Applied Geochemistry 18 (2003) 1479–1496

www.elsevier.com/locate/apgeochem

Vertical distribution of As(III) and As(V) in a coastal sandy

aquifer: factors controlling the concentration and speciation
of arsenic in the Stuarts Point groundwater system, northern
New South Wales, Australia
J.V.S. Smitha,*, J. Jankowskia, J. Sammutb
a
UNSW Groundwater Centre, School of Biological, Earth and Environmental Sciences, The University of New South Wales, Sydney,
N.S.W., 2052, Australia
b
Geography Program, Faculty of the Built Environment, University of New South Wales, Sydney, N.S.W., 2052, Australia

Abstract
Arsenic species were measured in a bundled-piezometer installed in the Holocene barrier of the Stuarts Point coastal
sands aquifer, northern New South Wales, Australia. Vertical distribution shows two peaks of elevated As concen-
tration. At a depth of 10–11 m, concentrations of AsTot, As(V) and As(III) are in the range of 52–85, 38–67 and 14–18
mg/l respectively and the ratio of As(V)/As(III) is well above 1 at 3.7–2.7. The second peak, at a depth of 25 m, shows
the highest concentrations of AsTot, As(V) and As(III) with values reaching 337, 125 and 212 mg/l, respectively. The
As(V)/As(III) ratio is below 1 at 0.6–0.7. High AsTot and As(V) concentrations at shallower depths are associated with
acidic conditions and very low concentrations of all ions. Desorption of As from Al-hydroxides and As-enriched Fe-
oxyhydroxides are plausible mechanisms releasing As into the groundwater system. The elevated concentration of
AsTot and As(III) at 25 m is potentially related to the leaching of the clay surfaces. Elevated HCO-3 and alkaline pH
conditions at this depth cause desorption of As which is later present as As(III) species in the reducing environment.
The high concentrations of HCO-3 further reduce the possible extent of As sorption on Fe and Mn oxyhydroxides. The
identification of As in a groundwater system associated with the coastal barrier sand-dune environment raises serious
questions of the suitability of human consumption of untreated groundwater, drawn from these aquifer types. Further
investigation both in Australia and globally are needed to classified the extent of this hydrogeochemical occurrence
near coastal communities that rely on groundwater.
# 2003 Elsevier Science Ltd. All rights reserved.

1. Introduction of groundwater environments, has been reported in

Elevated concentrations of As in drinking water are a
considerable hazard to human health (Hopemhayn-
Rich et al., 1996; Mandal et al., 1998; National
Research Council, 1999; Karim, 2000). The occurrence
of As in drinking water supplies, drawn from a variety
* Corresponding author. Fax: +61-2-9385-5935.
E-mail address: james.smith@unsw.edu.au (J.V.S. Smith).
0883-2927/03/$ - see front matter # 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0883-2927(03)00063-5
many places around the world. Of particular sig-
nificance are reported cases in Argentina (Nicolli et al.,
1989; Smedley et al., 1998), Taiwan (Chen et al., 1996;
Guo et al., 1997), Vietnam (Berg et al., 2001), India
(Bhattacharya et al., 1997; Acharyya et. al., 2000),
Mexico (Del Razo et al., 1990; Arminta et al., 1997),
USA (Matisoff et al., 1982; Welch et al., 1988, 2000;
Robertson, 1989; Welch and Lico, 1998; Peters et al.,
1999; Schreiber et al., 2000), and Bangladesh (Karim,
2000; Nickson et al., 2000; Kinniburgh and Smedley,
2001; McArthur et al., 2001; Ravenscroft et al.,
2001).
1480 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
The presence of natural inorganic aqueous con-
centrations of As in unconsolidated sedimentary sys-
tems has been shown to be associated with, but not
limited to, four dominant hydrogeochemical processes.
These processes consist of the oxidation of arsenical
pyrite through groundwater withdrawal or the influx of
O2 or oxyanions into groundwater (Dhar et al., 1997;
Mallick and Rajagopal, 1996; Mandal et al., 1998), the
reductive dissolution of Fe(III)-rich oxyhydroxides
(Tossell, 1997; Bhattacharya et al., 1997; Nickson et al.,
2000), the desorption of As from aluminosilicate miner-
als or Al oxides (Tourtelot, 1964; Forest and Griffin,
1977; Manning and Goldberg, 1997: Lin and Puls, 2000)
and competitive ligand exchange with PO4 anions
(Manning and Martens, 1997; Peryea and Kammereck,
1997; Acharyya, 1999; Jackson and Miller, 2000). It is
noted that arsenical pyrite is also referred to as arsenian
pyrite, As-enriched pyrite or As-bearing pyrite. These
terms are used interchangeably in the literature but
generally represent As in sedimentary based mineral
form which occurs when As is incorporated, during the
process of diagenesis of marine anoxic sediments, into
the pyrite structure or sequestered by authigenic bacte-
rially mediated pyrite growth, often occurring in
framboidal form.
In the current understanding of natural As occur-
rences, there is little information about elevated As
concentrations in coastal sand aquifer systems, and in
Australia generally (Smedley and Kinniburgh, 2002).
Coastal sand aquifer systems are used extensively in
many parts of the world due to their capacity to yield
high quality groundwater and to subsequently provide a
reliable source of drinking water in coastal commu-
nities. This paper presents initial information from
hydrogeochemical studies in the Stuarts Point aquifer,
northern New South Wales, Australia, where regional
studies have identified As concentrations of up to 70 mg/
l in the coastal-barrier sand beach and estuarine clay
deposits (Smith et al., 2000). The World Health
Organisation set the guideline concentration of As at
<10 mg/l (WHO, 1994). In Australia, the National
Health and Medical Research Council has recom-
mended a threshold of 7 mg/l (NHMRC, 1996). The
presence of As in this system presents a serious question
as to the extent of As occurrence in the coastal ground-
water environment and the subsequent implications for
drinking water supplies in these regions.
2. Geology
The study area is located within the unconsolidated
Holocene sand deposits of the Stuarts Point region,
northern New South Wales (NSW), Australia (Fig. 1).
The unconsolidated sediments of the Stuarts Point
coastal sands aquifer have largely been described by
Eddie (2000) and can be divided into 3 main geological
units:
(1) Poorly drained alluvial swamp deposits overlying
estuarine clayey sands;
(2) Holocene estuarine clay deposits, which overlay
the Pleistocene deposits and consist primarily of grey
silty sandy clays; and
(3) Pleistocene barrier and Holocene marine sand
deposits consisting primarily of siliceous sands,
deposited by wind and wave action.
Adjacent to the Holocene sand deposits, the Yarra-
hapinni Holocene clay deposits comprise estuarine mud
and silty clay sequences (Fig. 1), which are flocculated
with increasing pore water salinities at depth and
encompasses the Yarrahapinni Wetland. Hail (1969)
identified that a lack of peat material, yet abundance of
shell lenses in these deposits potentially indicates com-
plete submergence of the sequence during the Holocene
transgression. The Holocene clay deposits are classified
as having a high probability of Acid Sulfate Soils (ASS)
(Eddie, 2000). Indurated soils within both the Holocene
and Pleistocene barrier deposits are also present; the
soils are the result of natural leaching of decaying
organic material and subsequent cementation or
impregnation of barrier sands. The soils are present in
sporadic and non-continuous layers but are abundant
throughout the system (Hail, 1969).
The unconsolidated sediments overlie the Late Car-
boniferous to Early Permian lithic sandstones, mud-
stones, pebbly sandstones and minor conglomerates of
the Kempsey beds (Leitch, 1972). Lying to the north,
adjacent to the Kempsey beds and forming the upper
reaches of the catchment are the lithologically similar
Early Permian Dee Pee beds which are comprised pri-
marily of slaty siltstones, lithic sandstones and minor
diamictite (Gilligan et al., 1992; Leitch, 1972). The Yar-
rahapinni Adamellite intrudes into the Dee Pee beds in
the region. This intrusion consists of a series of massive
discordant coastal granitoids of Late Triassic age
(Thomson, 1975) composed of leucocratic hornblende-
biotite monzogranite, biotite monzogranite, granite and
alaskite (Gilligan, et al., 1992). The contact aureoles
associated with the Yarrahapinni granitoids in places
span up to 2 km wide and comprise foliated sandstones
and siltstones, phyllites and sandy slates (Masman,
1973).
Considerable mineralisation occurs within the Yarra-
hapinni Adamellite and the surrounding contact aur-
eoles. Mineralisation occurs as outward zoning deposits
grading from Ag–Pb zones to Ag–As zones (Gilligan et
al., 1992). Within these zones fracture-controlled silic-
eous sulfide veins are present and have been shown to
contain considerable arsenopyrite (FeAsS) with some
 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496 1481

mineralised deposits producing assays of up to 9.4% As
of the mineralised mass (Kenny, 1937; Suppel and
Hobbs, 1977).
3. Geomorphology
Within this part of the NSW North Coast, inner
Pleistocene and outer Holocene barrier formations
developed along the coastline during times of sub-
mergence and oceanic stillstands, resulting in dune or
beach ridges positioned adjacent to pre-existing shor-
elines. They are composed of sediments reworked dur-
ing Pleistocene sea level fluctuations and the subsequent
Holocene transgression. Hail (1969) describes the
sediments as polygenetic in origin, as opposed to sedi-
ments derived entirely from the actively eroded land-
scapes. Stuarts Point, like the majority of the mid-north
coast of NSW, is characterised by zeta-curved or arcu-
ate bays consisting of sand barriers bordering narrow
fluvial-deltaic plains (Roy and Thom, 1981). The barrier
formations in the Stuarts Point region are terminated by
the Grassy Head bedrock headland in the north of the
catchment, and the Macleay River in the south. The
estuarine deposits of the Yarrahapinni wetland have
subsequently separated the Pleistocene and Holocene
barriers in this region.
Wave action during the Late Quaternary produced
the current coastal landforms and associated deposi-
tional sequences. This process has influenced the delivery

