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Spatial and Temporal Variations of Groundwater Arsenic in South and Southeast


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Spatial and Temporal Variations of Groundwater
Arsenic in South and Southeast Asia
Scott Fendorf, et al.
Science 328, 1123 (2010);
DOI: 10.1126/science.1172974

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REVIEW
factors that will control changes in the distri-
bution of As over time.

Spatial and Temporal Variations of What Drives the Release of


Arsenic to Groundwater?
Groundwater Arsenic in South and Weathering of Himalayan-derived sediment dur-
ing erosion and transport leads to downstream dep-

Southeast Asia osition of As. The primary sources of As within


the Himalayas are thought to be eroding coal
seams and rocks containing sulfide minerals (12).
Scott Fendorf,1* Holly A. Michael,2* Alexander van Geen3* Exposed to the atmosphere, the minerals con-
tained within these deposits are oxidized, and
Over the past few decades, groundwater wells installed in rural areas throughout the major river basins much of their As content is transferred to sec-
draining the Himalayas have become the main source of drinking water for tens of millions of people. ondary phases including iron (Fe) hydroxides,
Groundwater in this region is much less likely to contain microbial pathogens than surface water but oxyhydroxides, and oxides, collectively referred
often contains hazardous amounts of arsenic—a known carcinogen. Arsenic enters groundwater naturally to as Fe oxides hereafter (13, 14). There is indeed
from rocks and sediment by coupled biogeochemical and hydrologic processes, some of which are a positive relation between As and Fe extracted
presently affected by human activity. Mitigation of the resulting health crisis in South and Southeast from hundreds of sediment samples from the

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Asia requires an understanding of the transport of arsenic and key reactants such as organic carbon that Ganges-Brahmaputra-Meghna, Mekong, and Red
could trigger release in zones with presently low groundwater arsenic levels. River basins (Fig. 2) (15–18). Grain-size separa-
tion of river-borne and aquifer sedi-

“T
he largest poisoning of a population ments has shown that the fine-grained,
in history” is how Smith et al. (1) high–surface area fraction (<10 mm)
described the health impact of el- contains five times as much As as bulk
evated groundwater arsenic (As) concentrations sediments or mica separates (9, 19–21).
in many parts of Bangladesh. Estimates of the Destabilizing As on these Fe oxides is
rural population exposed to unsafe As levels now recognized as a key step in the
by drinking untreated groundwater in India, widespread contamination of ground-
China, Myanmar, Pakistan, Vietnam, Nepal, and water, with other phases possibly
Cambodia have grown to over 100 million (2). playing a subordinate role (14, 22, 23).
Widespread symptoms of disease in people drinking Arsenic is released from Fe oxides
groundwater high in As in some of these countries into groundwater as a result of two
and epidemiological studies conducted elsewhere potentially concurrent processes un-
lead to predictions of a doubling of the lifetime der the anoxic conditions that pre-
mortality risk caused by cancers of the liver, blad- vail in the subsurface. First, field and
der, and lung (3, 4). Groundwater containing As laboratory evidence suggest that mi-
also causes cardiovascular disease and inhibits the crobial reduction of Fe(III) oxides
mental development of children (5, 6). liberates As into the dissolved phase
The affected areas of South and Southeast (23, 24). Reduction of As(V) to more
Asia are low-lying, topographically flat floodplains labile As(III) probably contributes to
of rivers that drain the Himalayas (Fig. 1A) (7). this release but is hard to distinguish
Unconsolidated sands underlying these floodplains India, tubewells extend to depths of ~350 m com- from the reduction of Fe oxides under natural
host increasing numbers of inexpensive wells pared to a maximum of ~100 m in Nepal, Cam- conditions given the rates of groundwater flow.
made of polyvinyl chloride pipe with a cast-iron bodia, and Vietnam, owing to difference in the Second, dissolution of Fe oxides is accompanied
handpump mounted on top (tubewells) that are thickness of unconsolidated sand deposits (8). by the release of other ligands such as phosphate
installed to avoid drinking surface water con- More than half the wells in at least one depth that compete with As for adsorption on the
taminated with microbial pathogens. Extensive, al- interval in each of the five affected countries do remaining Fe oxide surface sites (9).
though by no means sufficient, testing of tubewell not meet the World Health Organization (WHO) The restriction of high dissolved As concen-
water for As has been carried out in most of the guideline of 10 mg/liter As in drinking water trations to aquifers composed of gray-colored sands,
countries that are at risk, with Myanmar the glaring (Fig. 1B). There are also numerous wells con- indicative of coatings of reduced or mixed-valence
exception. taining <10 mg/liter As at all depths. The ex- Fe(II+III) oxides, and the absence of elevated con-
Within the arsenic-affected areas of South and tensive spatial variability of As concentrations at centrations from aquifers containing orange sands
Southeast Asia there is extensive variation in the shallow depths (9–11), even within a single village, coated with Fe(III) oxides (Box 1) suggest that Fe
depth distribution of wells (Fig. 1B). In Bangla- hinders comparisons among field sites and the rec- (III) reduction is a primary factor contributing to
desh and the bordering state of West Bengal, ognition of presumably common biogeochemical- high As concentrations in groundwater (9, 24–28).
hydrological processes that regulate As levels in A systematic analysis of the composition of hun-
groundwater. The source of As is not a mystery, dreds of groundwater samples from the Bengal,
1
Department of Earth System Sciences, Stanford University, however; what is less clear is how the current dis- Mekong, and Red River basins has shown that
CREDIT: SCOTT FENDORF

