluble in dilute alkaline media and will precipitate upon acidification; whereas fulvic

6
acid will remain in the solution at pH ≤ 2 (Steelink, 1977). The hydrophilic fraction is

composed of low molecular weight carbohydrates, proteins, and amino acids (Marhaba &

Yong Pu, 2003). Each fraction can act as a precursor to DBP formation in the presence

of chlorine, though hydrophobic fraction contains higher concentrations of DBP

precursors (Leenheer & Croué, 2003).

2.2 Conventional Treatment Processes for NOM removal

Conventional technologies used to remove NOM during drinking water treatment

include enhanced coagulation, membranes and activated carbon. Of these processes,

coagulation is the most widely used in water treatment. Enhanced coagulation is defined

as an excess amount of coagulant added to not only reduce turbidity but to reduce the

concentration of NOM (Singer, 2002). Negatively charged NOM creates a coagulant

demand for positively charged aluminum (Al3+) species resulting in a stoichiometric

relationship between the alum dose and the raw water concentration and composition

NOM that is pH dependent (Edzwald & Tobiason, 1999). Due to the negatively charged

carboxylic acids groups within the hydrophobic NOM fraction, NOM and turbidity are

removed during enhanced coagulation (Bell-Ajay et al., 2000; AWWA, 2000). Lowering

the pH to reach optimal NOM removal with aluminum based coagulants may not always

be cost effective, so alternative treatment processes may need to be evaluated (AWWA,

2000).

Activated carbon, in either powder (PAC) or granulated (GAC) forms, has been

used to remove NOM by adsorption to the carbon surface reducing the presence of DBP

7
precursors in the finished water prior to chlorination (Kim & Kang, 2008). PAC is

widely used to reduce the concentration of trace organics in drinking water. Activated

carbon processes are very costly do to the amount of PAC required for NOM removal or

the operation and maintenance of up flow GAC contactors or sand filter caps.

Since NOM is comprised of a wide range of molecular weights and functional

groups, membranes are an alternative method for NOM removal (Chang et al., 2009).

Membrane filtration consists of four different types of pressure driven processes: reverse

osmosis (RO), nanofiltration (NF), ultrafiltration (UF), and microfiltration (MF). RO has

been used for the removal of anions and cations from fresh water, which can be very

costly due to the power required to generate pressures of 150-1,200 psi. NF is used for

removing NOM, color, DBP precursors and hardness. NF has emerged as a reliable

treatment process for NOM removal and water softening because the membranes operate

at the lower pressures (75-150psi) (Jacangelo et al., 1995). UF membranes cover a wider

range of particle sizes and can provide NOM removal at high pressures or liquid-solid

separation at lower pressures (Jacangelo et al, 1995). MF primarily deals with particulate

and microbial removal due to the membrane pore size approximately 0.1 µm.

Membranes can substantially reduce NOM concentrations but require conventional

surface water pretreatment (coagulation, flocculation, and sedimentation) to reduce

constituents that can foul the membranes like hydrophobic NOM and divalent cations

such as calcium and magnesium (Chang et al., 2009).

8
2.3 Anion Exchange for NOM Removal

Anion exchange resins are efficient and emerging alternative technology for

removing NOM. Anion exchange resins are complex polymeric surfaces designed for

trapping and exchanging ions that are bounded to a bead like structure (Croue et al.,

1999; Singer, 2002; Tan et al., 2005). Anion exchange occurs when a resin exchanges its

negatively charged exchangeable ion with negatively charged NOM functional groups,

causing the NOM to absorb to the resin surface. Waters containing low molecular weight

humic substances, soluble microbial products and proteins can be difficult to remove by

coagulation (Edswald, 1993; Bolto et al., 2004); therefore, anion exchange resins (AERs)

have been used for the selective removal of these DBP precursors. AERs are capable of

removing high and low molecular weight (MW) organic components while

coagulation/flocculation mostly removes high molecular weight NOM components.

Humbert et al. (2008) examined the potential of AERs for NOM removal and found that

AERs are able to remove 75% of NOM after approximately 30 minutes of contact time.

MIEX is a strongly base anion exchange resin used to remove NOM from raw

water sources using chloride as the exchangeable anion. Ion exchange resins usually

have an exchange capacity value >1.0. Due to its innovative yet proprietary formation,

MIEX’s capacity is usually significantly less than other commercially available anion

exchange resins. However, the smaller size, 180µm, and magnetic iron bead structure

allows for selective removal of NOM and promotes bead aggregation increasing it

settling characteristics when compared to other AERs (Singer et al., 2007). MIEX resin

(Orica Watercare, Watkins, CO) has been successfully used to remove NOM and

9
bromide from a wide range of source waters with significantly different characteristics

(Hsu & Singer, 2010; Mergen et al., 2008; Tan & Kilduff, 2007; Drikas et al, 2009;

Singer & Bilyk, 2002). When MIEX was applied to waters containing higher

concentrations of bicarbonate, bromide, and chloride; NOM and bromide were effectively

removed although bromide removal was found to be a function of water hardness (Hsu &

Singer, 2010). Pre-treatment with MIEX has shown to reduce DBP formation potential

of HAAs (HAAFP) and THMs (THMFP) by up to 70% (Boyer & Singer, 2005). Based

on the chemical makeup of the raw water, pre-treatment with MIEX can remove up to

90% of DOC (Wert et al, 2005). MIEX has high selectivity for NOM with high specific

ultra-violet absorbance, SUVA, which has been found to be a reliable estimation of

source water aromaticity (Boyer et al, 2008; Hsu & Singer, 2010). MIEX has faster

kinetic removal of NOM compared to other AERs (Humbert et al., 2005).

2.4 Spectroscopic Techniques used to Determine NOM Removal

Spectroscopic techniques have been used to characterize the reaction of aqueous

chlorine with NOM. Initially, differential UV spectroscopy at λ = 272 nm, has been used

to characterize the reaction of aqueous chlorine with NOM (Korshin et. al., 1997).

Correlations were later developed to describe the formation of THMs and HAAs due to

changes in adsorption at 272 nm, which was used as a surrogate for NOM structural

changes due to reaction with aqueous chlorine (Korshin et. al., 2002). However, UV

spectroscopy provides a featureless spectra proving difficult to ascertain specific

information about structural changes in NOM due to reaction with aqueous chlorine.

10
 Fluorescence spectroscopy is an optical technique used to characterize NOM

based on concentration and composition. NOM fluorescence occurs when an electron in

the NOM structure absorbs energy from light which excites an electron and promotes it

into an unoccupied orbital (Stedmon et al., 2003). After the energy is relaxed, the

electron eases to its ground state emitting light. The difference in the initial state and the

excited state determines the range of light wavelengths emitted, which are generally

lower in energy than the excitation wavelength (Hudson et al., 2007). NOM profiling has

been achieved through the use of fluorescence excitation-emission matrices (EEM),

which captures the fluorescence spectra across a wide range of excitation and emission

wavelengths (Christensen et al., 2005). Coble (1996) characterized humic-like and

protein-like organics in freshwater, coastal, and marine environments by observing the

location of peak intensities within the matrix. Due to the complexity of the EEM spectra,

NOM has been characterized by peak intensity excitation-emission pairs taken from the

EEM (Marhaba and Kochar, 2000). The EEM spectra for most freshwaters used as

drinking water sources can be characterized through three main fluorescence intensities,

peak A (humic and fulvic-like), peak C (humic and fulvic- like) and peak T (protein-like).