Fig. 1. Location of the study area and unconsolidated geology of the Stuarts Point aquifer (modified from Eddie, 2000). Also shown
are sampling points for regional studies, AsTot concentrations, and bundled-piezometer location.
1482 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
of quartz-rich sand to the shoreline with sands being
transported onshore into bedrock embayments during
marine transgressions throughout the Last Interglacial
and Holocene. Under stillstand conditions, sands were
reworked into regressive barriers (Roy and Thom,
1981).
During the Pleistocene glacial stage, a rapid post-gla-
cial sea level rise occurred, resulting in a marine trans-
gression of what was previously a dissected Pleistocene
coastal plain. This landform was buried under a
sequence of sands, silts and clays, and the Macleay
River alluviated its entrenched valley. Since then, only
very limited sea level rise, delta formation and barrier
development have occurred (Hail, 1969). Sediment was
transported shoreward during submergences and much
of it was probably derived from ephemeral shorelines
which were formed seaward of the present coast when
the sea level was lower. As the sea level continued to
rise, barriers were eroded by wave action. The erosion
that occurred during the Pleistocene is similar to that on
the present coastline (Hail, 1969).
4. Hydrogeology
The Yarrahapinni-Stuarts Point region consists of
two dominant groundwater systems. The first of these is
the heterogeneous Stuarts Point coastal sands aquifer
comprising unconsolidated Pleistocene and Holocene
barrier deposits and Holocene estuarine clays. Hydrau-
lic conductivity varies greatly within this system, ran-
ging from approximately 0.01 to 35.7 m/day. The
Pleistocene and Holocene sands exhibit the highest
conductivity contrasting with the reduced values within
the estuarine and lensing clay units. Aquifer hetero-
geneity occurs vertically and horizontally, resulting
from facies changes, in the Quaternary geology as well
as the presence of fluvial processes throughout the bar-
riers’ evolution. The second system contains the con-
solidated Permian sandstone, Triassic coastal granitoids
and associated metasediments, forming the Yarrahapinni
fractured rock aquifer.
Groundwater flow within the systems was assessed via
the established monitoring network of piezometers and
generally follows the topographic gradient (Fig. 2d)
from recharge areas in the north-northwest of the
catchment, to discharge areas within the estuaries and
wetlands in the ESE (Fig. 2a and c). The installation of
eight water level data loggers and an Electrical Con-
ductivity (EC) logger within the catchment, by the NSW
Department of Land and Water Conservation, was
undertaken to obtain an understanding of the temporal
variation of groundwater levels within the unconsoli-
dated aquifer (Smith et al., 2001a). Data from the log-
gers indicate that the shallow groundwater system is
relatively dynamic and readily responds to precipitation
events with corresponding increases in groundwater
heads and decrease in EC. Indurated soils within the
Pleistocene barrier deposits act as temporary perched
aquifers during times of extended precipitation. These
layers influence localised infiltration patterns to a lim-
ited extent, but are not continuous and/or consolidated
to an extent where they would exhibit the properties of a
permanent perched aquifer.
5. Stable environmental isotopes
Stable isotope investigation of 18O and 2H for both
the consolidated and unconsolidated groundwater sys-
tems (n=136) were undertaken to obtain an under-
standing of the recharge conditions within the system
(Criss and Davisson, 1996; Huddart et al., 1999). All
groundwater samples were plotted on the 18O versus
2H graph (Fig. 3), and the majority of water samples
plotted to the left of the Global Meteoric Water Line
(GMWL) (Rozanski et al., 1993) and along the Brisbane
Meteoric Water Line (BMWL) (IAEA/WMO, 1998).
These groundwaters have 18O values ranging from

5.0 to
3.5% and 2H values ranging from
30.0 to

15.0% (Smith et al., 2001a). The coincidence of the
groundwater with the BMWL indicates coastal meteoric
precipitation as the groundwater recharge source.
Groundwaters with more negative 18O values are asso-
ciated with groundwater recharge in the Yarrahapinni
fracture rock system. This groundwater has undergone a
process of isotopic fractionation associated with oro-
graphic precipitation and the subsequent altitude effect
(Bortolami et al., 1979) along the Yarrahapinni Moun-
tain. The representative 18O and 2H values for these
waters are in the order of
5.2 and
26.3% respec-
tively. The spatial distribution of these waters (Fig. 2b)
indicates that precipitation quickly mixes with regional
groundwaters and consequently plots within waters
more representative of direct meteoric recharge. The
remaining groundwaters of this system are classified
into two groups of distinct isotopic signature.
The first group, labeled (A) in Fig. 3, includes waters
associated with a possible combination of seasonal and
amount effects. Selective groundwaters in the township,
as well as in naturally vegetated areas of the Stuarts
Point region, are characterised by 18O and 2H values
ranging from
7.3 to
6.5% and
44.2 to
37.5%
respectively (Fig. 3). These values are potentially attrib-
uted to fractionation via the amount effect (Friedman et
al., 1962; Dansgaard, 1964), i.e. being representative of
groundwater, which is recharged during large storm
events or conversely a variation in isotopic composition
of precipitation as a result of seasonal temperature var-
iations in the region (Rozanski et al., 1993). This sig-
nature is subsequently obscured via mixing, however, as
these waters interact with deeper regional waters (Fig. 3).
 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496 1483

The closed
6.0 to
7.0% contours presented in Fig. 2b
represents this group.
The second group (B) (Fig. 3) includes waters within
the Yarrahapinni Holocene clay deposits. This water is
characterised by higher 18O (
0.78%) and 2H
(
3.7%) values. Groundwater samples obtained from a
nest of piezometers, finished at depths of 4.9, 10.3, and
20.3 m, through the Yarrahapinni Holocene clay
deposits have 18O and 2H values of
4.33 and

18.3%,
2.48 and
10.2% and
0.99 and
1.7%,
respectively (Smith et al., 2001a). Comparative increases
in EC (1361; 29,100; 32,100 mS/cm), Na+ (219; 5271;
5720 mg/l) and Cl
(136; 9162; 10,745 mg/l) values with
depth would suggest that these waters represent marine
formation water at depth, which is progressively
becoming diluted by mixing with meteoric recharge and
approaching the isotopic composition of the regional
groundwater system. Also plotted within this group are
samples taken from shallow depths in the south of the
catchment near the banks of the Macleay River. The