Stanford, CA 94305, USA. 2Department of Geological Sciences, tribution of dissolved As in the subsurface reached high concentrations of As in groundwater prevail
University of Delaware, Newark, DE 19716, USA. 3Lamont-Doherty its current state. This review focuses on what has under advanced stages of reduction rather than
Earth Observatory of Columbia University, Palisades, NY 10964,
USA. been learned from a decade of field research the onset of Fe oxide reduction (29).
*To whom correspondence should be addressed. E-mail:
conducted in South and Southeast Asia about Microbial Fe(III) and As(V) reduction both
fendorf@stanford.edu (S.F); hmichael@udel.edu (H.A.M.); the processes that resulted in the current dis- require a supply of labile organic carbon. When
avangeen@ldeo.columbia.edu (A.v.G.) tribution of As in groundwater and the key the biological oxygen demand from the decom-

www.sciencemag.org SCIENCE VOL 328 28 MAY 2010 1123


REVIEW
position of organic carbon exceeds the rate of ox- domain within which As can be released to location by groundwater flow, could be an alter-
ygen infusion, anaerobic metabolism prevails and, groundwater is restricted in some shallow (<20 m) native allochtonous supply (26, 28). The reac-
following nitrate and manganese reduction, causes aquifers where sulfate supplied by recharge has tivity of organic matter needs to be considered as
microbially mediated reduction of Fe(III) to Fe(II), not been depleted. This is because sulfate re- well (32, 33), as indicated by dissolved inorganic
as well as As(V) to As(III). Elevated groundwater duction promoted by organic carbon produces carbon typically being younger than DOC (14, 28)
As concentrations that broadly correspond with sulfide that can bind As, forming sparingly sol- and by assays of microbial decomposition (34).
increased levels of metabolic by-products in uble sulfides mineral that effectively remove As The relative importance of different sources of
groundwater including inorganic carbon, ammo- from groundwater (13, 29). Marine-influenced organic carbon remains undetermined and even
nium, and methane, in addition to dissolved Fe(II), areas also show inhibition of As release by sul- controversial (32–34).
are consistent with the central role of organic- fate reduction along the coasts of Bangladesh (9) In principle, where As is released from aquifer
matter metabolism (18, 19, 28–30). and Vietnam (31). sediment and in what quantity will depend on the
The availability of labile organic carbon as a amount of reactive organic carbon and availability
Where Does Arsenic Release to driver of microbial reduction is possibly the most of As in the sediment. Sediment with recalcitrant
Groundwater Occur? prominent outstanding issue limiting our ability organic carbon and/or As-bearing Fe oxides is
There are three environmental requirements for to predict the distribution of As in groundwater. expected to release As slowly. In contrast, highly
groundwater As concentrations to increase: water Organic carbon necessary to drive reduction of reactive forms of both organic carbon and labile
saturation (which limits diffusion of atmospheric Fe(III) and As(V) can be supplied through various sediment-bound As should result in the strongest
oxygen), a limited supply of sulfur, and a source pathways. One is co-deposition of plant material release. Field evidence from Nepal, West Bengal,
of organic carbon to drive microbial dissolution with sediments over geologic time, also referred to Bangladesh, Cambodia, and Vietnam suggests

