PII: S0043-1354(00)00424-3

Wat. Res. Vol. 35, No. 7, pp. 16591664, 2001

# 2001 Elsevier Science Ltd. All rights reserved
Printed in Great Britain
0043-1354/01/$ - see front matter

ARSENIC REMOVAL DURING CONVENTIONAL

ALUMINIUM-BASED DRINKING-WATER TREATMENT
JAN GREGOR*
Institute of Environmental Science and Research Limited, PO Box 29-181, Christchurch, New Zealand
(First received 21 March 2000; accepted in revised form 25 August 2000)
Abstract}The changing forms and concentrations of arsenic through aluminium-based coagulation
treatment processes were tracked for three drinking-water treatment plants. This has provided direct
evidence of where and how arsenic is removed. In general, soluble As(V) is converted to particulate As(V)
by adsorption during rapid mixing, and is removed along with naturally occurring particulate arsenic
predominantly by clarication. Soluble As(III) tracks through the treatment processes and is converted to
soluble As(V) during nal chlorination. The ability of a water treatment process to achieve the maximum
acceptable concentration for arsenic in drinking water is dependent on the concentration of As(III) in the
source water. # 2001 Elsevier Science Ltd. All rights reserved
Key words}arsenic, forms, removal, aluminium, coagulation

INTRODUCTION

For decades, arsenic has been fortuitously removed

from contaminated waters during the coagulation
process, generally to a level acceptable for drinkingwater purposes. Previously in New Zealand, the
acceptable value had been 0.05 mg/L, which very few
sources of drinking-water exceeded and thus the need
for specic treatment was unwarranted. The current
US-EPA maximum contaminant level (MCL) is
0.05 mg/L (USEPA, 1998), but a value of 0.005 mg/
L is proposed (USEPA, 2000). In 1995, New Zealand
adopted a maximum acceptable value (MAV) for
arsenic in drinking-water of 0.01 mg/L. This is
considered to be the concentration below which the
presence of arsenic does not result in any signicant
risk to a consumer over a lifetime of consumption
(Ministry of Health, 1995). With the lowering of the
acceptable concentration, specic treatment for
arsenic removal has become necessary.
Arsenic exists in natural waters in a variety of
forms including the trivalent (As(III)) and pentavalent (As(V)) oxidation states, and soluble, particulate
and organic-bound. Eective treatment must target
all of these forms, either directly or after conversion
to a more readily removed form. The proportions of
these forms depend on factors such as pH, particle
and natural organic matter concentrations and

*Author to whom all correspondence should be addressed.

Tel.: +64-3-3516-019; fax: +64-3-3510-010; e-mail:
jan.gregor@esr.cri.nz

compositions, biological activity, and degree of

oxygen saturation, and thus will be spatially and
seasonally dependent. Chen et al. (1999) have
characterised the forms of arsenic in source water
samples, and Hering et al. (1997) have carried out
bench-scale studies with As(III) and As(V) to identify
the characteristics of source waters that have
pronounced eects on arsenic removal.
By far the most commonly used treatment in New
Zealand is aluminium-based coagulation with disinfection by chlorination. For river waters with
signicant inherent arsenic concentrations, the degree
to which this treatment removes arsenic is however
somewhat variable, as gauged by eld measurement
of total arsenic concentrations before and after
treatment (Davies et al., 1994; McLaren and Kim,
1995). At best, the 0.01 mg/L MAV was achieved for
most of the year, but seasonal arsenic concentration
uctuations in the river water were reected in the
treated water. At worst, less than 15% of the arsenic
was removed. Similarly in the USA, McNeill and
Edwards (1995) reported a wide range in decreases in
soluble As(V) concentrations for ve alum coagulation treatment plants (674%).
In this study, the changing forms and concentrations of arsenic through aluminium-based coagulation treatment processes were tracked for three
drinking-water treatment plants that abstract water
from the same river over a distance of no more than
40 km. The ndings provide insight into the critical
steps of coagulation, and identify when treatment
additional to aluminium-based coagulation is required in order to meet the MAV for arsenic.