Fig. 2. (A) Vector map of groundwater flow directions (B) spatial plot of 18O (C) spatial plot of groundwater levels and (D) 3D
surface elevation map of the Stuarts Point region.
1484 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
isotopic ratio of these waters are produced from the
influx of saline waters from the estuary.
6. Methodology
A bundled-piezometer was installed approximately 14
m from the water supply bore for Stuarts Point town
and approximately 1300 m from the estuary shore
(Fig. 1). The depth to the bedrock at this location is
about 40 m. Hollow stem augers were used to support
the sands during drilling and the borehole was com-
pleted at 27 m without the addition of a drilling fluid.
Drill returns indicated that the formation from beneath
the water table to the base of the bore consisted of fine
to medium grained quartz sands.
The bundled-piezometer comprised small PVC tubes
(5 mm ID, 8 mm OD) fastened around a central 50 mm
PVC tube. The small tubes were terminated at 1 m
intervals throughout the whole length of the piezometer
producing 24 mini-piezometers. A 50 mm screen was
formed at the end of each mini-piezometer which was
completed with a small filter unit and the whole assem-
bly taped together and clearly labelled prior to installa-
tion. The augers were withdrawn after installation of the
bundled-piezometer allowing the formation to collapse
and fill the annulus around the piezometer.
Groundwater samples were withdrawn from the
aquifer using a peristaltic pump (GEOPUMP-2) at a
rate of approximately 250 ml/min. Groundwater with-
drawn from the tube was circulated through a closed
cell and monitored for temperature, EC, pH, redox
potential (Eh) and dissolved O2 (DO). Field measure-
ments of the above general parameters were recorded
when the measurements became stable. Field determi-
nations of alkalinity and CO2 were also made. Tem-
perature and EC were measured using an ORION
Fig. 3. Relationship between 18O and 2H in the Stuarts Point
aquifer.
model 122 conductivity meter. The conductivity read-
ings were checked in the field against freshly prepared
KCl standards ranging from 0.0005 to 0.05 M.
Dissolved O2 was measured using an ORION model
820 oxygen meter. The pH and Eh measurements were
made using an ORION model 290A portable pH/con-
centration meter. A glass electrode with a Ag/AgCl
reference was used for the pH measurements, calibrated
against standard buffer solutions of 4.01, 7.00 and
10.01. The Eh measurements were made using a Pt
redox electrode calibrated in the field against Zobell’s
solutions (Nordstrom, 1977; Zobell, 1946). Two sets of
EC, pH, DO and Eh measuring equipment were used
throughout the field work to eliminate possible error.
Error can sometimes occur through sulfide contamina-
tion of the probes. Total alkalinity as HCO3 was deter-
mined by titration with 0.01 M HCl against methyl
orange and bromcresol green indicators (American
Public Health Association, 1998). Carbon dioxide (free)
was determined by the titration of water samples using
0.025 M NaOH against phenolphthalein and metacresol
purple indicators (American Public Health Association,
1998). Water samples for chemical analyses of major
ions were filtered in the field using 0.45 mm Millipore
cellulose acetate membrane filters. Samples for major,
minor and trace elements determination were preserved
in the field by acidification using 0.4 ml of concentrated,
analytical grade HNO3 and analysed in the laboratory
using ICP-AES and ICP-MS. Chloride was determined
by an argentometric method and SO4 (as total S) by
ICP-AES. The ions, Fe2+, S2-, NH+ -
4 , NO3 and PO4
3-
were also analysed in the field by the HACH DR/2010
Spectrophotometer (Hach, 2000). The bore was com-
pleted in September 2000. The first round of chemical
sampling occurred in November 2000.
Due to the study site being located at significant dis-
tance from analytical facilities the ability to obtain reli-
able As speciation data was raised. The inherent
instability of As species, combined with the complex
nature of the sample matrix lead to considerable pro-
blems of sample preservation (Burguera and Burguera,
1997). Considerable Fe concentrations within the sam-
ples obtained from the site (up to 2.2 mg/l) and the evi-
dence of Fe oxyhydroxide precipitation in discarded
oxidised waters, precluded the use of anion-exchange
resins (Ficklin, 1983; Kim and Nriagu, 2000) as a means
of sample preservation. Arsenic in particulate form can
constitute a significant percentage of the As concen-
tration in any given sample (Le et al., 2000; Edwards et
al., 1998) commonly being present as adsorbed As on Fe
oxyhydroxide colloidal material. The implications of
generating error due to an exchange resin’s ineffective
removal of As(V) adsorbed on colloidal material and
the difficulty of rapidly pre-filtering with <0.1 mm mem-
brane filters to effectively remove them, generated con-
cern over the applicability of this method. Alternatively
 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
As(III) was determined in the field at the time of sam-
pling using the silver diethyldithiocarbamate method
described in the American Public Health Association
(1998). Field-robust equipment was designed, developed
and trialed in collaboration with the Australian Nuclear
Science and Technology Organisation (ANSTO) prior
to sampling. During field analysis standards, blanks and
duplicates were run at the commencement, during and
at the conclusion of each sampling day with an analy-
tical error of 4 10%. Three HACH model DR/2010
spectrophotometers were used in the field with indivi-
dually generating absorbency curves. A final detection
limit of  3 mg/l was obtained for As(III). Total As was
determined in the laboratory by ICP-MS, as Cl
con-
centrations in these samples were relatively low thus
reducing any potential of mass interference between
ArCl+ and As; As(V) was determined by deduction.
7. Regional groundwater chemistry
The chemical composition of groundwater in the
fractured aquifer systems west of Stuarts Point is closely
related to water–rock interaction. Recharge ground-
waters are oxidised (DO up to 7 mg/l) and acidic (pH 4–
5) and has a very low concentration of dissolved ions
(EC values 100 mS/cm). Oxidation of metal sulfides
and weathering of aluminosilicates in the fractured sys-
tem rapidly elevates EC values to more than 3000 mS/
cm, DO values decrease and pH is around 4. Sodium
and Cl are dominant ions with appreciable SO2
4 con-
centrations and low content of Ca2+, Mg2+ and HCO
3 FeOOH, with the highest As concentrations being pre-
(Smith et al., 2000).
The Stuarts Point coastal sands aquifer is recharged
by the flux of water from the underlying bedrock aquifer
(Smith et al., 2001a) but predominately from the direct
infiltration of precipitation through the unconsolidated
sands. The shallow system in the sandy aquifer contains
very fresh (EC values 30–100 mS/cm), oxidised and
strongly acidic (pH values 3–4) groundwaters due to
oxidation of FeS2 present in ASS and by interaction
with organic material producing organic acids. The
major ions are Na+ and Cl
, SO2
4 and HCO
3 con-
centrations are variable and the content of Ca2+ and
Mg2+ is low. Ion exchange reactions remove Ca2+ and
Mg2+ from solution and thereby dissolve carbonates.
Oxidation of FeS2 produces elevated Fe and SO4 con-
centrations (Smith et al., 2000).
7.1. Regional arsenic hydrogeochemistry
The presence of As in the Yarrahapinni fractured
rock groundwater system is putatively linked to the
presence of mineralised veins containing FeAsS, asso-
ciated with FeS2, pyrrhotite (Fe1-xS) and chalcopyrite
(CuFeS2) within the Yarrahapinni adamellite Ag–AS
1485
zone. Bores completed within weathered gravel zones
have considerably decreased As concentration. This
would support a mechanism of localised As release and
subsequent mobilisation within the fractured system.
Identified FeAsS enriched mineralised fractures run
parallel to regional lineaments and comprise northerly
strikes, complementing flow systems and observed As
concentration in bores within the fractured system. The
concentration of As reaches 17 mg/l in the fractured
aquifer system (Fig. 1) (Smith et al., 2000).
In the heterogeneous coastal sandy aquifer system, As
concentration reaches 70 mg/l (Fig. 1) (Smith et al.,
2000). The absence of meaningful correlations between
As and SO2
4 , As and S
2

and As and HCO3 in the sys-
tem potentially indicates a complex of groundwater
mixing and As release and loss conditions (Smith et al.,
2000). This concept is supported by the poor corre-
lations between As and FeTot, Fe2+ and Fe3+ (Smith et
al., 2000) as well as from the highest concentrations of
As being present over two pH ranges of 4.5–5.5 and 7–8.
The discharging groundwater from the bedrock poten-
tially brings As as a dispersed phase into the sandy
aquifer. However, As concentrations in the sandy aqui-
fer vary considerably across the groundwater system,
suggesting a complex origin of As. If a good correlation
is present between Fe(II) and As the origin of As can be
associated with the reductive dissolution of FeOOH.
The As associated with acidic groundwaters, however, is
probably from the oxidation of FeS2 present in ASS.
Arsenic present in circumneutral groundwaters is asso-
ciated to some extent with the reductive dissolution of
sent over low values of DO and a slightly reduced
environment from 0 to
200 mV (Smith et al., 2000).
8. Vertical variations in groundwater chemistry
The groundwater EC in the bundled-piezometer ran-
ges from 90 to 450 mS/cm and is dominated by two ions:
2+
HCO
3 and Ca . The high concentration of these ions
is attributed to the dissolution of shell debris (Roy and
Peat, 1974), which are extensively distributed through-
out the sandy material. The dissolution of shell material
also elevates Mg2+ and Sr2+ concentrations in ground-
water. Sodium and Cl
are delivered by marine pre-
cipitation and diffusion of marine aerosols into the soil
phase, and later leaching by rainwater. The metal con-
tent is associated with the dissolution/weathering of
carbonates, sulfates, oxides and hydroxides. The SO2
4
concentration is affected by several processes; oxidation
of FeS2 present in the ASS, dissolution of CaSO4 and
flux from the marine aerosols and precipitation. The low
concentration of SO2
4 compared with other coastal
aquifers in eastern Australia (Jankowski and Beck,
2000) is attributed to the redox reactions and formation
1486 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496

of S2
. The weathering of aluminosilicate minerals Substantial hydrogeochemical vertical variations

modifies cation concentrations. The concentration of
Ba2+, ranges from 5 to 23 mg/l and potentially origi-
nates from clay material. The pH is lower in the upper
part of the aquifer with a minimum of 5.74 in compar-
ison with 7.53 at depth. Throughout the depth profile,
DO is below 3 mg/l; it is generally less than 1 mg/l to
below detection limits. This is well correlated with the
Eh values, which show strongly reducing conditions in
association with concentrations of Fe2+ and S2
.
occur within the sandy aquifer at distinct depths and are
attributed to sequences of oxidation, reduction, ion
exchange, dissolution and precipitation reactions. Fig. 4a
illustrates the vertical distribution of pH in the ground-
water. At a depth of 9–11 m a considerable decrease in
pH from 7.22 to 5.74 was observed. This significant
decrease in pH is correlated with an increase in Eh (Eh-
171 mV, Fig. 4b), significant decreases in HCO
3 con-
centrations (50 mg/l), as well as depletions in dissolved