Downloaded from www.sciencemag.org on June 4, 2010


of Fe oxides. The height of the water table, typ- as an autochthonous source of carbon (9). Dis- both rapid, shallow release of As as well as more
ically within 5 m of the surface, indicates where solved organic carbon (DOC), produced by re- gradual release at depth (9, 17, 18, 25, 28, 35, 36).
oxygen supply is limited and reductive dissolu- cent degradation of plants in modern soils or in The available data show that the geological
tion can potentially be initiated (Fig. 3B). The buried peat layers and transported to a different setting likely plays an important role, but there

us
Ind utra
h map
Gan
ges Bra
na y
dd
gh
Me
wa

R
Irra

ed

Me
ko
ng

0 400 800 km

B
Nepal India (West Bengal) Bangladesh Cambodia Vietnam

Well water As ( g/liter)


1 10 100 1000 1 10 100 1000 1 10 100 1000 1 10 100 1000 1 10 100 1000
0

100
Depth (m)

200

300 Ganges
Brahmaputra Red
Ganges Ganges Meghna Mekong Mekong
400
0.0 0.3 0.6 0.9 0.0 0.3 0.6 0.9 0.0 0.3 0.6 0.9 0.0 0.3 0.6 0.9 0.0 0.3 0.6 0.9
Fraction of wells with >10 g/liter per depth quartile

Fig. 1. Distribution of arsenic in groundwater of South and Southeast Asia. (A) are shown on a logarithmic scale. Symbols are color-coded according to the major
Map of four major river basins draining the Himalayas. (B) Depth distribution of river basins shown in (A). The pink line depicts the fraction of wells that exceed
As in groundwater determined for five affected countries. Concentrations of As the WHO As guideline of 10 mg/liter for each depth quartile of the available data (54).

1124 28 MAY 2010 VOL 328 SCIENCE www.sciencemag.org


REVIEW
remain notable uncertainties regard- The main river basins affected
ing rates of carbon metabolism cou- 20 by As (Fig. 1A) share similar hy-
pled to As release. drogeologic features, most notably
The pool of labile As within an a monsoonal climate and rapid
interval of an aquifer sediment is fi- sediment accumulation. Ground-
nite and can become depleted despite water flow systems range in scale

Extractable Fe (g/kg)
15
continued reduction of Fe oxides. from the local (tens of meters) to
Such a situation has been docu- the regional (hundreds of kilo-
mented for deeper aquifers of Bang- meters). Studies of local-scale flow
ladesh where dissolved As levels are 10 systems (39–42), which are most
low despite elevated Fe(II) concen- relevant to the distribution of As in
trations in groundwater (16). In other shallow aquifers, illustrate the com-
situations, the available pool of labile plex, site-specific, and transient na-
organic carbon has been depleted al- Bangladesh ture of natural patterns of recharge
5
though some labile As is still bound Cambodia and discharge (Fig. 3B). Further,
to sediment particles. Sediments de- Vietnam (18) abundant surface water bodies such
posited prior to about 20,000 years Vietnam (50) as rivers, ponds, and wetlands inter-
ago and that were well drained be- 0 act with the groundwater systems.
cause of incision during the last glacial 0 2 4 6 8 10 Monsoonal rains and dry-season