1659

1660

Jan Gregor
MATERIALS AND METHODOLOGY

Source water
Arsenic concentrations in the Waikato River, one of
New Zealands major sources of drinking-water, range from
approximately 0.01 mg/L at its source (Lake Taupo) to
0.030.06 mg/L after natural and anthropogenic geothermal
discharges. The three drinking-water supplies selected for
this study (Hamilton City, Pukerimu Rural, Lake Karapiro)
draw essentially the same quality water (Table 1, duplicate
samples were collected on dierent days in the same week)
and use aluminium-based coagulation. The one notable
exception to water quality consistency is the higher pH at
Lake Karapiro.
Both Hamilton City and Pukerimu Rural water supplies
abstract water from the run of the river. The Lake Karapiro
water supply is dierent, being from an articial lake
formed on the river. Lake Karapiro is the last of eight
hydroelectric lakes formed on the Waikato River with an
area of 7.7 km2 and a retention period of 2.8 days
(Magadza, 1979).
Treatment plants and sampling sites
The Hamilton City water supply serves approximately
100,000 people, whereas Pukerimu Rural and Lake Karapiro serve small communities of 3000 and 10,000 people
respectively. Alum is used as the coagulant at both
Hamilton City and Lake Karapiro, and polyaluminium
chloride is used at Pukerimu Rural. All three treatment
plants use a synthetic occulant aid. Lake Karapiro prechlorinates prior to rapid mixing. Both Hamilton City and
Lake Karapiro pH-adjust upwards immediately post-lter.
Hamilton City adjusts from approximately pH 6.8 to 8.0,
and Lake Karapiro adjusts from approximately pH 7 to
8.08.5 in the winter and to pH 7.5 in the summer.
Five sampling sites were identied for each water
treatment plant: source water, during the initial stages of
coagulation (rapid mix micro-oc formation, 2 to 3 min
mixing), after occulation/clarication (macro-oc development, 60120 min slow mixing), after ltration, and after
nal chlorination.
Sample collection and analysis
At each treatment plant, and for each sampling site,
water samples were collected twice during the summer and
twice during the winter to coincide with extremes of river
ow and composition, and the demand for treated water
(treatment plant ow rate). The duplicate samples were
collected on dierent days in the same week.
At each treatment plant, and for each sampling site, the
concentrations of total arsenic, soluble arsenic (and
particulate-bound arsenic, by dierence), soluble As(III)
(and soluble As(V), by dierence), and natural organic

matter (NOM)-bound arsenic were determined. Total

arsenic was determined from an acid preserved sample by
ICP-MS, and soluble arsenic was determined from a eldltered (0.45 mm) acid-preserved sample. Soluble As(III) was
determined from a eld-ltered sample that was subsequently eluted through an anion exchange column (Amberlite CG-400 resin). The As(V) was retained by the resin, and
the non-ionic As(III) passed through. NOM-bound arsenic
was determined from dialysis against Milli-Q water through
a Spectra/Por MWCO3,500 membrane for the source water
only, with the NOM-bound arsenic being retained outside
the dialysis bag and inorganic arsenic reaching equilibrium
inside and outside the dialysis bag. Ultraviolet absorbance
(UV) measurements indicated that only approximately 1%
of the UV-active NOM was small enough to pass through
the dialysis membrane. Details of this method, used for
alginate bound-aluminium, have been reported previously
(Gregor et al., 1996).