Fig. 4. Vertical profiles of groundwater chemistry in the Stuarts Point aquifer: (A) depth versus pH, AsTot, As(III) and As(V); (B)
depth versus Eh and Dissolved O2; (C) depth versus FeTot, Fe(II), Fe(III) and Mn2+; (D) depth versus Na+ and K+.
 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496 1487

Fe2+ (390 mg/l), Fe3+ (50 mg/l) and Mn2+ (17 mg/l)
(Fig. 4c). At this depth Na+, Cl
and EC are also con-
siderably depleted (5.9 mg/l, 8.4 mg/l and 94 mS/cm,
respectively) (Figs. 4d and 5a). The low concentration of
these ions and EC suggests the influx of relatively fresh
meteoric recharge. With more oxidising redox condi-
tions the precipitation of Fe- and Mn-oxyhydroxides is
removing Fe2+ and Mn2+ (Fig. 4c) from solution gen-
erating acidity and decreasing HCO
3 (Smith et al.,
2000). Aluminium and Zn2+ increase to 190 and 253 mg/
l, respectively (Fig. 5b). The decreases in pH and
presence of meteoric waters at this depth are geologi-
cally supported by the occurrence of dipping indurated
sands, which are consolidated to an extent where they
act as sufficient localised confining layers. The humic
properties of indurated soils would also contribute con-
siderable organic acids to groundwaters. These waters
are also depleted in Ca2+, Mg2+ and Sr2+ (Fig. 5c),
which correlates well with the absence of shell material
in the geological unit and hence absence of CaCO3 buf-
fering capacities facilitating the observed pH conditions
(Smith et al., 2000).

Fig. 5. Vertical profiles of groundwater chemistry in the Stuarts Point aquifer: (A) depth versus EC, TDS and Cl
; (B) depth versus
+ 3

Zn2+, Al3+and HCO
3 ; (C) depth versus Mg
2+
, Sr2+and Ca2+; (D) depth versus NO
3 , NH4 and PO4 .
1488 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496

The presence of shell material at a depth of 12.5 m concentrations of NH+ 4 (280 mg/l), S
2

(22 mg/l) and
results in an increased concentration of Ca2+ (80 mg/l), decreases in NO3 (3.1 mg/l) and SO2



4 (4.3 mg/l)
Mg2+ (3.6 mg/l), Sr2+ (2.2 mg/l) (Fig. 5c) and HCO
3 (Figs. 5d and 6a). At a depth of 11 m concentrations of
(226 mg/l) (Fig. 5b) in solution. The increase of pH to S2
and SO2
4 are 17 mg/l and 5.6 mg/l respectively
slightly alkaline levels (7.45) (Fig. 4a) distinguishes the (Fig. 6a).
water from that at 9–11 m. Concentrations of Fe2+ At a depth of 18 m there is a considerable increase in
(1530 mg/l), Fe3+ (680 mg/l) and Mn2+ (63 mg/l) sig- DO (2.8 mg/l) (Fig. 4b) and subsequent decrease in
nificantly increase via the reductive dissolution of both Mn2+, Fe2+, HCO-3 and NH+

4 and increases in NO3 . It
Mn- and Fe-oxyhydroxides in the aquifer material. This is clear that redox processes are being controlled by this
zone of reduced water is characterised by the increased distinctive presence of O2. 18O values obtained at this

Fig. 6. Vertical profiles of groundwater chemistry in the Stuarts Point aquifer: (A) depth versus SO2
2

4 and S ; (B) depth versus Cu,
Cr and Ba2+; (C) depth versus 18O and d2H.
 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
depth show a sharp variation to
3.67% (Fig. 6c). In
comparison to surrounding depths this 18O composi-
tion could be associated with a particular rainfall event,
enriched in dissolved O2, which has subsequently
recharged through the aquifer to this current depth. The
presence of a municipal abstraction bore adjacent to this
bundled-piezometer site is potentially influencing loca-
lised flow conditions and contributing to the observed
DO concentrations.
Water chemistry at a depth of 24–26 m is char-
acterised by increasing Cl
(26 mg/l), Na+ (14 mg/l)
and Mn2+, decreased FeTot and the lowest concentra-
tions of PO3
4 (Fig. 5d). This increase of Na
+
and Cl

potentially represents the influx of more saline water
from the leaching of adjacent Holocene marine clay
deposits. Increasing positive 18O values at depth
(Fig. 6c), however, would indicate against this assump-
tion, though the mixing of saline with fresh recharge
waters could account for the observed 18O values.
More probable, however, would be the influence of
localised terrestrial clay material on Na+ and Cl
con-
centrations. Alternatively the upward flux of fractured
Fig. 7. Relationship between: (A) Ca2++Mg2++Sr2+ versus HCO

and As(V) versus FeTot; (D) Fe2+ versus HCO

3 , for groundwaters from the Stuarts Point bundled-piezometer.
1489
rock water from the basement into the unconsolidated
sediments could be responsible for the increase. The
former process is favoured as groundwater within the
Yarrahapinni fractured rock aquifer is enriched in
Mg2+ and Li
, while the sandy aquifer is depleted in
these ions (Smith and Janowski, 2001). Additionally the
distance to the bedrock from the base of this piezometer
is much too high (about 13 m). With regard to the influx
of marine waters increased concentrations of SO2
4
would be expected, however, due to reducing conditions
SO2

4 is removed from solution to form S .
2

8.1. Vertical variation of arsenic
The AsTot, As(III) and As(V) concentrations from the
vertical profile were plotted against pH and Eh (Fig. 9a
and b). AsTot, As(III) and As(V) are present in elevated
concentrations in two relatively narrow pH ranges.
They are 5.7–5.8 and 7.4–7.6. This is similar to pH and
As occurrences identified in the regional system (Smith
et al., 2000), however, on the catchment scale elevated
As also occurs in very acidic waters (pH4.5). The As
3 ; (B) As
Tot
, As(III) and As(V) versus HCO

3 ; (C) As
Tot
, As(III)
1490 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
versus Eh graph (Fig. 9b) of the vertical profile shows
that the highest concentrations of As are limited to
reduced conditions at Eh values between
140 and

180 mV and between
200 and
220 mV. Regional
studies have indicated, however, that elevated As con-
centrations in this system occur in both oxidised and
reduced waters (Smith et al., 2000).
Vertical variation of As from the bundled-piezometer
is shown in Fig. 4a. Total As, As(III) and As(V) are
elevated in concentration at 10–11 m and 24–26 m
within this vertical section of the aquifer (Smith et al.,
2001b). At 10–11 m water is relatively acidic (pH - 5.74)
and As(V) (67 mg/l) is the dominant As species con-
sistent with the pH-controlled adsorption behaviour of
As(V) (Welch et al., 1988; Masscheleyn et al., 1991;
Hamasaki et al., 1995). The elevated concentrations of
As(V) occur with increased concentrations of Al3+ and
Zn2+ and overall decreased concentrations of both
Fe2+ and Mn2+ as discussed above. Arsenic(V) at this
depth is present due to either the dissolution of Al
hydroxides and release of adsorbed As(V) (Ferguson
Fig. 8. Relationship between: (A) Fe2+ versus SO2
4 ; (B) As
Tot
, As(III) and As(V) versus SO2

S2
; (D) AsTot, As(III) and As(V) versus PO3

4 , for groundwaters from the Stuarts Point bundled-piezometer.
and Gavis, 1972) or concurrently via pH-influenced
desorption of As enriched Fe oxides (Owen-Joyce, 1984;
Robertson, 1989).
At 24–26 m, As(III) (212 mg/l) dominates with water
being slightly alkaline (pH 7.46), slightly reduced (Eh -
166 mV) (Fig. 4a), elevated in HCO
3 (216 mg/l) and
depleted in Fe2+ (100 mg/l), Fe3+ (30 mg/l), S2
(3 mg/l)
and SO2
4 (6.5 mg/l). Factors controlling the increases in
As concentrations appear to be processes associated
with neither redox nor dissolution reactions. Arsenic
concentrations at this depth are not associated with the
oxidation of sulfide-based minerals (Robertson, 1989;
Peters et al., 1999; Schreiber et al., 2000) owing to the
absence of a significant correlation with SO2
4 and the
slightly alkaline pH conditions. Arsenic concentrations
also appear to be unrelated to the reductive dissolution
of Fe- and Mn-oxyhydroxides (Thornton, 1996; Nick-
son et al., 2000, Yan et al., 2000) due to the lack of
correlation between As, and Fe2+ and Mn2+. The high
concentrations of As in correlation with high pH and
2