The A and C peaks are evaluated because the humic/fulvic- like material are primarily

responsible for the formation of DBPs during chlorination (Coble, 1996). The intensities

of peaks A, C, and T have been successfully used to monitor DOC removal (Gone et al.,

2009). Fluorescence peaks A, C generally decrease throughout water treatment

procedures like enhanced coagulation, while peak T (i.e., protein-like peak) is less

affected by conventional surface water treatment processes.

11
 Specific components within the EEM spectra have been correlated with both DBP

formation and chlorine consumption. Johnstone and Miller (2009) used regional analysis

of fluorescence EEMs before and after chlorination to predict chlorinated DBP formation

through parallel factor analysis (PARAFAC). PARAFAC is a statistical model that

decomposes data into tri-linear components, which is well suited to describe three

dimensional EEM spectra (Stedmon et al., 2003). Combined with multifactor regression

analysis, the three components determined from PARAFAC modeling and chlorine

consumption were found to correlate to chloroform, TCAA, and DCAA formation.

Using the PARAFAC component model to analyze fluorescence spectra could be an

effective tool to predict DBP formation and identify DBP precursors in the EEM spectra.

12
 CHAPTER III

EXPERIMENTAL PROCEDURES

3.1 Materials

Chlorination experiments were conducted with commercial 10-15% sodium

hypochlorite (NaOCl) purchased from Sigma Aldrich (St. Louis, Missouri). Aqueous

stock solutions and experiments utilized laboratory-prepared deionized water (18.2 MΩ-

cm-1) from a Barstead ROPure/DiamondPure system (Barnestead-Thermolyne Corp.,

Dubuque, IA). All water samples, prior to analysis, were 0.45 µM filtered with

membrane filters purchased from Millipore (Billerica, MA), which was prerinsed with

deionized water. The pH for each experiment was adjusted with either 1 N H2SO4 or

NaOH and measured using a Thermo Scientific Orion 5 star meter with a ROSS ultra

combination pH electrode probe. All other organic and inorganic chemicals were

certified ACS reagent grade. The glassware used in this study was soaked in a

concentrated free chlorine solution for 24 hours, and rinsed multiple times with deionized

water and dried prior to use. All chlorination experiments were conducted at constant

temperature (25± 1 ˚C). Source waters used in the experiments were collected from the

Akron and Barberton water treatment plant intake prior to conventional surface water

treatment. Akron and Barberton were chosen in this study due to their different water

13
characteristics. Akron is more humic and fulvic like while Barberton is more microbial.

The Akron/Barberton source water characteristics are shown in Table 3.1.

14
Table 3.1 NOM and Source Water Characteristics
Fluorescence Base Pairs (RU)
pH TOC (mg/L) UV254 UV272 A C T SUVA (L/mg)
Akron 8.2 6.43 0.126 0.101 53.56 25.77 18.08 1.96
Barberton 8 4.15 0.047 0.038 22.82 10.21 13.35 1.13

15
Alkalinity (mg Chloride Sulfate Fluoride Nitrate Sodium Potassium Hardness (mg
CaCO3/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) CACO3/L)
Akron 83 35.8 42.5 0.1 0.7 23.4 2.4 126
Barberton 65 37.2 69 0.1 0.7 32.2 2.4 121
3.2 Methods and Procedures

In order to compare the three commercial resins as well as the two coagulants the

following experiments were ran.

3.2.1Anion exchange resin (AER) preparation and experiments

MIEX anion exchange resin (Orica Water Care, Watkins, CO) arrived in a sodium

chloride brine solution. Amberlite IRA-910 and IRA-958 (Rohm and Haas, Philadelphia,

PA) were purchased from Sigma Aldrich. Before use the Amberlite resins were first

rinsed with 6 liters of deionized water. Approximately 50 g of the Amberlite resins were

added to 200 mL of methanol and shaken for 30 minutes, collected from the methanol

with Whatman GF/C glass filter, and repeated until three full methanol rinses were

achieved. Storage solution for the Amberlite IRA-910 was 7.5% NaOH solution and the

Amberlite IRA-958 was stored in 20% NaCl and 2% NaOH solution, and MIEX was

stored in the 5%NaCl solution it arrived in. Prior to use, each resin was filtered with a

0.45µm membrane filter using a Fisher Scientific Maxima C vacuum pump, rinsed with

5L of deionized water, and then dried under vacuum. The characteristics of the three

strong anionic resins used are listed in Table 2.

16
Table 3.2 Anion exchange resin structural characteristics and capacities

AER Type Structure Size Capacity Water

(µm) (meq/mL) Content (%)

MIEX (OricaWatercare) MP Acrylic 180 ------ ------

IRA-910 (Rohm & Haas) MP Styrene 510 >1.0 54-61

IRA-958 (Rohm & Haas) MP Acrylic 630 >0.8 66-72

17
 The efficacy of the three selected AERs was evaluated with batch experiments

performed on 1.5 L rough filtered (20-25µm pore size) source water under constant

stirring at 150 rpms with a Phipps and Bird stirrer (Richmond, VA) in the presence of 3.2

g/L of AER. Samples of treated water (20 mL) were taken at five different contact times

(15, 30, 45, 60, and 75 minutes) and UV254, 272, TOC, and fluorescence peaks A, C, and T

were monitored as a function of time.

Additional MIEX experiments were conducted over the pH 6.5-9.0 for both source

waters. The pH of 1 L of source water was adjusted to pH 6.5 and 7.5 using 1 N sulfuric

acid, 1 L adjusted to pH 9.0 using 1 N sodium hydroxide and 1 L was kept at its native

pH (≈ 8, see Table 3.1). Then each pH adjusted source water was stirred for

approximately 1 hour at 150 rpms, as previously described. After settling, the water was

then filtered through pre-rinsed 0.45 µm filters. All the experiments were performed in

duplicate.

3.2.2 Coagulation Experiments

The two coagulants were used to compare their NOM removal capacity compared

to anion exchange. Aluminum chloro hydrate (ACH) and aluminum sulfate (Alum) were

chosen due to their wide-spread use in the water treatment industry. Previous dose-

response jar tests found the optimal doses of ACH and Alum were 10mg/l and 40 mg/l

respectively for effective NOM removal. The coagulants were first rapid mixed using a

Phipps and Bird stirrer at 100 rpms for 1 minute, then 30 rpms for 30 minutes to promote

flocculation, and allowed to settle for 1 hour.