Downloaded from www.sciencemag.org on June 4, 2010


sea-level low stand, for instance, con- irrigation pumping cause reversals
tain limited reactive organic matter. Extractable As (mg/kg) in hydraulic gradients that can trans-
The orange color of these oxidized form a water body from a source to
deposits indicates that they were de- Fig. 2. Relation between As and Fe concentrations for a suite of sediment samples a sink of groundwater and back
from three countries based on different extraction methods (9, 14, 18, 50).
posited with a low concentration of over a year (39–42). Constructed
organic carbon or that their initial ponds, for instance, are numerous
organic carbon was oxidized during the low stand groundwater flow, even if adsorption sites may be in the Bengal Basin and vary in their contribu-
(9, 15, 16, 25, 26). saturated in aquifer sands under certain conditions tion to aquifer recharge (34, 39, 43), depending
After the initial biogeochemical transforma- (9, 28). on the accumulation of fine-grained bottom
tions that result in As release from the sediment, sediment. Such seasonally and spatially varia-
adsorption on residual or newly formed aquifer How Does Groundwater Flow Affect the ble forcing can result in highly complex ground-
solids will control dissolved As concentrations. Distribution of Arsenic? water flowpaths connecting recharge and discharge
Weaker surface complexes of As(III) and the Groundwater flow transports dissolved As as well areas.
degradation of Fe oxides (9) mean that adsorption as DOC, oxygen, sulfate, and competing adsorb- High groundwater pumping can substantially
is less pronounced than for As(V) in oxidized ates, all of which influence As concentrations. alter natural flow patterns. In Bangladesh, the rate
surface environments (37). Nevertheless, adsorp- When the system is not in a steady state, either of groundwater pumping for irrigation is at least
tion of As(III) does occur within reduced aquifers, hydrologically or biogeochemically, As concen- an order of magnitude higher than integrated
as indicated by a fairly systematic relation between trations can be expected to change over time. flow from hand pumps (16, 39, 44). Irrigation
dissolved and adsorbed As across a broad range of Groundwater flow therefore plays a key role in the pumping and return flow through fields rearrange
conditions in Bangladesh (38). This implies that current distribution of groundwater As and its recharge and discharge areas, increase recharge
As transport is substantially retarded relative to evolution. rates, and modify regional and local flow patterns
(34, 39, 44–46). Groundwater use for irrigation is
greatest in the Bengal Basin and the Terai Basin
Box 1: The color of aquifer along the southern border of Nepal, less in the
sands is a useful visual indicator Red River Basin (17), and least in the Mekong
River Basin (41). Because elevated As concen-
of the redox state of an aquifer. trations are observed in all these areas (Fig. 1B),
(Bottom) Orange sands from processes associated with irrigation pumping,
Vietnam indicate the presence though potentially important, cannot be the only
trigger of As release to groundwater.
of Fe(III) oxides that are
The time since recharge, or groundwater age,
consistently associated with is also an important factor that influences ground-
low- As water, whereas gray water As concentrations. Groundwater age, mea-
sands with reduced or mixed- sured by two different radioactive clocks, ranges
from less than 1 year to a few decades in shallow
valence Fe(II+III) oxides (top) (<20 m deep) aquifers in Bangladesh and Vietnam
are often, though not always, and from centuries to thousands of years in deeper
associated with higher dissolved strata of Bangladesh (50 to 400 m deep) (Fig. 3A).
The vertical gradient in groundwater ages reflects
As. Sand color has been used by regional flow systems and flowpaths that link
drillers to target low-As distant recharge and discharge areas beneath more
groundwater in spatially vigorous shallow and local groundwater circula-
tion (Fig. 3B). Irrigation water is typically drawn
heterogeneous aquifers. [Photo
from shallow (<100 m) depths and may be partly
courtesy of Benjamin Bostick] responsible for the pronounced difference in age
between shallow and deeper aquifers (39, 45).