HCO


3 suggest that HCO3 competition with HAsO4 is
4 ; (C) As
Tot
, As(III) and As(V) versus
 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
reducing the possible extent of As sorption on Fe- and
Mn-oxyhydroxides in water (Smedley et al., 1998). As
discussed above, water chemistry at this depth is prob-
ably influenced by localised or terrestrial marine clay
deposits as Na+ and Cl
are increasing. With regards to
the marine clays, continual submersion of these sedi-
ments during the Holocene with marine waters would
facilitate the potential for As present in seawater to
become absorbed to the clay sequences (Manning and
Goldberg, 1997; Khan et al., 2001). The release of As
into the water column and subsequent transport since
the deposition of the Holocene barrier sands is poten-
tially generating the concentrations of both As(III) and
As(V) observed.
9. Discussion
To explain the relationship between groundwater
chemistry and As concentrations several hydro-
geochemical processes have to be discussed. The dis-
solution of shell material is contributing HCO
3 , Ca
2+
, the regional groundwater chemistry (Smith et al., 2000).
Mg2+ and Sr2+ to the aquatic system. An excellent
correlation between Ca2++Mg2++Sr2+ versus HCO
3 Fe3+ also occur in the bundled-piezometer (Fig. 7c).
(r2=0.99) is shown in Fig. 7a. The ratio of
Ca2++Mg2++Sr2+/HCO
3 is along the line 1:2 sug-
gesting that simple dissolution is the major process sup-
plying these ions into solution. Stratigraphic logs and
subsequent analyses of acid extracts of sediment
obtained during the bundled-piezometer installation,
show strong correlations between the recorded presence
of shell material and the concentrations of Ca2+, Mg2+
and Sr2+ in the solid phase. These occurrences subse-
quently directly correlate with the observed liquid phase
concentrations throughout the profile.
Fig. 9. Relationship between: (A) AsTot, As(III) and As(V) versus pH; (B) AsTot, As(III) and As(V) versus Eh, for groundwaters from
the Stuarts Point bundled-piezometer.
1491
Reductive dissolution of Fe(III) oxyhydroxides has
been discussed as a major cause of As release into
aquatic systems in Bangladesh and India (Nickson et al.,
2000; Kinniburgh and Smedley, 2001; McArthur et al.,
2001; Ravenscroft et al., 2001). The release of As from
arseniferous Fe-oxyhydroxides by the reducing ground-
water is valid for sediments, where rapid consumption
of O2 by the microbial metabolism of organic matter
(Lovley, 1997; Banfield et al., 1998; Chapelle, 2000;
Lovley and Anderson, 2000) produces a strongly
reduced aquatic system (Nickson et al., 2000; Kinni-
burgh and Smedley, 2001). This process releases As,
HCO
3 and Fe
2+
into solution according to the equation:
8FeOOH þ CH3 COO
þ 15H2
) 8Fe2þ þ 2HCO

3 þ 12H2 O ð1Þ
If the process is valid, a correlation between HCO
3
and As would occur. Fig. 7b shows the relationship
between As and HCO
3 which illustrates an absence of
such a correlation. This observation is consistent with
Negative correlations between As and FeTot, Fe2+ and
This again is consistent in the regional chemistry, low-
ering support for the adsorption of As on Fe(III) oxy-
hydroxides as the dominant process controlling As
concentrations in the system (Smith et al., 2000; Matis-
off et al., 1982). The relationship between Fe2+ and
HCO
3 also shows no correlation (Fig. 7d); which
should plot along a line developed from the molar ratio
of HCO
3 /Fe
2+
. All samples plot to the right of such a
line (Fig. 7d). However, this relationship is obscured by
the high concentrations of HCO
3 being produced by the
dissolution of shell material.
1492 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
The oxidation of arsenical pyrite is also regarded as
an important process that supplies As into groundwater
systems. It has been shown that As has the potential to
accumulate in ASS (Dudas, 1987; Gustafsson and Tin,
1994). The Stuarts Point coastal sands aquifer contains
significant amounts of ASS (Eddie, 2000). The oxidation
of arsenical pyrite can be described by the following
reaction:
ðFeS
AsÞðsÞ þ7=2O2 þ H2 O
¼ Fe3þ þ SO2
3

4 þ AsO4 þ 2H
þ
ð2Þ
The products of this reaction are Fe3+, arsenate
(As(V)), SO4 and acidity. The reaction will occur as long
as there is sufficient O2 or oxyanions present to sustain
the oxidation reaction. In oxidising and alkaline condi-
tions Fe3+ will be removed from solution to form
Fe(III) oxyhydroxides, and correspondingly, partial
absorption of As(V) onto the FeOOH, will cycle As
back to the solid phase. Sulfate, however, will still be
present in the groundwater, unless groundwater condi-
tions become more reducing, upon which O2 can be
completely removed, SO2
4 will be reduced to S
2

and
As(V) will be released from FeOOH with As(V) being
slowly reduced to As(III). No correlation has been
found between Fe3+ and SO2
4 (Fig. 8a), and As and
SO2

4 (Fig. 8b), however, some negative correlation
exists between As and S2
(Fig. 8c). Concentrations of
SO2

4 in the groundwater system are below 11 mg/l and
the highest concentrations of As are present where SO2
4
concentrations are below 10 mg/l (Fig. 8b). The regional
data set also shows no correlation between As and SO2
4
and from more than 140 groundwater samples, more
than 80% of As is present where SO2
4 concentrations
are below 100 mg/l. Because of the lack of any sup-
porting correlation between As and SO2
4 , and As and
Fe3+ the oxidation of arsenical pyrite is not the major
source of As. However, on a minor scale, because of the
presence of pyrite in the sediments, the oxidation of
arsenical pyrite is not completely discounted as a possi-
ble contributing source of As in the system.
Application of PO4-rich fertilisers can enhance the
mobility of As in the groundwater systems (Perya and
Kammereck, 1997; Acharyya et al., 2000). The presence
of organic matter and its decay can also be responsible
for an increase of PO4 in aquatic systems. The relation-
ship between As and PO3
4 is shown in Fig. 8d. Negative
correlation between these elements suggests that com-
petitive exchange can be a process delivering As into
groundwater (Hongshao and Stanforth, 2001). How-
ever, the highest concentration of As occurs at a depth
of 25 m, and application of PO4 fertilisers in this area is
very small. Studies by Manning and Martens (1997)
have shown that a much larger amount of P is necessary
to significantly increase leaching of As-rich sediments.
In this regard the presence of P and its relationship with
As can only have a marginal effect on As concentration
in the Stuarts Point coastal sands aquifer (McArthur et
al., 2001; Ravenscroft et al., 2001).
Adsorption, desorption, oxidation and dissolution of
As at clay sites are very important processes for
attenuation and mobilisation of As (Lin and Puls, 2000;
Forest and Griffin, 1977). Arsenic can be adsorbed onto
Al–OH groups as particles on the edges of mineral par-
ticles (Manning and Goldberg, 1997). Manning and
Goldberg (1997) and Lin and Puls (2000) have found
that As(V) is preferentially adsorbed over As(III) on
illitic and kaolinitic clays. Oxidation of As(III) to As(V)
occurs on the clay surfaces, however, desorption of As
from the clays is higher for As(III) than As(V) (Man-
ning and Goldberg, 1997). The low EC (90 to 450 mS/
cm) and the absence of strong correlations between
Na+, Ca2+, Mg2+ and As at shallow depths, in the
presence of clay in the profile, suggests that As from
clay minerals is not associated with the dominate pro-
cess of As release. However, at greater depths, increas-
ing concentrations of these ions in the presence of clay
indicates that it should not be discounted as a significant
release process.
Several factors are responsible for the AsTot, and
speciation of As(III) and As(V) in the groundwater sys-
tems; the two most important factors are pH and Eh.
Arsenic solubility is extensively influenced by redox and
pH conditions and hence varies considerably within soil
profiles (Cherry et al., 1979; Holm and Curtis, 1989;
Masscheleyn et al., 1991). Arsenic speciation in aquatic
systems, however, is predominantly controlled by pH
(Cullen and Reimer, 1989; Korte and Fernando, 1991;
Hamasaki et al., 1995). Arsenic is present in oxidised
aquatic systems at low pH ( < 3) as orthoarsenic acid
(H3AsO4); in less acidic waters (pH 3–7), As occurs as
monovalent arsenate anion H2AsO
4 , whereas in alka-
line waters (pH 7–11) it is present as the divalent arse-
nate anion HAsO2
4 .
10. Mobilisation and sink of arsenic species
The mobilisation of As in the Stuarts Point coastal
sands aquifer involves a complex series of hydro-
geochemical processes. No single hydrogeochemical
process can convincingly describe the release of As from
the solid phase into the groundwater system. At a depth
of 10–11 m high concentration of AsTot and As(V) in the
presence of Al3+ could be associated with mobilisation
from Al-hydroxides. However, the possibility that As(V)
is present because of the oxidation of arsenical pyrite
should not be excluded. During mobilisation of As from
the oxidation of sulfide-bearing sediments, pH decreases,
if mineral oxidation is in excess of the buffering capacity
 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
of shell material. In this situation pH conditions would
remain acidic as is the case at this depth. However, sul-
fide-bearing minerals can also be a sink for As in a
reducing environment, thus the process of redox cycling
plays an important role in determining the
concentration of As in solution at any given point in
time (Moore et al., 1988; Webster, 1990; Rittle et al.,
1995; Dowdle et al., 1996; Ahmann et al., 1997; Stolz
and Oremland, 1999; Zobrist et al., 2000).
At the depth of 24–26 m a plausible mechanism for
the increase of As could be associated with the influence
of clay minerals. Leaching of the aquifer’s sandy-clayey
matrix by groundwaters rich in HCO
3 and of high pH
can also elevate the As concentration, a process also
described by Kim et al. (2000). Very often high con-
centrations of As are associated with HCO3-Ca-rich
groundwaters (Schlottman and Breit, 1992; Planer-
Friedrich et al., 2001). At pH values above 7 the leach-
ing of sandy-clays by groundwater of high pH can pro-
duce carbonate complexation (Schlottman and Breit,
1992; Kim et al., 2000). At this depth, increasing con-
centration of Cl
and Na+ show good correlation with
elevated As concentrations, which would be suggestive
of a clay associated As origin. The lack of increased
SO2-
4 content can be explained by the reduction of SO4
to S2
in the strongly reducing environment. However
the presence of As in clay minerals through adsorption
and as a later source of As in groundwater, generally is
more likely with terrestrial clay. Arsenic in marine clays
is predominantly present in organic matter and pyrite
(Tourtelot, 1964). Therefore if clay is playing a role in
the occurrence of As in this system, localised lenses
would be significant.
An important sink for As in the Stuart Point coastal
sands aquifer could be associated with the precipitation
of As with S2
. In the reducing environment, S2
in the
presence of As(III) will produce favourable conditions
for the precipitation of orpiment (Moore et al., 1988;
Rittle et al., 1995). A second process that removes As
from solution is precipitation of barium arsenate
(Ba3(AsO4)2). Recent studies in Mexico (Planer-Frie-
drich et al., 2001) have found that barium arsenate can
theoretically precipitate under conditions applicable to
those found in the Stuarts Point coastal sands aquifer.
Jimenez and Prieto (2000) have discussed the precipita-
tion of this mineral during interaction of As-rich redu-
cing waters with barite, and Schlieker et al. (2001) have
found from experimental studies that the redox pro-
cesses can significantly enhance precipitation of
Ba3(AsO4)2 in a sandy aquifer. Concentration of Ba2+
increases in groundwaters when conditions are more
reducing and SO2- 4 is low. In reduced groundwater Ba
2+
behaves conservatively (Jankowski and Schofield, 2001)
and concentration can increase as long as it does not
react with As(V) present in the aquifer. The concentra-
tions of Ba2+ in the vertical profile are relatively low
1493
however and are probably more tentatively linked to
clay material than associated with Ba3(AsO4)2.
11. Conclusions
This study of a coastal aquifer system shows that the
presence and distribution of elevated concentrations of
As involves a complex series of hydrogeochemical pro-
cesses. No single hydrogeochemical process can describe
on a regional or local scale the release of As from the
solid phase to the groundwater system. Processes of
competitive exchange with PO3