RESULTS

The changing forms and concentrations of arsenic

through the three aluminium-based coagulation
treatment processes are shown in Fig. 1 and Table
2. The duplicate results for each sampling site
(Source, Rapid Mix, Claried, Filtered, and Chlorinated) have been averaged. The agreement in results
for duplicate samples is considered reasonable, given
the experiment scale of an operational water treatment plant. In the gure, the height of each bar
represents the total arsenic in the water. This is then
subdivided into particulate arsenic, soluble As(III),
and soluble As(V).
Arsenic has been removed to a concentration

5 mg/L during summer and winter at Hamilton
City and Pukerimu Rural, and during winter at Lake
Karapiro. For all three treatment plants, better
percent removals and lower concentrations in the
treated water were achieved in winter (range
513 mg/L) than in summer (range 310 mg/L).
The total arsenic concentration in the Waikato
River in summer was 1.5 times higher than in winter.
Regardless of season and except for Pukerimu Rural
winter, the arsenic was predominantly soluble
(85100%), and except for Lake Karapiro summer,
90% or more of the soluble arsenic was soluble
As(V). The predominance of soluble arsenic was
mimicked in the treated water. Between source and

Table 1. Waikato river water quality

pH

Turbidity (NTU)

Absorbance at 270 nma

Total arsenic (mg/L)

Hamilton city
Summer
Winter

8.2, 7.6
7.2, 7.5

3.0, 1.8
1.5, 1.4

0.03, 0.03
0.05, 0.05

27, 28
18, 18

Pukerimu rural
Summer
Winter

7.5, 7.3
7.5, 7.5

1.0, 1.4
0.7, 0.5

0.03, 0.02
0.03, 0.04

29, 29
16

Lake Karapiro
Summer
Winter

8.4, 8.5
8.7, 8.5

2.5, 2.1
1.7, 1.0

0.03, 0.03
0.04, 0.04

25, 28
18, 18

An estimate of natural organic matter content.

Arsenic removal by aluminium coagulation

1661

Fig. 1. Changing forms and concentrations (mg/L) of arsenic during treatment. Duplicate results have
been averaged.

treated water, the soluble As(V) component was

converted to a particulate form and removed
predominantly by settling (clarication). The soluble
As(III) travelled through the treatment process until
chlorination, where it was mostly oxidised to As(V).
Unlike Hamilton City and Pukerimu Rural, a
signicant portion (22%) of the Lake Karapiro
summer source sample was soluble As(III). This
soluble component travelled through the remaining
treatment, resulting in treated water that struggled to
achieve the MAV of 0.01 mg/L. The oxidation state
of this soluble arsenic changed several times during
treatment. It was converted to soluble As(V) during
rapid mixing due to pre-chlorination. Between rapid
mixing and the exit of the clarier, it was reduced to
soluble As(III), then nally converted back to soluble
As(V) during ltration and chlorination.
Approximately 4 mg/L of NOM-bound arsenic was
found in the three source waters (the only sampling

site for which sucient NOM was present to make

this measurement), regardless of season. Given that
the total arsenic concentration in summer was 1.5
times higher than in winter, the fraction of total
arsenic bound to NOM was lower in the summer, coincident with the lower NOM content as estimated by
absorbance at 270 nm (Table 1).

DISCUSSION

Achieving the MAV

In addition to the intended purpose of particulate
and natural organic matter (NOM) removal, aluminium-based coagulation has a role to play in reducing
the concentration of arsenic. The goal is to consistently reduce the concentration of arsenic to below
the acceptable value for drinking water. Two of the
three water treatment plants in this study achieved

1662

Jan Gregor
Table 2. Changing forms and concentrations (mg/L) of arsenic during treatment. Duplicate results have been averaged
Source

Rapid mix

Claried

Filtered

Chlorinated

Hamilton city summer

Particulate As
Soluble As(V)
Soluble As(III)

0.6
25.5
1.6

24.8
50.5
3

50.5
50.5
4.3

50.5
50.5
4.8

50.5
4.4
0.5

Hamilton city winter

Particulate As
Soluble As(V)
Soluble As(III)

2
14.8
0.8

16.4
50.5
0.6

0.8
50.5
0.8

50.5
50.5
0.6

50.5
1
0.6

Pukerimu rural summer

Particulate As
Soluble As(V)
Soluble As(III)

4
24.2
0.6

25.4
50.5
1.8

2
50.5
2.6

50.5
50.5
3.1

50.5
2.7
50.5

4
8.2
0.5

16.4
50.5
0.8

1.5
50.5
1

50.5
50.5
1.4

50.5
50.5
0.5

Lake Karapiro summer

Particulate As
Soluble As(V)
Soluble As(III)