18
3.2.3 Chlorine Experiments

Chlorination experiments were performed on raw, anion exchange (i.e., MIEX),

and coagulant treated source waters over the pH range of 6.5-9. Initially, 500-mL of

either treated or native source water was dosed with aqueous chlorine under rapid mix

conditions achieving an initial aqueous chlorine concentration of 3.55 mg/L-Cl2. After

chlorination, the 500mL of treated water was transferred to four 120 mL chlorine

demand-free amber bottles. The chlorinated samples were stored in the dark and

incubated at 25±1 ˚C. After 24 hours, chlorine residuals were quenched with sodium

sulfite at 20% stoichiometric excess of the initial aqueous chlorine concentration prior to

analysis for DBPs, pH, fluorescence, and UV254 and UV272 measurements. The amber

bottles were used in their entirety and pH was monitored to ensure it did not vary by

more that ±0.2 of their original pH over the time course of the experiment.

Additional chlorination experiments were performed at a chlorine concentration

of 10.5 mg/L to clearly define the effect each treatment process on DBP formation. After

1, 4, 12, and 24 hours, bottles were quenched and 100 mL samples were analyzed for

DBPs, pH, fluorescence, and UV254 and UV272 were also monitored. Chlorine residuals

were measured at 1 and 24 hours.

3.2.4 DBP Analysis

Samples for DBP analysis were extracted immediately after quenching to avoid

potential artifacts due to sample storage. These samples were first acidified with

concentrated sulfuric acid to pH < 0.5, then 30 g of dried sulfate was added to each

19
sample and initially mixed by hand prior to being spiked with 1.0 µg/L of 1, 2

dibromopropane (internal standard). Finally, 3-mL of Methyl tert-Butyl Ether (MtBE)

was added for DBP extraction. Samples were mixed for 30 minutes with a Burrell wrist

action shaker (Pittsburgh, PA). The organic phase was then removed and transferred to

amber vials. For THM analysis, 0.5 mL of the organic phase from each sample was

transferred into the 2.0mL amber vials for analysis. Diazomethane was used to derivatize

the neutral HAA species to either corresponding methyl esters. To the inner tube of the

diazomethane generator, 367mg of diazold and 1.0mL of carbitol were added. The outer

generator tube contained 3mL of MtBE. Using a glass body syringe, 1.5mL of 37%

KOH was added slowly and diazomethane was generated for approximately 30 minutes.

Then 0.25mL of diazomethane was added to 0.5 mL of the sample extract and mixed

together in 2.0 mL vials. Derivatization was allowed to proceed for 30 minutes prior to

quenching excess diazomethane with silica gel. The four regulated THMs and all nine

HAAs were quantified from extracted standards over the calibration range of 0-100 ppb.

HAA and THM analysis was performed with an Agilent 7980A gas

chromatograph/mass spectrometer (GC/MS) (Santa Clara, CA) operated in constant

pressure mode. A 30 meter, 250µm diameter Restek RTX-5ms column with a film

thickness of 0.5µm was used for the analysis. The THM temperature initially started at

35˚C and was held for 5 minutes before ramping at 20˚C/minute until 250˚C. The HAA

method had an initial temperature of 35̊C and held for 5 minutes, and then ramped in

three steps: 1) 5˚C/ minute to 7 5˚C that held for 15 minutes, 2) 5˚C/ minute to 100˚C that

held for 5 minutes, 3). 5˚C/ minute to 135˚C and held for 5 minutes.

20
3.2.5 Fluorescence and UV Spectroscopy

Fluorescence and UV spectroscopy was used to obtain the spectral characteristics

for the source waters as well as to monitor spectral changes as a function of treatment

process. Prior to obtaining the fluorescence spectra, the sample was first acidified with

sulfuric acid to lower the pH to 2.75-3.25 and the ionic strength was adjusted with 0.1M

KCl. The fluorescence spectra for both the raw and treated samples were obtained with a

Hitachi F-7000 fluorescence spectrophotometer (Schaumburg, IL). From the

fluorescence spectra, three peaks (A, C, T) were selected to best describe the source

water Table 3.1. The three peaks values are provided in Raman Units (RU). A Shimadzu

UV-1601 spectrophotometer (Columbia, MD) was used to obtain the UV absorbance of

samples containing NOM at 254 nm and 272 nm.

3.2.6 Ion Analysis

Ion analysis was performed using a Dionex ICS-3000 ion chromatograph (IC)

(Sunnyvalle, CA). The IC was calibrated for anions: Fluoride, nitrite, bromide and

arsenate are from 0-100µM; iodate from 0-40 µM; nitrate and phosphate from 0-250 µM;

sulfate and chloride from 0-3000 µM. The IC is calibrated for cations: sodium,

potassium, magnesium, calcium from 0-500 µM and ammonia for 0-100 µM. Anion

analysis was performed with an AS20 column with an AG20 guard and a potassium

hydroxide eluent gradient of 5mM for 0-5 minutes, 5mM-30mM for 5-15 minutes, 30-

55mM for 15-30 minutes. Cation analysis was performed with a CS12A column with a

CG12A guard under isocratic conditions with 20 mM Methanesulfonic acid eluent. The

21
IC flow rate, for both the cations and anions, was 1mL/min, under constant temperature

30˚C, and a 10mL injection volume.

22
 CHAPTER IV

RESULTS AND DISCUSSION

This chapter was divided into three sections to discuss the experimental results.

The first section presents experimental results of NOM removal by anion exchange resins

(AERs). Section two compares the effect of magnetic ion exchange (MIEX) resin and

other removal NOM removal strategies as a function of pH. The final section compares

DBP formation upon chlorination of the treated source water (i.e., enhanced coagulation

or MIEX) over the pH range 6.5-9.0 and at different initial chlorine concentrations.

4.1 Kinetic Removal of NOM with select AERs

AERs have shown to be a treatment option to remove NOM components that

conventional treatment processes do not. However, very little is known about the kinetic

rate of NOM removal in the presence of different AERs. Therefore, three AERs

commonly used in drinking water treatment, MIEX, IRA-910, and IRA-958, were

examined for their capacity to remove NOM as monitored by TOC and UV absorbance at

λ 254 and λ272 as a function of time (Figures 4.1-4.3). An AER resin dose of 3.2 g/L was

chosen based on the suggested manufacture MIEX resin dose of 5ml/L, which was used

for all three resins. The three resins were found to be effective at removing NOM;

however, MIEX removed NOM at faster rate than the other Amberlite resins. At an

initial NOM concentration of 6.43 mg/L, MIEX reduced the NOM concentration
23
approximately 68% within 15 minutes of contact time to 2.04 mg/L while the residual

NOM concentrations in the presence of IRA-910 and IRA-958 resins were 3.66 and 3.46

mg/L respectively (Figure 4.1). IRA-910 and IRA-958 removed approximately 60% of

the NOM initially present, while MIEX removed 77% of the NOM after 75 minute

contact time as measured by TOC. While MIEX appeared to remove NOM more rapidly,

all AERs were found to be highly proficient at NOM removal, specifically the moieties

that absorb UV light at 254 and 272 nm over 75 minutes of contact time (Figures 4.2 and

4.3). When monitoring NOM removal with UV spectroscopy, the IRA-910 and IRA-958

resins removed approximately 80% of UV254 and UV272 absorbing moieties, while MIEX

removed 91% of NOM components initially present that absorb UV light. This appears

to indicate that the AERs prefer sorption of aromatic moieties; however, MIEX was

found to remove more NOM and the components that absorb UV light as a function of

time.