4 and HCO3 , reductive
dissolution of Fe oxyhydroxides and arsenical pyrite
oxidation, though not forming dominant correlations,
are still evident and influence As chemistry at this site.
From investigations of the factors controlling the con-
centration and vertical distribution of As(III) and As(V)
in this coastal sandy aquifer, the following principal
conclusions are drawn:
1. The elevated concentrations of As in the shallow
system (10–11 m) are present in very fresh, acidic
water, where the occurrence of As can be attri-
buted to hydrolysis reactions of Al-hydroxides
or pH-influenced desorption of As enriched Fe-
oxyhydroxides in the absence of the buffering
capacity generated by shell material in the strata.
The dominant As species is As(V) which is stable
in acidic conditions.
2. Elevated concentration of AsTot and As(III) at
25 m is related to the leaching of clay material
releasing Na+ and Cl
. The leaching of the clay
surfaces in elevated HCO-3 and alkaline pH
conditions causes desorption of As which is
later present as As(III) species in the reducing
environment.
The identification of As in the coastal groundwater
environment raises serious questions of the suitability of
untreated groundwater as a drinking water source from
these aquifer types. Further investigation is paramount
to quantify the Australian and global extent of As
occurrences in current and future water supplies drawn
from the coastal groundwater environment.
Acknowledgements
The authors would like to acknowledge funding pro-
vided by the Natural Heritage Trust (Coast and Clean
Seas Program), Yarrahapinni Wetland Reserve Trust,
the NSW Department of Land and Water Conservation
(Kempsey and Grafton offices), the Macleay River
Total Catchment Management Committee and the
1494 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
analytical assistance of M. T. Emett (ANSTO, Envir-
onment Division).
References
Acharyya, S.K., 1999. Comment on Nickson et al. Arsenic
poisoning of Bangladesh groundwater. Nature 401, 545.
Acharyya, S.K., Lahiri, S., Raymahashay, B.C., Bhowmik, A.,
2000. Arsenic toxicity of groundwater in parts of the Bengal
Basin in India and Bangladesh: the role of Quaternary stra-
tigraphy and Holocene sea-level fluctuation. Environ. Geol.
39, 1127–1137.
Ahmann, D., Krumholz, L.R., Hemond, H.F., Lovley, D.R.,
Morel, F.M.M., 1997. Microbial mobilization of arsenic
from sediments of the Aberjona Watershed. Environ. Sci.
Technol. 31, 2923–2930.
American Public Health Association, 1998. Standard Methods
for the Examination of Water and Wastewater, Twentieth
ed. APHA-AWWA-WET, Washington DC.
Arminta, M.A., Rodriguez, R., Cruz, O., 1997. Arsenic content
in hair of people exposed to natural arsenic polluted
groundwater at Zimapan, Mexico. Bull. Environ. Contam.
Toxicol. 9, 583–589.
Banfield, J.F., Nealson, K.H., Lovley, D.R., 1998. Geomicro-
biology: interaction between microbes and minerals. Science
280, 54–55.
Berg, M., Tran, H.C., Nguyen, T.C., Pham, H.V., Schertenleib,
R., Giger, W., 2001. Arsenic contamination of groundwater
and drinking water in Vietnam: a human health threat.
Environ. Sci. Technol. 35, 2621–2626.
Bhattacharya, P., Chatterjee, D., Jacks, G., 1997. Occurrence
of arsenic-contaminated groundwater in alluvial aquifers
from delta plains, Eastern India: options for safe drinking
water supply. Water. Resour. Develop. 13, 79–92.
Bortolami, G.C., Ricci, B., Susella, G.F., Zuppi, G.M., 1979.
Isotope hydrology of the Val Corsaglia, Maritime Alps,
Piedmont, Italy. In: Isotope Hydrology 1978, Vol I, IAEA
Symp. 228, June 1978, Germany, pp. 327–350.
Burguera, M., Burguera, J.L., 1997. Analytical methodology
for speciation of arsenic in environmental and biological
samples. Talanta 44, 1581–1604.
Chapelle, F.H., 2000. The significance of microbial processes
in hydrogeology and geochemistry. Hydrogeol. J. 8, 41–
46.
Chen, S.L., Dzeng, S.R., Yang, M.H., Chiu, K.H., Shieh,
G.M., Wai, C.M., 1996. Arsenic species in groundwaters of
the Blackfoot disease area, Taiwan. Environ. Sci. Technol.
28, 877–881.
Cherry, J.A., Shaikh, A.U., Tallman, D.E., Nicholson, R.V.,
1979. Arsenic species as an indicator of redox conditions in
groundwater. J. Hydrol. 43, 373–392.
Criss, R.E., Davisson, M.L., 1996. Isotopic imaging of surface
water/groundwater interactions, Sacramento Valley, Cali-
fornia. J. Hydrol. 178, 205–222.
Cullen, W.R., Reimer, K.J., 1989. Arsenic speciation in the
environment. Chem. Rev. 89, 713–764.
Dansgaard, W., 1964. Stable isotopes in precipitation. Tellus
16, 436–468.
Del Razo, L.M., Arellano, M.A., Cebrián, M.E., 1990. The
oxidation states of arsenic in well water from a chronic
arsenicism area of Northern Mexico. Environ. Pollut. 64,
143–153.
Dhar, R.K., Biswas, B.K., Samanta, G., Mandal, B.K., Chak-
raborti, D., Roy, S., Jafar, A., Islam, A., Ara, G., Kabir, S.,
Khan, A.W., Ahmed, S.K., Hadi, S.A., 1997. Groundwater
arsenic calamity on Bangladesh. Current Sci. 73, 48–59.
Dowdle, P.R., Laverman, A.M., Oremland, R.S., 1996. Bac-
terial dissimilatory reduction of arsenic(V) to arsenic(III) in
anoxic sediments. Appl. Environ. Microbiol. 62, 1664–1669.
Dudas, M.J., 1987. Accumulation of native arsenic in acid sul-
phate soils in Alberta. Can. J. Soil Sci. 67, 317–331.
Eddie, M.W., 2000. Soil Landscapes of the Macksville and
Nambucca 1:100 000 Sheets. Department of Land and Water
Conservation, Sydney.
Edwards, M., Patel, S., McNeill, L., Chen, H., Frey, M.,
Eaton, A.D., Antweiler, R.C., Howard, T.E., 1998. Con-
siderations in As analysis and speciation. J. AWWA 90, 103–
113.
Ferguson, J.F., Gavis, J., 1972. A review of the arsenic cycle in
natural waters. Water Res. 6, 1259–1274.
Ficklin, W., 1983. Separation of arsenic (III) and arsenic (V) in
ground waters by ion-exchange. Talanta 30, 371–373.
Forest, R.R., Griffin, R.A., 1977. Effect of pH on adsorption of
arsenic and selenium from landfill leachate by clay minerals.
Soil Sci. Soc. Am. J. 41, 53–57.
Friedman, I., Machta, L., Soller, R., 1962. Water vapour
exchange between a water droplet and its environment. J.
Geophys. Res. 67, 2761–2766.
Gilligan, L.B., Brownlow, J.W., Cameron, R.G., Henley, H.F.,
1992. Dorrigo–Coffs Harbour 1:250 000 Metallogenic Map
SH/56-10, SH/56-11: Metallogenic Study and Mineral
Deposit Data Sheets. New South Wales Geol. Surv, Sydney.
Guo, H.R., Chiang, H.S., Hu, H., Lipsitz, S.R., Monson, R.R.,
1997. Arsenic in drinking water and incidence of urinary
cancers. Epidemio 8, 545–550.
Gustafsson, J.P., Tin, N.T., 1994. Arsenic and selenium in
some Vietnamese acid sulphate soils. Sci. Total. Environ.
151, 153–158.
Hach, 2000. Dr 2010 Spectrophotometer. Procedures Manual.
Hail, J.R., 1969. The Late Quaternary History of Three Areas