50.5
23
5

21.6
4.8
0.6

2.2
1.8
6.4

0.8
6.4
2

50.5
8.4
0.6

Lake Karapiro winter

Particulate As
Soluble As(V)
Soluble As(III)

50.5
17.4
0.6

15.4
50.5
0.5

1.8
1.4
0.5

50.5
1.7
0.5

50.5
2
0.5

Pukerimu rural winter

Particulate As
Soluble As(V)
Soluble As(III)

this goal based on the New Zealand MAV of

0.01 mg/L, and the third achieved it for part of the
year. However, with the possibility of the acceptable
concentration being lowered even further in the
future, as it is proposed in the USA, it is important
to understand whether existing treatment processes
are capable of doing better.
Comparison of arsenic fractionation in New Zealand
and other source waters
The arsenic in the Waikato River originates from
natural geothermal sources and from geothermal
power station discharges. The seasonal variation in
concentrations of arsenic in the Waikato River found
in this study was similar to that reported at the
Hamilton City intake in 1993/1994 (McLaren and
Kim, 1995). The samples of the present study were
taken in March and September 1999, and the
concentrations of 2829 mg/L and 1318 mg/L
matched the 30 mg/L and 1820 mg/L respectively
reported by McLaren and Kim (1995) for the same
time of the year.
It was found in this study that the dominant form
of arsenic in the Waikato River is soluble. This is in
contrast to the results of a recent USA national
survey of drinking water sources which found for
surface waters typically 2354% of the total arsenic
to be particulate (Chen et al., 1999). The high
proportion of soluble arsenic in the Waikato River
may be related to its geothermal origin and the
consequential eect of water composition. For
example, mono-silicic acid has been identied as the

component of geothermal bore water that inhibits

arsenic adsorption to onto hydrous ferric oxide
surfaces (Swedlund and Webster, 1998). An elevated
concentration of mono-silicic acid in the Waikato
River could thus inhibit adsorption of arsenic onto
iron-bearing colloids and particles.
The results of this study are in agreement with
previous studies that As(V) predominates in the
Waikato River (Aggett and Aspell, 1980). That the
proportion of As(III) increases in spring/summer in a
lake setting (Lake Karapiro) is also in agreement
with previous studies. This has been attributed to
biologically mediated reduction in the sediments
(Aggett and Aspell, 1980; Kuhn and Sigg, 1993)
and anoxic conditions and thermal stratication of
the water trapping the reduced As(III) (Aggett and
Kriegman, 1988). An oxygen decit at depth has been
reported for Lake Karapiro during summer months
(Magadza, 1979), which will sustain the presence of
As(III). Anabaena oscillaroides, present in Waikato
River water, is also reported to reduce As(V) to
As(III) (Freeman, 1985). Taste and odour problems
were reported in the Lake Karapiro water supply at
the time of summer sampling. The chemicals
responsible for these problems derive from bacteria
and algae present in the water or sediment, supporting the presence of biological activity.
In summary, the Waikato River water contains
seasonally-variable concentrations of arsenic, contains very little particulate arsenic, and soluble
As(III) can contribute signicantly to the total
arsenic concentration during spring/summer. The
consequences for treatment eectiveness of the

Soluble and particulate As(V) and As(III)

Soluble and particulate As(V)
Soluble As(V)
None
None
None
Particulate As(V)
Soluble and particulate As(V)
and As(III)
None
As(III) ! As(V)
Soluble As(V) ! particulate As(V); soluble As(III) ! soluble As(V)
Soluble As(III) ! soluble As(V); soluble As(V) ! particulate As(V)
No treatment
Chlorination only
Aluminium-based coagulation and chlorination
Pre-chlorination, followed by aluminium-based coagulation
and chlorination

Expected removal
Expected changes in forms
Treatment

Table 3. A guide to forms of arsenic expected in drinking waters arising from various treatment options

Expected forms in drinking water

Arsenic removal by aluminium coagulation

1663

dierences in forms of arsenic in the Waikato River

water are discussed in the following sections.