Fluorescence spectroscopy was also used to monitor the reduction of specific

components within NOM-EEM spectra in the presence of the AERs as a function of time.

The fluorescence spectra showed that EEM base pairs designated A and C sharply

decrease with increasing contact times in the presence of all three AERs. MIEX showed

a slightly higher removal after 75 minutes resulting in a reduction of 71% and 75% for

peaks A and C respectively, while the IRA-910 and IRA-958 had a reduction of EEM

base pairs A and C of 67-68% and 72-73% respectively.

24
 7

6 IRA 910
IRA 958
MIEX
DOC content (mg/L)

1
0 20 40 60 80 100
Contact Time (minutes)

Figure 4.1 Monitoring DOC removal for Akron as a function of time in the presence of
AERs: [AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C, .

25
 0.12

0.10 IRA 910

UV Absorbance at 254nm (1/cm)

IRA 958
MIEX
0.08

0.06

0.04

0.02

0.00
0 20 40 60 80 100
Contact Time (minutes)

Figure 4.2 Monitoring UV254 reduction for Akron as a function of time in the presence of
AERs: [AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C.

26
 0.10

IRA 910
UV Absorbance at 272nm (1/cm)

0.08 IRA 958

MIEX

0.06

0.04

0.02

0.00
0 20 40 60 80 100
Contact Time (minutes)

Figure 4.3 Monitoring UV272 reduction for Akron as a function of time in the presence of
AERs: [AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C.

27
 60

50 IRA 910
IRA 958
MIEX
40
Intensity (RU)

30

20

10

0
0 20 40 60 80 100
Contact Time (minutes)

Figure 4.4 Monitoring EEM base pair A reduction for Akron as a function of time in the
presence of AERs: [AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C.

28
 25

IRA 910
20 IRA 958
MIEX
Intensity (RU)

15

10

0
0 20 40 60 80 100
Contact Time (minutes)

Figure 4.5 Monitoring EEM base pair C reduction for Akron as a function of time in the
presence of AERs: [AER] = 3.2 g/L and [DOC]o = 6.43 mg/L-C.

29
 MIEX was found to perform better then the Amberlite anion exchange resins for

NOM removal, especially the components with high aromatic character. This could be

due to its physical characteristics that differ from the conventional ion exchange resins.

The resin particle size is approximately 180µm, which is 3-3.5 times smaller than the

Amberlite resins. The smaller resin size creates a higher external surface area allowing

for quicker NOM sorption kinetics, which resulted in a reduction in 68% NOM

concentration within 15 minutes of contact time. This differs from previously published

results that show a slightly faster NOM removal rate due to higher AER concentration

(Humbert et al., 2005). The magnetic iron oxide that is incorporated into the resin’s

structure allows it to aggregate faster, which creates larger particles with better settling

characteristics than other the AERs. Therefore, MIEX was chosen to perform additional

experiments in order to further assess removal of NOM and potential DBP precursors.

4.2 Comparison of NOM Removal Processes

MIEX is now compared at a range of pHs in order to determine if MIEX is pH

dependent. After determining if MIEX is pH dependent, MIEX will be compared to two

coagulants for NOM removal.

4.2.1 MIEX removal of NOM as a function of pH

Preliminary jar-tests experiments were conducted to determine of the effect of pH

on NOM removal in the presence of MIEX. Figures 4.6-4.9 show the reduction of

intensities of UV254, UV272 and fluorescent peaks A and C for Akron source water over

the pH range of 6.5-9.0 in the presence of MIEX. Results show that pH had no
30
significant effect on the removal of chromophores and fluorophores (i.e. EEM base pairs

A and C) when treated with MIEX. Chromophore and fluorophore intensities were

within 5% regardless of pH throughout 90 minutes of contact time. Monitoring UV254

and UV272 reduction over time, 83% of UV absorbing moieties was removed after 90

minutes of contact time with approximately 65% within the first 15 minutes.

Fluorescence peaks A and C were reduced by approximately 63% within 15 minutes of

contact time with MIEX, and the peak intensities were overall reduced by 80% after 90

minutes of contact time. The pH of the aqueous system appears to have no effect on

NOM removal in the presence of MIEX.

31
 0.14

0.12
pH 9.0
UV Absorbance at 254nm (1/cm)

pH 8.2
0.10
pH 7.5
pH 6.5
0.08

0.06

0.04

0.02

0.00

0 20 40 60 80 100
Contact Time (minutes)

Figure 4.6 Monitoring UV254 reduction as a function of time in the presence of MIEX:
[MIEX] = 3.2 g/L and [DOC] o = 6.43 mg/L-C.

32
 0.12

0.10 pH 9.0
UV Absorbance at 272nm (1/cm)

pH 8.2
0.08 pH 7.5
pH 6.5
0.06

0.04

0.02

0.00

0 20 40 60 80 100
Contact Time (minutes)

Figure 4.7 Monitoring UV272 reduction as a function of time in the presence of MIEX:
[MIEX] = 3.2 g/L and [DOC] o = 6.43 mg/L-C.

33
 1.2

1.0 pH 9.0
pH 8.2
pH 7.5
Fluorescence Reduction

0.8 pH 6.5

0.6

0.4

0.2

0.0
0 20 40 60 80 100
Contact Time (minutes)

Figure 4.8 Monitoring EEM base pair A reduction as a function of time in the presence of
MIEX: [MIEX] = 3.2 g/L and [DOC]o = 6.43 mg/L-C.

34
 1.2

1.0 pH 9.0
pH 8.2
pH 7.5
Fluorescence Reduction

0.8 pH 6.5

0.6

0.4

0.2

0.0
0 20 40 60 80 100
Contact Time (minutes)

Figure 4.9 Monitoring EEM base pair C reduction as a function of time in the presence of
MIEX: [MIEX] = 3.2 g/L and [DOC]o = 6.43 mg/L-C.

35
4.2.2 MIEX and Enhanced Coagulation Treatment Processes for NOM Removal

Akron and Barberton source waters were treated with MIEX, ACH, and alum and

were the effectiveness of each process to remove NOM. NOM was evaluated by

measuring DOC concentration, UV absorbance at λ254 and λ272 and fluorescence EEM

base pairs peaks A and C. The initial DOC concentration for Akron source water was

6.43 mg/L, which the residual DOC concentration was observed to decrease after each

treatment process. After 60 minutes of contact time, MIEX significantly decreased DOC

concentration by 76% to 1.52 mg/L, while treatment with ACH and alum reduced the

DOC concentration to 4.2 and 4.08 mg/L respectively (Tables 4.1 and 4.2). However,

DOC reduction may not correspond to reduction in DBP precursors, which is generally

indicated by reduction in UV-absorbing moieties. MIEX was also observed to

significantly reduce the concentration of UV-absorbing moieties by approximately 80%

after one hour of contact time. Although the coagulants may not have achieved similar

reduction in DOC concentration when compared to MIEX, ACH and alum were able to

remove 50% to 63% of UV-absorbing moieties respectively. For the Akron source water,

all three NOM removal processes achieved significant reductions in potential DBP

precursors as measured by UV254 and UV272.