www.sciencemag.org SCIENCE VOL 328 28 MAY 2010 1125


REVIEW
Within the river basins considered here, the flowpaths containing organic carbon, As concen- affected region, even within orange sand de-
highly variable As concentrations in young ground- trations typically increase. This is consistent with a posits. The vulnerability of shallower and deeper
water in shallow strata may be due to differences correlation between As and groundwater age or low-As zones to human perturbation must be un-
in topography on multiple scales. Slightly ele- flow rate within shallow aquifers (21, 40), and derstood because millions of households in
vated, often coarse, sandy deposits appear to be with As plumes that originate from natural wet- Bangladesh have switched their consumption to
associated with lower As concentrations in lands high in organic carbon (18, 30) or con- a nearby low-As well identified by testing in the
Bangladesh and Cambodia (47–49). Such obser- structed ponds (34). The subsurface maximum in field (51).
vations suggest that rapid recharge through these groundwater As frequently observed within shal- Low-As zones can be protected against in-
deposits locally inhibits the release of As, pos- low gray reduced aquifers is likely the result of trusion of high-As groundwater by favorable
sibly by supplying oxygen, nitrate, or sulfate as layering of groundwater flow having different hydraulics or geochemical processes. Hydraulic
alternatives to Fe oxides for oxidizing organic evolutionary histories. High-As groundwater indi- protection occurs where the source area that con-
carbon (34, 48). Similar processes prevent release cates a plume evolved from active Fe/As reductive tributes water to a particular zone is not high in
of arsenic in water recharged through rice field dissolution/desorption; low-As water can reflect dissolved As or solutes that can mobilize As.
bunds (34). In contrast, low-lying areas in the flowpaths that lack Fe/As reduction, secondary Geochemical protection occurs because of As ad-
river basins are typically covered with finer-grained As-sulfide precipitation, various extents of sedi- sorption or precipitation (e.g., As-bearing sulfides).
sediment, frequently flooded, and associated with ment flushing, or mixing near irrigation well intakes Experiments and modeling indicate that break-
high dissolved As concentrations at shallow depths. (16, 28, 34, 38, 45). through of As through 10 m of orange sands may
Rapid release of As under these conditions is lag groundwater flow by hundreds of years
attributed to co-deposition of labile carbon and How Vulnerable Are Low-Arsenic Zones? because of adsorption (37).

Downloaded from www.sciencemag.org on June 4, 2010


As-bearing Fe oxides in the seasonally saturated Low-As zones within the aquifer systems of the Shallow low-As zones are particularly vul-
surface sediments (18, 30), infiltration of recharge affected basins are rarely distinct aquifers and can nerable to As invasion owing to complex and rapid
with abundant DOC (17, 39), or simply slow flow be associated with reduced gray [Fe(II) domi- flow combined with the patchy distribution of
of water through As-releasing sediment (48). nated] or oxidized orange [Fe(III) dominated] dissolved and solid-phase As (Fig. 3B). The
Along the pathway of groundwater flow, sands (16). Zones of low dissolved As occur in adsorption capacity of gray sands that prevail at
changes in As concentration will depend on local gray sands where As is removed by sulfide (13) shallow depths is lower than that of orange sands
partitioning (adsorption/desorption) with the sed- and along flowpaths where adsorbed As has been and further contributes to the vulnerability of
iment as well as reductive release. Arsenic can be flushed by sustained recharge or has never been shallow low-As zones. A primary threat is ad-
released from the sediment and eventually flushed released (16, 38). Low-As zones associated with vective transport from adjacent high-As zones
from the aquifer in areas where the concentration oxidized orange sands are often deeper (>100 m) because groundwater flows much more easily
of As in inflowing water is below that dictated by but, depending on the local geology, are occa- laterally than vertically through stratified sediments.
partitioning, even within reduced gray sands de- sionally preserved at shallower depths (9, 10, 50). Deeper groundwater (>100m deep) is more
pleted in Fe(III) (38). Along anaerobic, shallow Groundwater is typically anoxic throughout the uniformly low in As (Fig. 1B) and already a

A Groundwater (years)
10-1 10 0 101 102 103 104 105
0

100 B
Depth (m)

NORTH
200
Transfer of As from
sulfide to Fe oxide
by weathering
Release of As
300 from Fe oxides
As sorbs more strongly to groundwater
to orange Fe(III) oxides by reduction
As (μg/liter) than to gray sediments SOUTH
Trapping of As
400 Flushing decreases at oxic interface
<10 >10
14 mobilizable during discharge Wet season
C As pool flooding
3
Local
H - 3He groundwater
flow Potentially sustainable
low-As tubewell Dry season
Fe(III) + As(V) water table

Fe(II) + As(III)
SO42- S2

As trapping by Saline groundwater


sulfate reduction SO42- S2-
Regional groundwater flow

Fe(II) + As(III)

Fig. 3. (A) Depth distribution of groundwater ages in Bangladesh de- light blue circles but are likely to be low; the age of samples shown as gray
termined by either the 3H-3He method (red symbols) or radiocarbon in those circles is uncertain owing to their low 3He content. (B) Conceptual diagram
cases where 3H was measured and not detected (blue symbols) (54). modified from (9) showing the key processes affecting the distribution of As in
Concentrations of As were not reported for three deep samples shown as groundwater.