General removal mechanism

Entrapment during coagulation will remove particulate arsenic. However, the Waikato River water
contains predominantly soluble arsenic for which a
mechanism other than entrapment is required.
Removal of the soluble fraction will be by surface
interactions between the arsenic and the aluminium
oc. It is well reported in the literature that soluble
As(V) is removed by adsorption to aluminium-based
oc, but that soluble As(III) is not (Hering et al.,
1997; Edwards, 1994). Figure 1 clearly shows this
As(V) adsorption occurring during the rapid mixing
stage, taking only a few minutes, and the As(III)
fraction remaining soluble.
Clarication was eective in removing in excess of
90% of the entrapped and adsorbed As(V), with the
remaining particulate fraction being retained by the
lters.
Chlorination, as well as serving as the disinfectant,
is capable of oxidising soluble As(III) to soluble
As(V). This oxidation can be benecial in at least two
ways, the rst being conversion to the least toxic
As(V) form (World Health Organisation, 1996), just
prior to water entering the distribution system.
Second, oxidation of As(III) to As(V) prior to
coagulation is a recommended treatment option
(USEPA, 1998), given that As(V) adsorbs to
aluminium-based ocs much better than As(III).
However, pre-oxidation can have an adverse eect
on other water quality parameters. In particular,
chlorination of waters before removal of natural
organic matter can result in the formation of elevated
concentrations of undesirable disinfection by-products. Chlorination before the removal of algal cells
will result in taste and odour problems, typically
earthy/musty descriptors. Lake Karapiro treatment
includes pre-chlorination and, as can be seen in
Fig. 1, most of the As(III) in the summer sample is
consequently converted to As(V). However, this
As(III)-derived As(V) is not converted to particulate
arsenic, possibly because pre-chlorination occurs
shortly after coagulant addition, too late to be
incorporated with the natural As(V) during rapid
mixing. Surprisingly, this As(III)-derived As(V) did
not adsorb to the oc surface during the prolonged
contact of clarication, probably due to its conversion back to the reduced form, As(III), before exiting
the clarier. This reduction could be biologicallymediated and/or chemically-driven by anoxic conditions created within the oc blanket by the signicantly accumulated biomass (Kawamura, 1991).
Supporting evidence of the reason for this conversion
of As(V) to As(III) was not investigated at the time.
Further work should be done if there is a need to
understand the mechanism(s).

1664

Jan Gregor

SUMMARY: CRITICAL STEPS AND LIMITATIONS OF

ALUMINIUM-BASED COAGULATION

Notwithstanding other water quality parameters,

the goal of water treatment is to consistently reduce
the concentration of arsenic to below the acceptable
value for drinking water. For aluminium-based
coagulation with disinfection by chlorination, the
form of arsenic most likely to be present in the
treated water is soluble As(V): soluble because
particulate arsenic should have been removed by
clarication and ltration, and As(V) because nal
chlorination should have converted any remaining
As(III) to As(V). Thus, the key to low concentrations
of arsenic in the treated water is the presence and
eective removal of particulate arsenic. Where
naturally occurring particulate arsenic is minimal in
the source water, conversion of soluble arsenic to
particulate arsenic is required. This conversion may
arise unassisted by adsorption to ocs during
coagulation and occulation, such as happens for
soluble As(V). In the case of soluble As(III),
conversion to As(V) is necessary and conditions that
support As(V) must be maintained until ltration.
Table 3 provides a guide to the forms of arsenic
expected in drinking waters arising from various
treatment options. Although treatment involving prechlorination appears the best for arsenic removal, the
success or otherwise depends on the position of prechlorination, as was observed in this study. Furthermore, pre-chlorination can have an adverse eect on
other water quality parameters such as the formation
of disinfection by-products and the release of taste
and odour compounds from algal cells.
Acknowledgements}The Author wishes to thank Hamilton
City Council and Waipa District Council for their support
and time to collect samples.

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