The treatment processes were then applied to the Barberton source water. MIEX

was able to reduce the DOC from an initial concentration of 4.15 mg/L to 1.51 mg/L.

Treatment with ACH and alum reduced DOC to 2.89 and 2.98 mg/L respectively. The

36
Table 4.1 DOC concentration and UV spectral characteristics for Akron and Barberton
source waters before and after MIEX over the pH range of 6.5-9. Percent removals are
given in brackets in respect to the initial value.

DOC (mg/L) UV254 (cm-1) UV272 (cm-1)

Akron Raw 6.43 0.126 0.101
Akron MIEX 1.52 (76%) 0.024 (81%) 0.021 (79%)
Barberton Raw 4.15 0.047 0.038
Barberton MIEX 1.51 (63%) 0.016 (66%) 0.014 (63%)

Table 4.2 DOC concentration and UV spectral characteristics for Akron and Barberton
source waters before and after enhanced coagulation over at pH 6.5 and 8.2. Percent
removals are given in brackets in respect to the initial value.

DOC (mg/L) UV254 (cm-1) UV272 (cm-1)

Akron Raw 6.43 0.126 0.101
Akron ACH 4.2 (35%) 0.058 (54%) 0.051 (50%)
Akron Alum 4.08 (37%) 0.046 (63%) 0.042 (58%)
Barberton Raw 4.15 0.047 0.038
Barberton ACH 2.89 (30%) 0.031 (34%) 0.028 (24%)
Barberton Alum 2.98 (28%) 0.035 (25%) 0.033 (13%)

37
amount of DOC removed for Barberton is comparable to the amount of UV-absorbing

materials removed. MIEX was able to remove 66% while ACH and alum removed 13-

34%. The NOM removal process were found to be less effect for the Barberton source

water when compared to Akron; however, MIEX significantly reduced the DOC

concentration and intensities of UV absorbing moieties with respect to enhanced

coagulation.

The coagulants were observed to be more effective in removing DOC and UV-

absorbing moieties for the Akron source water when compared to the Barberton source

water. SUVA is the ratio of the intensity of UV-absorbing moieties at λ254 to DOC

concentration (UV254 expressed as per meter divided by the concentration of DOC

expressed in milligrams per liter). Carbon-13 nuclear magnetic resonance has been used

to determine a strong correlation between SUVA254 and the aromatic carbon content for a

large number of NOM fractions (Croué et al., 1999), which has been used as a surrogate

for DBP formation potential. The initial SUVA254 value for Akron was 1.96 L/mg-m and

Barberton was 1.13 L/mg-m. After alum treatment for both Akron and Barberton source

waters, the SUVA value dropped for Akron to 1.12 L/mg-m while the SUVA for

Barberton increased to 1.17 L/mg-m. Similar results were found for MIEX as well as

ACH. This suggests that DOC removed by each treatment process for the Barberton

source water may not significantly contribute to DBP formation upon chlorination.

Previous research has found DBP formation to be dependent on SUVA, with higher

SUVA values yielding greater THM and HAA formation potentials in the presence of

aqueous chlorine (Liang and Singer, 2003). Therefore, the DBP precursors in the

38
Barberton source water are not significantly removed by any of the treatment processes

applied here.

Fluorescence spectroscopy was also used to monitor the reduction of specific

components within in the NOM matrix. The Akron and Barberton source water were

characterized by peak intensity excitation-emission pairs taken from the EEM spectra

(Marhaba and Kochar, 2000). The locations of the Akron peaks are: peak A is located

on excitation λ= 219 nm, emission λ= 404 nm, peak C is located on excitation λ= 304

nm, emission λ=414 nm and peak T is located on excitation λ= 224 nm and excitation λ=

298 nm. The Akron source water has initial peak intensities for A, C and T equal to

53.56, 25.77 and 18.08 RU (Figure 4.10). The region where the T peak occurs for the

Akron source water was not well defined assumed to be due to relaxation of the A peak,

which the fulvic peak is substantial. Peak T is related to microbial activity resulting in

low molecular weight compounds containing amine moieties and other soluble protein

material, therefore, no protein-like moieties appear to be present in the Akron source

water. MIEX reduced peaks A and C for Akron by 86% and 89% respectively. ACH

coagulation reduced peak intensities 45% for peak A and 44% for peak C. Alum also

reduced peak intensities by 42%for peak A and 47% for peak C. Though all the

treatments showed adequate removal of NOM, MIEX was found to significantly reduce

humic/fulvic components in the Akron source water.

Fluorescence spectroscopy was then used to examine the effectiveness each

treatment had on reducing the intensities of the A, C, and T peaks in the EEM spectra of

Barberton source water. The locations of the EEM peaks for Barberton are: peak A is

39
located on excitation λ= 219 nm and emission λ= 406 nm, peak C is located on excitation

λ= 309 nm and emission λ= 416 nm, and peak T is located on excitation λ= 224 nm and

excitation λ= 298 nm. The Barberton source water had initial peak intensities for A, C

and T equal to 22.82, 10.21 and 13.35 RU respectively. MIEX reduced peak intensities

for A, C, and T by 74%, 76% and 26% respectively. ACH coagulation reduced peak

intensities for A, C, and T by 42%, 43% and 12% respectively. Alum was also found to

reduce peak intensities for the Barberton source water with a 36% reduction in peak A,

37% for peak C and 16% for peak T. Overall, reduction in peak intensities A and C were

observed to be similar with respect to each treatment process for both source waters;

however, the peak intensity T was found to be relatively resilient to each NOM removal

process for the Barberton source water. In order to determine which DOC components

are effectively removed during coagulation, Gone et al. 2009 plotted the reduction of

fluorescence intensity peaks A, C, and T to DOC removal. Their results showed that Al

and Fe salts do not efficiently coagulate nitrogen compounds and proteins found in the T

region of the EEM spectra; however, iron and aluminum salts were found to be very

effective at reducing peak intensities in the A and C region of the EEM spectra that are

mostly associated with humic and fulvic materials.

40
 (a) (b)

(c) (d)

Figure 4. 10 EEM spectra for (a) Akron Raw, (b) MIEX, (c) ACH, and (d) Alum ([DOC]
Raw = 6.43 mg/L, [DOC] MIEX = 1.52 mg/L, [MIEX]Dose= 3.2 g/L, [DOC]ACH = 4.20
mg/L, [ACH]Dose= 10 mg/L, [DOC]Alum= 4.08, [Alum]Dose= 40 mg/L).