on the New South Wales Coast, Australia. PhD thesis, Univ.
Sydney.
Hamasaki, T., Nagase, H., Yoshioka, Y., Sato, T., 1995. For-
mation, distribution and ecotoxicity of methylmetals of tin,
mercury and arsenic in the environment. Crit. Rev. Environ.
Sci. Technol. 25, 45–91.
Holm, T.R., Curtis, C.D., 1989. A comparison of oxidation-
reduction potentials calculated from the As(V)/As(III) and
Fe(III)/Fe(II) couples with measured platinum-electrode
potentials in groundwater. J. Contan. Hydrol. 5, 67–81.
Hongshao, Z., Stanforth, R., 2001. Competitive adsorption of
phosphate and arsenate on goethite. Environ. Sci. Technol.
35, 4753–4757.
Hopemhayn-Rich, C., Biggs, M.L., Fuchs, A., Bergoglio, R.E.,
Nicolli, H.B., Smith, A.H., 1996. Bladder cancer mortality
associated with arsenic in drinking water in Argentina. Epi-
demio 7, 117–124.
Huddart, P.A., Longstaffe, F.J., Crowe, A.S., 1999. dD and
d18O evidence for inputs to groundwater at a wetland coastal
boundary in the southern Great Lakes region of Canada. J.
Hydrol. 214, 18–31.
 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
IAEA/WMO, 1998. Global Network for Isotopes in Precipita-
tion. The GNIP Database. Release 3, October 1999. URL:
http://www.iaea.org/programs/ri/gnip/gnipmain.htm.
Jackson, B.P., Miller, W.P., 2000. Effectiveness of phosphate
and hydroxide for desorption of arsenic and selenium species
from iron oxides. Soil Sci. Soc. Am. J. 64, 1616–1622.
Jankowski, J., Beck, P., 2000. Aquifer heterogeneity: hydro-
geological and hydrochemical properties of the Botany Sands
aquifer and their impact on contaminant transport. Aust. J.
Earth Sci. 47, 45–64.
Jankowski, J., Schofield, S., 2001. Trace elements as an indi-
cator of redox processes in a fractured aquifer system, Balli-
more, central New South Wales, Australia. In: Seiler, K.P.,
Wohnlich, S. (Eds.), Proc. XXXI Cong. IAH, Munich, Ger-
many, 10–14 September, 2001. Balkema, Rotterdam, pp.
971–975.
Jimenez, A., Prieto, M., 2000. Cristalizacion de Ba3(AsO4)2 e
interaciones As(V)-barita en medios porosos. Cadernos do
Laboratorio Xeoloxico de Laxe, 197–198.
Karim, M., 2000. Arsenic in groundwater and health problems
in Bangladesh. Water Res. 34, 304–310.
Kenny, E.J., 1937. A Geological Reconnaissance of Portions of
the North Coast of New South Wales (Report GS1937/054).
New South Wales Geol. Surv, Sydney.
Khan, A.A., Alam, S.M.M., Akhter, S.H., 2001. Clay and fate
of arsenic transport in the Ganges delta plains of Bangla-
desh. In: Proc. Internat Symp. Suction, Swelling, Perme-
ability and Structure of Clays. Schizuoka, Japan, 11–13
January, 2001. Balkema, Rotterdam.
Kim, M.J., Nriagu, J., Haack, S., 2000. Carbonate ions and
arsenic dissolution by groundwater. Environ. Sci. Technol.
34, 3094–3100.
Kim, M.J., Nriagu, J., 2000. Oxidation of arsenite in ground-
water using ozone and oxygen. Sci. Total. Environ. 247, 71–
79.
Kinniburgh, D.G. Smedley, P.I. (Eds.), 2001. Arsenic Con-
tamination of Groundwater in Bangladesh, Vol. 2. Final
Report. BGS Technical Report WC/00/19.
Korte, N.E., Fernando, Q., 1991. A review of arsenic(III) in
groundwater. Crit. Rev. Environ. Control 21, 1–39.
Le, X.C., Yalcin, S., Ma, M., 2000. Speciation of sub-
microgram per litre levels of arsenic in water: on-site species
separation integrated with sample collection. Environ. Sci.
Technol. 34, 2342–2347.
Leitch, E.C., 1972. The Geological Development of the Bellin-
ger–Macleay Region. A study of the Tectonics of the New
England Fold Belt. PhD. thesis, Univ. New England.
Lin, Z., Puls, R.W., 2000. Adsorption, desorption and oxida-
tion of arsenic affected by clay minerals and aging process.
Environ. Geol. 39, 753–759.
Lovley, D.R., 1997. Microbial Fe(III) reduction in subsurface
environment. FEMS Microbiol. Rev. 30, 305–313.
Lovley, D.R., Anderson, R.T., 2000. Influence of dissimilatory
metal reduction on the fate of organic and metal con-
taminants in the subsurface. Hydrogeol. J. 8, 77–88.
Mallick, S., Rajagopal, N.R., 1996. Groundwater development
in the arsenic-affected alluvial belt of West Bengal—some
questions. Current Sci. 70, 956–958.
Mandal, B.K., Chowdhury, T.R., Samanta, G., Mukherjee,
D.P., Chanda, C.R., Saha, K.C., Chakraborti, D., 1998.
Impact of safe water for drinking and cooking on five
1495
arsenic-affected families for 2 years in West Bengal, India.
Sci. Tot. Environ. 218, 185–201.
Manning, B.A., Goldberg, S., 1997. Adsorption and stability of
arsenic(III) at the clay mineral-water interface. Environ. Sci.
Technol. 31, 2005–2011.
Manning, B.A., Martens, D.A., 1997. Speciation of arsenic(III)
and arsenic(V) in sediments extracts by high-performance
liquid chromatography—hydrite generation atomic adsorp-
tion spectrophotometry. Environ. Sci. Technol. 31, 171–177.
Masman, K.A., 1973. Geology of the Way Way Area New
South Wales. BAppSc. thesis, Univ. New South Wales.
Masscheleyn, P.H., Delaune, R.D., Patrick Jr., W.H., 1991.
Effect of redox potential and pH on arsenic speciation and
solubility in a contaminated soil. Environ. Sci. Technol. 25,
1414–1419.
Matisoff, G., Khourey, C.J., Hall, J.F., Varnes, A.W., Strain,
W.H., 1982. The nature and source of arsenic in North-
eastern Ohio ground water. Ground Water 20, 446–456.
McArthur, J.M., Ravenscroft, P., Safiullah, S., Thirlwall, M.F.,
2001. Arsenic in groundwater: testing pollution mechanisms
for sedimentary aquifers in Bangladesh. Water Resour. Res.
37, 109–117.
Moore, J.N., Ficklin, W.H., Hayes, T.H., 1988. Partioning of
arsenic and metals in reducing sulfidic sediments. Environ.
Sci. Technol. 22, 432–437.
National Research Council, 1999. Arsenic in Drinking Water.
National Academy Press, Washington, DC.
National Health and Medical Research Council and Agri-
culture and Resources Management Council of Australia
and New Zealand (NHMRC), 1996. Australian Drinking
Water Guidelines. National Water Quality Management
Strategy, Canberra.
Nickson, R.T., McArthur, J.M., Ravenscroft, P., Burgess,
W.G., Ahmed, K.M., 2000. Mechanism of arsenic release to
groundwater, Bangladesh and West Bengal. Appl. Geochem.
15, 403–413.
Nicolli, H.B., Suriano, J.M., Gomez Peral, M.A., Ferpozzi,
L.H., Baleani, O.A., 1989. Groundwater contamination with
arsenic and other trace elements in an area of the Pampa,
Province of Cordoba, Argentina. Environ. Geol. Water Sci.
14, 3–16.
Nordstrom, D.K., 1977. Thermochemical redox equilibria of
Zobell’s solution. Geochim. Cosmochim. Acta 41, 1835–
1841.
Owen-Joyce, S.J., 1984. Hydrogeology of a stream-aquifer sys-
tem in the Camp Verde Area, Yavapai Country, Arizona.
Arizona Dept. of Water Res. Bull. 3.
Peryea, F.J., Kammereck, R., 1997. Phosphate-enhanced
movement of arsenic out of lead arsenate-contaminated top-
