Science of the Total Environment 366 (2006) 701 – 721

www.elsevier.com/locate/scitotenv

Occurrence of arsenic contamination in Canada: Sources,

behavior and distribution
Suiling Wang, Catherine N. Mulligan *
Department of Building, Civil and Environmental Engineering, Concordia University, 1455 de Maisonneuve Boulevard W., EV 006-187,
Montreal, QC, Canada H3G 1M8
Received 16 February 2005; received in revised form 2 September 2005; accepted 2 September 2005
Available online 3 October 2005

Abstract

Recently there has been increasing anxieties concerning arsenic related problems. Occurrence of arsenic contamination has been
reported worldwide. In Canada, the main natural arsenic sources are weathering and erosion of arsenic-containing rocks and soil,
while tailings from historic and recent gold mine operations and wood preservative facilities are the principal anthropogenic
sources. Across Canada, the 24-h average concentration of arsenic in the atmosphere is generally less than 0.3 Ag/m3. Arsenic
concentrations in natural uncontaminated soil and sediments range from 4 to 150 mg/kg. In uncontaminated surface and ground
waters, the arsenic concentration ranges from 0.001 to 0.005 mg/L. As a result of anthropogenic inputs, elevated arsenic levels,
above ten to thousand times the Interim Maximum Acceptable Concentration (IMAC), have been reported in air, soil and sediment,
surface water and groundwater, and biota in several regions. Most arsenic is of toxic inorganic forms. It is critical to recognize that
such contamination imposes serious harmful effects on various aquatic and terrestrial organisms and human health ultimately.
Serious incidences of acute and chronic arsenic poisonings have been revealed. Through examination of the available literature,
screening and selecting existing data, this paper provides an analysis of the currently available information on recognized problem
areas, and an overview of current knowledge of the principal hydrogeochemical processes of arsenic transportation and
transformation. However, a more detailed understanding of local sources of arsenic and mechanisms of arsenic release is required.
More extensive studies will be required for building practical guidance on avoiding and reducing arsenic contamination.
Bioremediation and hyperaccumulation are emerging innovative technologies for the remediation of arsenic contaminated sites.
Natural attenuation may be utilized as a potential in situ remedial option. Further investigations are needed to evaluate its
applicability.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Arsenic; Speciation; Biota; Canada; Mining; Soil; Sediments; Water