41
 (a) (b)

(c) (d)

Figure 4. 11 EEM spectra for: (a) Barberton Raw, (b) MIEX treated water, , (c) ACH,
and (d) Alum ([TOC] Raw = 4.15 mg/L, [TOC]MIEX = 1.51 mg/L, and [MIEX]Dose= 3.2
g/L,[DOC]ACH = 2.89 mg/L, [ACH]Dose= 10 mg/L, [DOC]Alum= 2.98, [Alum]Dose= 40
mg/L).

42
4.3 DBP Formation
MIEX was compared to two coagulants to determine its DBP formation

capabilities. Two sets of these experiments were done, one at a chlorine concentration of

3.55mg/L and another at 10.5 mg/L.

4.3.1 DBP Formation After Coagulation/MIEX Treatment During Simulated Drinking

Water Treatment Conditions

DBP formation was examined under simulated drinking water treatment

conditions after MIEX and enhanced coagulation treatment processes for both the Akron

and Barberton source water. The effect of MIEX on DBP formation was evaluated over

the pH range of 6.5-9.0 in the presence of 3.55 mg/L-Cl2. The effect of enhanced

coagulation on DBP formation for the two coagulants was evaluated at pH 6.5 and the

native pH of the source water, which were approximately 8 for both the Akron and

Barberton source waters. After 24 hours, the chlorine residuals were quenched and

samples were analyzed for THMs and HAAs.

Since the bromide ion concentrations in Akron and Barberton source waters were

approximately < 20µg/L, chloroform (CHCl3), trichloroacetic acid (TCAA), and

dichloroacetic acid (DCAA) were the only chlorinated DBP detected. Tables 4.3 and 4.4

represent the average DBP concentrations water with and without treatment over the pH

range. With respect to each treatment process, DBP concentrations did not significantly

vary as a function of pH. Therefore, concentrations for chloroform, TCAA, and DCAA

43
in the tables are shown as the average concentrations over the pH range indicated with

respect to each treatment process.

The NOM removal processes significantly reduced the chloroform concentrations

compared to chlorination of raw Akron source water. The chloroform concentration in

the raw Akron source water was found to be 32.4± 2.1 µg/L after 24 hours (Table 4.3).

MIEX resulted in the largest reduction in chloroform formation after 24 hours yielding a

74% reduction compared to the raw water. The ACH and alum coagulants reducing

chloroform formation after 24 hours by 36% and 68% respectively (Table 4.4). MIEX

and alum appear to be equivalent in reducing the DBP precursors that result in

chloroform formation although bulk NOM removal was significantly different.

Chloroform formation as a function of treatment process for Barberton source water was

found to be different from the Akron. The chloroform concentration in the Barberton

source water after 24 hours was 18.2± 3.6 µg/L (table 4.3). MIEX, ACH and alum

reduced the 24 hour chloroform concentration by 66%, 26%, and 36% respectively.

TCAA was also detected in both the Akron and Barberton source waters after 24

hours. For the Akron source water, TCAA formation after 24 hours was 25.2 ± 3.1µg/L.

MIEX, ACH, and alum reduced TCAA formation at 24 hours by 67%, 33% and 46%

respectively. Barberton had an initial TCAA concentration of 14.7 ±3.1 µg/L after 24

hours in the presence of aqueous chlorine. MIEX, ACH and alum all reduce TCAA

formation by 56%, 31% and 36% respectively. DCAA had an initial concentration of

17.4 ± 2.1µg/L for the Akron source water after 24 hours in the presence of aqueous

chlorine. MIEX, ACH, and alum reduce DCAA concentrations after 24 hours by 62%,

44
29%, and 57% respectively. While DCAA formation in the Barberton was initially

12.7±2.8 µg/L, MIEX, ACH, alum treatment processes reduced DCAA formation by

60%, 23%, and 28% respectively.

The difference in DBP formation appears to a function of NOM characteristics.

MIEX resulted in significant reduction in DBP concentrations for both source waters

when compared to raw DBP formation in the chlorinated source water. For Akron, alum

was found to be almost as effective as MIEX in order to reduce the formation of DBPs.

DBP formation in the Barberton source water was significantly reduced with MIEX over

enhanced coagulation. For Akron source water, MIEX and alum effectively removed the

DBP precursors located in peaks A and C of the fluorescence spectra. For Barberton,

peak T in the fluorescence spectra appears to significantly contribute to DBP formation.

Peak T is related to microbial activity and may be transported in the system or created by

microbial activity within the system resulting in high concentrations of positively charged

amine moieties (Coble, 1996). Coagulation has been found to be ineffective in removing

NOM in the T region of the EEM spectra (Gone et al., 2009). However, MIEX has been

found to effectively remove low-molecular weight soluble microbial products in the T

region that do not contain positively charged amine moieties, which are not removed

during enhanced coagulation (Humbert et al., 2005). Therefore, MIEX appears to be

more effective than enhanced coagulation for removing DBP precursors in the T region

of the fluorescence spectra.

45
Table 4.3 Average DBP concentrations for treated both source waters MIEX treatment
after 24 hours in the presence of aqueous chlorine ([Cl2]T = 3.55 mg/L, pH 6.5-9.0,
Temp.= 25˚C, 95% confidence interval is provided).

Disinfection By Products (µg/L)

DOC (mg/L) CHCl3ave DCAAave TCAAave
Akron Raw 6.43 32.4 ± 4.5 17.4± 2.1 25.2 ± 3.1
Akron MIEX 1.52 (76%) 8.2 ± 1.4 6.6 ±1.8 8.3 ± 1.8
Barberton Raw 4.15 18.2 ± 3.6 12.7 ± 2.8 14.7 ± 3.1
Barberton MIEX 1.51 (63%) 6.2 ± 1.7 5.0 ± 2.1 6.4 ± 2.0

Table 4.4 Average DBP concentrations for after enhanced coagulation ([Cl2] T = 3.55
mg/L pH 6.5 and 8.2, Temp.= 25˚C, 95% confidence interval is provided).

Disinfection By
Products (µg/L)
DOC
(mg/L) CHCl3ave DCAAave TCAAave
Akron Raw 6.43 32.4 ± 4.5 17.4± 2.1 25.2± 3.1
Akron ACH 4.2 20.8 ± 4.2 12.4 ± 2.0 16.8 ± 2.8
Akron Alum 4.08 10.4 ± 3.3 7.4 ± 2.0 13.6 ± 2.0
Barberton Raw 4.15 18.2 ± 3.6 12.7 ± 2.8 14.7± 3.1
Barberton ACH 2.89 13.4 ± 2.1 9.8 ± 2.8 10.1 ± 1.0
Barberton Alum 2.98 11.7 ± 2.5 9.1 ±2.0 9.4± 1.1

46
4.3.2 DBP Formation after Coagulation/MIEX Treatment at Elevated Chlorine

Concentrations

While the 24 hour chlorination experiments yielded relative information about

DBP formation as a function of NOM removal treatment process and pH. To gain insight

into DBP formation as a function of pH and treatment process, additional experiments

were conducted on the Akron source water at elevated chlorine concentrations. As pH

increased from 6.5 to 8.2 for chlorination of the raw source water, chloroform

concentrations increased by 50µg/L at 24 hours, while TCAA concentrations decreased

by 30µg/L, and DCAA concentrations were approximately the same for both pH (Figures

4.12-4.17). These trends, as a function of pH, are consistent with observations by

previous researchers (Liang & Singer, 2003). DBP formation after treatment with MIEX

does not significantly change as a function of pH. When compared to untreated source

water, DBP formation was drastically reduced by approximately 90% for all three DBPs.