soil and through uncontaminated subsoil. Water Air Soil
Pollut. 93, 243–254.
Peters, S.C., Blum, J.D., Klaue, B., Karagas, M.R., 1999.
Arsenic occurrence in New Hampshire drinking water.
Environ. Sci. Technol. 33, 1328–1333.
Planer-Friedrich, B., Armieta, M.A., Merkel, B.J., 2001. Origin
of arsenic in the groundwater of the Rioverde basin, Mexico.
Environ. Geol. 40, 1290–1298.
Ravenscroft, P., McArthur, J.M., Hoque, B.A., 2001. Geo-
chemical and palaeohydrological controls on pollution of
groundwater by arsenic. In: Chappell, W.R., Abernathy,
C.O., Calderon, R.L. (Eds.), Proc. 4th Internat. Conf.
1496 J.V.S. Smith et al. / Applied Geochemistry 18 (2003) 1479–1496
Arsenic Exposure and Health Effects. Elsevier Science Ltd,
Oxford.
Rittle, K.A., Drever, J.I., Colberg, P.J.S., 1995. Precipitation of
arsenic during bacterial sulfate reduction. Geomicrobiol. J.
13, 1–11.
Robertson, F.N., 1989. Arsenic in ground-water under oxidis-
ing conditions, south-west United States. Environ. Geochem.
Health 11, 171–186.
Roy, P.S., Peat, C., 1974. Shell Deposits in the Clybucca
Creek–Andersons Inlet Area of the Macleay Fluvial—Del-
taic Plain. Geological Survey of New South Wales, Depart-
ment of Mines. Technical Report, GS 1974/007.
Roy, P.S., Thom, B.G., 1981. Late Quaternary marine deposi-
tion in New South Wales and Southern Queensland—an
evolutionary model. J. Geol. Soc. Aust. 28, 471–489.
Rozanski, K., Araguas-Araguas, L., Gonfiantini, R., 1993.
Isotopic patterns in modern global precipitation. In: Con-
tinental Isotope Indicators of Climate, American Geophysi-
cal Union Monograph.
Schlieker, M., Schüring, J., Hencke, J., Schulz, H.D., 2001. The
influence of redox processes on trace element mobility in a
sand aquifer—an experimental approach. J. Geochem
Explor. 73, 167–179.
Schlottman, J.L., Breit, G.N., 1992. Mobilization of As and U
in the Central Oklahoma aquifer, USA. In: Kharaka, Y.F.,
Maest, A.S. (Eds.), Proc. 7th Internat. Symp. Water-Rock
Interaction, Park City, Utah, USA, 13–18 July, 1992. Balk-
ema, Rotterdam, pp. 835–838.
Schreiber, M.E., Simo, J.A., Freiberg, P.G., 2000. Stratigraphic
and geochemical controls on naturally occurring arsenic in
groundwater, eastern Wisconsin, USA. Hydrogeol. J. 8, 161–
176.
Smedley, P.L., Nicolli, H.B., Barros, A.J., Tullio, J.O., 1998.
Origin and mobility of arsenic in groundwater from the
Pampean Plain, Argentina. In: Arehart, G.B., Hulston, J.R.
(Eds.), Proc. 9th Internat. Symp. Water-Rock Interaction,
Taupo, New Zealand, 30 March–3 April, 1998. Balkema,
Rotterdam, pp. 275–278.
Smedley, P.L., Kinniburgh, D.G., 2002. A review of the source,
behaviour and distribution of arsenic in natural waters.
Appl. Geochem. 17, 517–568.
Smith, J.V.S., Jankowski, J., Sammut, J., 2000. Arsenic and
acidity in a groundwater system affected by acid sulphate
soils, Stuarts Point, Australia. In: Sililo, O., Appleyard, S.,
Barrett, M., Braune, E., Burgess, W., Cave, L., Chiang, W.,
Chilton, J., Colvin, C., Conrad, J., Dennis, I., Beer, J., Dil-
lon, P., Dottridge, J., Eiseirth, M., Engelbrecht, P., Fraser,
L., Frengstad, B., Gale, I., Harris, C., Hughes, S., Lerner,
D., Meyer, R., Morton, K., Murray, R., Parsons, R., Rivett,
M., Saayman, I., Stevens, N., Talma, S., Taylor, R., Tellam,
J., Tredoux, G., Weaver, J., Tonder, G., Verhagen, B.,
Woodford, A. (Eds.), Proc. XXX Cong. IAH, Cape Town,
South Africa, 26 November–1 December 2000. Balkema,
Rotterdam, pp. 615–621.
Smith, J.V.S., Jankowski, J., Acworth, I., 2001a. Hydro-
geochemical, isotopic and hydrogeological investigations of a
proposed coastal wetland restoration: Yarrahapinni Wet-
land, Northern New South Wales, Australia. In: Seiler, K.P.,
Wohnlich, S. (Eds.), Proc. XXXI Cong. IAH, Munich, Ger-
many, 10–14 September 2001. Balkema, Rotterdam, pp.
1291–1295.
Smith, J.V.S., Jankowski, J., 2001. The application of rare
earth elements hydrogeochemistry in the delineation of coastal
heavy mineral placer deposits. In: Seiler, K.P., Wohnlich, S.
(Eds.), Proc. XXXI Cong. IAH, Munich, Germany, 10–14
September 2001. Balkema, Rotterdam, pp. 201–205.
Smith, J.V.S., Jankowski, J., Sammut, J., 2001b. Vertical dis-
tribution of As(III) and As(V) in a coastal sandy aquifer:
marine clays, a potential reservoir for arsenic in coastal
groundwater systems. In: Cidu, R. (Ed.), Proc. 10th Internat.
Symp. Water-Rock Interaction, Villasimius, Italy, 10–15
June 2001. Balkema, Rotterdam, pp. 1009–1012.
Stolz, J.F., Oremland, R.S., 1999. Bacterial respiration of
arsenic and selenium. FEMS Microbial. Rev. 23, 615–627.
Suppel, D.W., Hobbs, J.J., 1977. Mineralisation in and Geo-
chemical Survey of the Yarrahapinni–Way Way State Forest
Area, Macksville, New South Wales (Report GS1977/124).
New South Wales Geological Survey, Sydney.
Thomson, J., 1975. Results of radiometric dating programme,
1971–1973. The New South Wales Geological Survey, Syd-
ney, Records 16, 230–244.
Thornton, I., 1996. Sources and pathways of As in the geo-
chemical environment: health implications. Environ. Geo-
chem. Health 113, 153–161.
Tossell, J.A., 1997. Theoretical studies on arsenic oxide and
hydroxide species in minerals and in aqueous solution. Geo-
chim. Cosmochim. Acta 61, 1613–1623.
Tourtelot, H.A., 1964. Minor element composition and organic
carbon content of marine and non-marine shales of late
Cretaceous age in the western interior of the United States.
Geochim. Cosmochim. Acta 28, 1579–1604.
Webster, J.G., 1990. The solubility of As2S3 and speciation of
As in dilute and sulphide-bearing fluids at 25 and 90 C.
Geochim. Cosmochim. Acta 54, 1009–1017.
Welch, A.H., Lico, M.S., 1998. Factors controlling As and U in
shallow ground water, southern Carson Desert, Nevada.
Appl. Geochem. 13, 521–539.
Welch, A.H., Lico, M.S., Hughes, J.L., 1988. Arsenic in ground
water from the western United States. Ground Water 26,
333–347.
Welch, A.H., Westjohn, D.B., Helsel, D.R., Wanty, R.B., 2000.
Arsenic in ground water of the United States: occurrence and
geochemistry. Ground Water 38, 589–604.
World Health Organisation (WHO), 1994. Recommendations,
second ed. In: Guidelines for Drinking Water Quality, Vol. 1.
World Health Organisation, Geneva.
Yan, X.P., Kerrich, R., Hendry, J.M., 2000. Distribution of
arsenic(III), arsenic(V) and total inorganic arsenic in pore-
waters form a thick till and clay-rich aquitard sequence,
Saskatchewan, Canada. Geochim. Cosmochim. Acta 62,
2637–2648.
Zobell, C.E., 1946. Studies on redox potential of marine sedi-
ments. Bull. Amer. Assoc. Petrol. Geol. 30, 477–513.
Zobrist, J., Dowdle, P.R., Davis, J.A., Oremland, R.S., 2000.
Mobilization of arsenite by dissimilatory reduction of adsor-
bed arsenate. Environ. Sci. Technol. 34, 4747–4753.