1126 28 MAY 2010 VOL 328 SCIENCE www.sciencemag.org


REVIEW
widely used and potentially sustainable source of lagers in the affected regions live within walking 17. M. Berg et al., Chem. Geol. 249, 91 (2008).
safe water in certain portions of the Bengal Basin. distance of a well that is low in As or within 18. D. Postma et al., Geochim. Cosmochim. Acta 71, 5054
(2007).
Hydraulic protection of deep groundwater requires drilling distance of such a zone. Governments 19. C. B. Dowling et al., Water Resour. Res. 38, 1173 (2002).
geologic separation of high- and low-As strata or a and international organizations should therefore 20. A. A. Seddique et al., Appl. Geochem. 23, 2236 (2008).
regional flow system in which the recharge location reinvigorate moribund well-testing campaigns and 21. B. Nath et al., J. Hydrol. (Amst.) 364, 236 (2009).
is low in As. Deep, regional systems likely occur in encourage periodic monitoring of wells using field 22. B. J. Mailloux et al., Appl. Environ. Microbiol. 75, 2558
(2009).
much of the Bengal Basin despite low regional kits. Better use should also be made of existing 23. F. S. Islam et al., Nature 430, 68 (2004).
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Hydraulic gradients in the Mekong (41), Red River of community wells. Even if wells tapping deeper 25. A. Horneman et al., Geochim. Cosmochim. Acta 68, 3459
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26. J. M. McArthur et al., Water Resour. Res. 44, W11411
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29. J. Buschmann, M. Berg, Appl. Geochem. 24, 1278 (2009).
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1329 (2004). conference held in Siem Reap, Cambodia, in March 2009
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drawn from a community hand pump is therefore Johnson, Nat. Geosci. 1, 536 (2008). conference was contributed by the Woods Institute for the
preferable to a mechanized pump connected to a 8. S. L. Goodbred Jr., S. A. Kuehl, Sediment. Geol. 133, 227 Environment at Stanford University and the European
piped-water supply system. Where feasible, wells (2000). Union Asia-Link CALIBRE Project. We also acknowledge
9. D. G. Kinniburgh, P. L. Smedley, Eds., Arsenic research funding by the Environmental Venture Projects
should extend as deep as possible into deep
Contamination of Ground Water in Bangladesh, Final program of Stanford’s Woods Institute for the
orange sands rather than into gray sands or shallow Report (BGS Technical Report WC/00/19, British Environment and the Stanford NSF Environmental
orange sands. These recommendations are con- Geological Survey, Keyworth, UK, 2001), vol. 2. Molecular Science Institute (NSF-CHE-0431425) (S.E.F.),
sistent with the outcome of monitoring a set of 10. A. van Geen et al., Water Resour. Res. 39, 1140 (2003). the U.S. Geological Survey, the U.S. Agency for
hand-pumped community wells in Bangladesh 11. R. Nickson et al., J. Environ. Sci. Health Part A Tox. International Development, the British Department for
Hazard. Subst. Environ. Eng. 42, 1707 (2007). International Development, and UNICEF (H.A.M.),
during which a few increases in As concentrations 12. S. K. Acharyya et al., Nature 401, 545, discussion 546 National Institute of Environmental Health Sciences SRP
were recorded during the initial years (mostly in (1999). grant 1 P42 ES10349, NIH FIC grant 5 D43 TW05724,
wells <60 m deep) and none since (53). 13. H. A. Lowers et al., Geochim. Cosmochim. Acta 71, 2699 and NSF grant EAR 0345688 (AvG). We thank R. Beckie,
(2007). G. Breit, C. Harvey, J. Lloyd, and an anonymous reviewer
Priorities for the Future 14. B. D. Kocar et al., Appl. Geochem. 23, 3059 (2008). for helpful comments. This is Lamont-Doherty Earth
15. C. H. Swartz et al., Geochim. Cosmochim. Acta 68, 4539 Observatory contribution no. 7355.
The laterally and vertically heterogeneous dis- (2004).
tribution of As has one advantage—many vil- 16. Y. Zheng et al., Geochim. Cosmochim. Acta 69, 5203 (2005). 10.1126/science.1172974

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