The largest reductions were found to be in the chloroform concentrations followed by

TCAA and DCAA.

The two coagulants both reduced DBP formation compared to the chlorinated raw

water; however, alum appeared to reduce DBP concentrations more significantly than

ACH at pH 8.2. ACH coagulation followed the same general DBP formation trends as a

function of pH then what was found for chlorinated raw Akron source water (Figures

4.12-4.17). TCAA formation decreased as pH increases from 6.5 to 8.2, chloroform

concentrations increased as pH increased, and DCAA formation was relatively the same

regardless of pH. At pH 6.5, DCAA formation for ACH and alum was found to be

47
similar while alum slightly reduced chloroform and TCAA concentrations compared to

ACH. However, alum significantly reduced DBP formation as pH increased to 8.2.

Although, reduction in EEM peaks A and C were approximately the same, alum removed

10% more UV-absorbing moieties than ACH, which resulted in DBP concentrations

similar to MIEX. This could have been due to the amount of coagulant dosed. Alum was

dosed at 40 mg/L (0.157mM) while the ACH dose was 10mg/L (0.057mM). This excess

amount of aluminum appears to be responsible the additional DBP precursor removal at

pH 8.2. This also appears to indicate that specifically monitoring EEM base pairs in the

fluorescence spectra may not be as representative in determining the concentration of

DBP precursors when compared to integrating the entire fulvic and humic EEM spectral

regions and comparing reduction in spectral volumes, which is done during PARFAC

modeling (Johnstone and Miller, 2009).

48
 120
Raw
MIEX
100
ACH
Alum
80
TCAA (µg/L)

60

40

20

0
0 5 10 15 20 25 30
Time (hours)

Figure 4. 12 TCAA formations at pH 6.5 for Akron source water as a function of NOM
removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC] MIEX =1.52 mg/L-
C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C).

49
 80
Raw
MIEX
ACH
60 Alum
TCAA (µg/L)

40

20

0
0 5 10 15 20 25 30
Time (hours)

Figure 4. 13 TCAA formation at pH 8.2 for Akron source water as a function of NOM
removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC] MIEX =1.52 mg/L-
C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C).

50
 70
Raw
60 MIEX
ACH
50 Alum
DCAA (µg/L)

40

30

20

10

0
0 5 10 15 20 25 30
Time (hours)

Figure 4. 14 DCAA formation at pH 6.5 for Akron source water as a function of NOM
removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC] MIEX =1.52 mg/L-
C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C).

51
 80

Raw
MIEX
ACH
60
Alum
DCAA (µg/L)

40

20

0
0 5 10 15 20 25 30
Time (hours)

Figure 4.15 DCAA formation at pH 8.2 for Akron source water as a function of NOM
removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC] MIEX =1.52 mg/L-
C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C).

52
 120
Raw
MIEX
100
ACH
Alum
80
Chloroform (µg/L)

60

40

20

0
0 5 10 15 20 25 30
Time (hours)

Figure 4. 16 Chloroform formation at pH 6.5 for Akron source water as a function of

NOM removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC]MIEX =1.52
mg/L-C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C).

53
 180
Raw
160
MIEX
ACH
140
Alum
120
Chloroform (µg/L)

100

80

60

40

20

0
0 5 10 15 20 25 30
Time (hours)

Figure 4. 17 Chloroform formation at pH 8.2 for Akron source water as a function of

NOM removal process. ([Cl2]T = 10.5 mg/L, [TOC] Raw = 6.43 mg/L-C, [TOC]MIEX =1.52
mg/L-C, [TOC]ACH = 4.20 mg/L-C, [TOC]Alum=4.08 mg/L-C, and Temp.= 25˚C).

54
 To further understand DBP precursor removal as a function of treatment process,

the percent of carbon from the NOM that results in the formation of the three detected

DBPs was determined. Calculations were made for all three treatments at both pH. In

order to develop this ratio, DBP and DOC concentrations were converted to µM (Tables

4.6 and 4.7). After being converted micromolar concentrations, the sum of DBPs

(CHCl3, TCAA, and DCAA) was divided by DOC and multiplied by 100 (Equation 4.1).

Larger the ratio indicates the degree as to the residual NOM participates in DBP

formation as well as the DBP precursor effectiveness for each process as a function of

pH. At pH 6.5, the ratios ranged 0.5-0.7 and correlated with the observed results that

MIEX was more effective at not only removing NOM but DBP precursors. However,

alum at a pH 8.2 proved to contribute the least amount of carbon to DBP formation at

0.26%, which was significantly less than the observed range of 0.62-0.81 for MIEX,

ACH and the source water respectively. Therefore, alum coagulation dosed at excess

concentrations maybe the most effective treatment process for removing DBP precursors

from water that contain high humic/fulvic content at slightly alkaline pH.

[CHCl 3 ] + 2[DCAA] + 2[TCAA]

DBP − Carbon Ratio = (4.1)
[DOC]

55
Table 4.5 DBP-Carbon Ratio for Akron in final DBP formation for pH 6.5 ([Cl2=
10.5mg/L])

TOC DCAA TCAA CHCl3

(µM) (µM) (µM) (µM) % C for DBP formation
Raw 535.40 0.90 1.26 1.61 0.70
MIEX 126.60 0.16 0.13 0.33 0.49
ACH 350.00 0.59 0.60 1.19 0.68
Alum 340.00 0.59 0.39 0.95 0.57

Table 4.6 DBP-Carbon Ratio for Akron in final DBP formation for pH 8.2 ([Cl2=
10.5mg/L])

TOC DCAA TCAA CHCl3

(µM) (µM) (µM) (µM) % C for DBP formation
Raw 535.40 1.01 0.89 2.46 0.81
MIEX 126.60 0.22 0.15 0.54 0.71
ACH 350.00 0.56 0.39 1.21 0.62
Alum 340.00 0.21 0.21 0.45 0.26

56
 CHAPTER V

SUMMARY AND RECOMMENDATIONS

5.1 Summary

The overall objective of this study was to compare the effectiveness and

selectivity of NOM removal processes in order to reduce DBP formation in finished

drinking water. First objective was to compare the performance of three strong anion

exchange resins for their application in drinking water treatment. The second objective

was to determine which process (i.e., MIEX or enhanced coagulation) removed the

greatest amount of NOM as a function of pH. Objective three was to determine DBP

formation based on a function of pH and treatment process. All three objectives were

met through this study.

Three AERs commonly used in drinking water treatment, MIEX, IRA-910, and

IRA-958, were examined for their capacity to remove NOM as monitored by TOC and

UV absorbance at λ254 and λ272 as a function of time. All the AERs were found to be

highly proficient at NOM reduction specifically the moieties that absorb UV light at λ254

and λ272 over 75 minutes of contact time; however, MIEX removed NOM at faster rate

than the Amberlite resins. Fluorescence spectroscopy was also used to monitor specific

components of the NOM-EEM spectra in the presence of the AERs. The fluorescence

57
spectra showed that EEM base pairs designated A and C sharply decrease with increasing

contact times in the presence of all three AERs.

The next objective was to determine the effect of pH had on NOM removal as a

function of treatment process by fluorescence spectroscopy. Results show that pH had no

significant effect on the removal of chromophores and fluorophores (i.e. EEM base pairs

A and C) when treated with MIEX or enhanced coagulation at pH 6.5 or the native pH of

the source water. Chromophore and fluorophore intensities over the pH range were

within 5% of each other throughout the entire experiment. Peaks A and C for Barberton

source water reduced by 40% and 35%. The region where the T peak occurs for the

Akron source water was not well defined assumed to be due to relaxation of the A peak;

however, the peak intensity T was found to be relatively resilient to each NOM removal

process for the Barberton source water.

The final objective was to determine DBP formation over as a function of pH for

the different NOM removal processes. MIEX resulted in significant reduction in DBP

concentrations for both source waters when compared to DBP formation in the

chlorinated raw source waters. MIEX out performed both coagulants reducing the

formation of DBPs in both source waters. At an elevated chlorine concentration in the

raw samples, as pH increases from 6.5 to 8, chloroform formation increase, TCAA

concentrations decrease and dichloroacetic acid (DCAA) is not affected. The two

coagulants both reduced DBP formation; however, alum appeared to reduce DBP

concentrations more significantly than ACH at pH 8.2.

58
5.2 Recommendations

The following are recommendations for future research:

1. Investigate differences between ACH and alum optimal dose to determine the

coagulant selectivity on removal of DBP precursors.

2. Perform additional coagulation studies on different source waters using iron and

aluminum salts to determine which coagulant reduces DBP precursors more

effectively.

3. Relate changes in DBP formation to integrated regional volumes of the EEM spectra

instead of EEM base pairs.

4. Examine precipitate structure with x-ray diffraction (XRD) to determine if crystalline

structures are formed that enhance DBP precursor removal.

5. Investigate the application of AERs for removal of emerging water quality issues

such as removal of arsenic and pharmaceuticals.

59
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63
 APPENDIX A

A.1 Kinetic Removal of NOM by AERs

Resin IRA-910 data for AER Comparison-Akron Source Water

IRA-910 Fluorescence (RU)

TOC
Time UV254 UV272 (mg/L) A C T
0 0.113 0.093 6.43 53.56 23.77 13.11
15 0.057 0.046 3.66 18.50 8.14 15.02
30 0.04 0.032 2.81 13.28 5.97 15.42
45 0.028 0.022 2.75 9.40 4.48 11.04
60 0.024 0.019 2.62 8.32 3.90 17.48
75 0.02 0.016 2.53 8.66 3.60 3.99

Resin IRA-958 data for AER Comparison-Akron Source Water

IRA-958 Fluorescence (RU)

Time
(min) UV254 UV272 TOC (mg/L) A C T
0 0.113 0.093 6.43 53.56 23.77 13.11
15 0.052 0.042 3.46 19.36 8.98 16.25
30 0.042 0.034 2.89 13.67 6.26 16.72
45 0.038 0.031 2.82 12.42 5.15 16.53
60 0.033 0.026 2.75 9.35 3.73 15.05
75 0.024 0.02 2.61 8.70 3.70 15.32

64
MIEX resin data for AER Comparison- Akron Source Water

MIEX Fluorescence (RU)

Time TOC
(min) UV254 UV272 (mg/L) A C T
0 0.113 0.093 6.43 53.56 23.77 13.11
15 0.025 0.021 2.04 9.68 4.32 15.77
30 0.019 0.014 1.69 9.43 4.29 22.20
45 0.015 0.011 1.67 8.88 3.52 20.02
60 0.011 0.009 1.52 8.18 3.27 24.23
75 0.01 0.008 1.5 7.76 3.24 17.88

65
A.2 MIEX Removal of NOM while varying pH

MIEX removal varying pH from 6.5-9.0

pH, Time
(min) UV254 UV 272 A C T
9, 0 0.128 0.11 38.7235 20.3853 30.0789
9,15 0.041 0.037 14.4246 7.54257 15.0925
9,30 0.023 0.022 9.9447 4.78031 14.0507
9, 45 0.017 0.018 10.8365 4.50339 22.0374
9, 60 0.018 0.018 9.71784 4.61525 21.2239
9, 75 0.014 0.015 15.0997 7.41569 29.0933
9, 90 0.013 0.014 9.80389 4.25542 17.0154
7.5,0 0.125 0.106 39.936 18.6566 36.994
7.5,15 0.044 0.04 15.0215 7.10279 21.0831
7.5,30 0.025 0.025 11.5874 4.90077 22.7493
7.5,45 0.016 0.016 8.41149 3.64448 13.9255
7.5,60 0.013 0.015 9.41277 4.27419 21.2161
7.5,75 0.014 0.015 6.44805 3.06249 12.5801
7.5,90 0.013 0.014 10.7582 5.15813 18.8146
6.5,0 0.121 0.105 44.8329 23.4596 42.5792
6.5,15 0.044 0.04 15.9132 7.07542 21.0909
6.5,30 0.026 0.026 13.1128 5.45147 23.7662
6.5,45 0.017 0.018 9.59268 3.61398 17.2344
6.5,60 0.015 0.016 9.44406 4.01449 17.2266
6.5,75 0.013 0.014 8.59141 3.49429 15.842
6.5,90 0.013 0.014 10.0542 3.99024 16.6087
8.21,0 0.113 0.092 39.0967 17.5692 25.1414
8.21,15 0.037 0.03 16.8957 7.7724 15.5432
8.21,30 0.022 0.017 12.2727 5.26843 22.6617
8.21,45 0.012 0.01 11.3887 4.64811 16.083
8.21,60 0.008 0.006 9.35488 4.02153 12.0309
8.21,75 0.003 0.002 6.53097 2.72143 4.20848
8.21,90 0.006 0.005 9.55044 4.75449 13.7519

66
A.3 Chlorine Consumed in Akron for an Elevated Chlorine Concentration

Chlorine consumed at Elevated Chlorine Dose

Chlorine Residual (mg/L)

Raw MIEX ACH Alum
pH 6.5 2.2 5.9 3.9 4.2
pH 8.2 2.4 6.1 4.1 4.1

67