1. Introduction and soils, and natural waters and is present in trace

Arsenic is of increasing concern due to its high
toxicity and widespread occurrence in the environ-
ment. It is widely distributed throughout the rocks
* Corresponding author. Tel.: +1 514 848 2424x7925; fax: +1 514
848 7965.
E-mail address: mulligan@civil.concordia.ca (C.N. Mulligan).
0048-9697/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.scitotenv.2005.09.005
amounts in all-living matter. Elevated levels of arsenic
have resulted from both natural and anthropogenic
occurrence. Most arsenic compounds are odorless
and tasteless and readily dissolve in water, which
creates an elevated health risk. Ingesting food or
water containing more than 0.01 mg/L of inorganic
arsenic is harmful to the body, while an inorganic
arsenic content exceeding 60 mg/L can be fatal
702 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
(WHO, 1993). Many cases of acute and chronic
arsenic poisoning have been reported in various part
of the world (Gray et al., 1989; WHO, 1993; Senesse
et al., 1999; Saha, 2003). Symptoms of acute poison-
ing usually occur within 30 min of ingestion and may
result in gastrointestinal discomfort, vomiting, coma,
and sometimes even death, while chronic poisoning is
much more insidious in nature, resulting in anemia,
leucopenia, skin cancer, and other internal cancers
(WHO, 1993; Gorby, 1994). It is also demonstrated
that arsenic can cause toxic effects for plants or may
accumulate in plants and thereby enter the animal and
human food chain. An average toxicity threshold of
40 mg inorganic arsenic/kg soil was established for
rice plants (Sheppard, 1992). Higher arsenic concen-
trations will introduce inhibitory effects for crop
yields.
Arsenic exists essentially in four oxidation states
( III, 0, +III, and + V), as both inorganic and organo-
metallic species. The forms of arsenic present are depen-
dent on the type and amounts of sorbents, pH, redox
potential (Eh), and microbial activity (Yong and Mulli-
gan, 2004). Arsenic metal rarely occurs and the ( III)
oxidation state is found only in extremely reduced envi-
ronment. Arsenate ions [As(V)] are most prevalent in
oxic conditions whereas arsenite ions [As(III)] are found
in anaerobic conditions. Methylated arsenic species,
such as monomethylarsonous acid [MMA(III)], mono-
methylarsonic acid [MMA(V)], dimethylarsinous acid
[DMA(III)], dimethylarsinic [DMA(V)], trimethylarsine
[TMA(III)], and trimethylarsenic oxide (TMAO), can be
7000
6000
Arsenic Production (tonnes)
5000
4000
3000
2000
1000
0
1885
Fig. 1. Canadian arsenic production, 1885–1990 (modified from Cranstone, 2001).
formed through biomethylation by microorganisms
under favorable conditions (Challenger, 1945; Braman,
1975; Cullen and Reimer, 1989). The toxicity and mo-
bility of arsenic species differ with their chemical forms
and oxidation states (NRC, 1999; Thomas et al., 2001).
Generally, inorganic forms are more toxic and mobile
than organoarsenic species, while arsenite is considered
to be more toxic and mobile than arsenate (Gulens et al.,
1979; Squibb and Fowler, 1983; Xu et al., 1988; Lamble
and Hill, 1996). Gulens et al. (1979) reported that As(III)
is 5 to 8 times more mobile than As(V) in a non-adsorb-
ing sandy loam. Squibb and Fowler (1983) found that
As(III) was 10 times more toxic than As(V) and 70
times more toxic than MMA(V) and DMA(V). How-
ever, the trivalent methylated arsenic species [i.e.,
MMA(III) and DMA(III)] have been found to be
more toxic than inorganic arsenic because they are
more efficient at causing DNA breakdown (Styblo et
al., 2000; Dopp et al., 2004). The potency of the DNA
damage decreases in the order DMA(III) NMMA(III) N
[As(III), As(V)] N MMA(V) NDMA(V) NTMAO(V)
(Dopp et al., 2004).
In Canada, arsenic is produced mainly as arsenic
trioxide through the roasting of arsenious gold ores.
Canadian arsenic production from 1885 to 1990 is
illustrated in Fig. 1. Arsenic is used mainly in metal-
lurgical applications and in the manufacture of wood
preservatives. Release from natural weathering and
erosion processes of arsenic-bearing rocks and soils,
doubled with anthropogenic activities such as historic
and recent gold- and base-metal processing, the use of
1900 1915 1930 1945 1960 1975 1990
Year
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721 703

arsenical pesticides and wood preservatives, thermal Table 1

and coal-fired power generation, and the disposal of Estimated fluxes of arsenic transfer
domestic and industrial waste materials, attributes to From: To: Estimated fluxes (108 g/yr)
the elevated arsenic concentrations in the Canadian Land Oceans 3000
environment. High levels of arsenic have been reported Atmosphere 1000
Biota 300
in the air up to 6.5 Ag/m3, surface water and ground-
Atmosphere Oceans 2000
water up to 1570 mg/L, and soils and sediments up to Land 1000
25,000 mg/kg in several regions (ENVIRDOQ, 1997; Oceans Sediments 2500
Coumans, 2003; Newhook et al., 2003). As a result, Biota 1300
Canadians are exposed to arsenic by a number of ways Dissolved 1000
Sediments Land 2400
such as food, drinking water, soil and ambient air,
Mining, smelting 500
mainly through ingestion of arsenic in drinking water Terrestrial biota Land 300
or food (CEPA, 1993). Especially, people near the Volcanoes Land 54
vicinity of industrial and geological sources are ex- Sediments 40
posed to higher levels, which can cause severe delete- Atmosphere 3
rious impacts on the environment and human health. (Mackenzie et al., 1979).
The Canadian Environmental Protection Act (CEPA)
listed arsenic and its compounds in Group 1 of the selecting existing data, site-specific problems are
Priority Substances List, a list to identify substances, discussed. This adds to our expanding knowledge of
including chemicals, effluents and wastes which may global arsenic issues.
be harmful to the environment or constitute a danger to
human health. 2. Arsenic sources
The occurrence, distribution, origin and mobility of
arsenic have received significant attention in recent 2.1. Natural sources
years. Knowledge of natural geochemical and biologi-
cal processes that govern arsenic transportation and The ubiquity of arsenic in the environment origi-
transformation in the environment is necessary for gain- nates from natural enrichments and is intensified by
ing a better understanding. Fig. 2 shows the occurrence anthropogenic activities. The most common sources of
and flow paths of arsenic in the environment. The arsenic in the natural environment are volcanic rocks,
estimated fluxes of arsenic transfer among different specifically their weathering products and ash, marine
reservoirs are summarized in Table 1. The purpose of sedimentary rocks, hydrothermal ore deposits and as-
this paper is to give a comprehensive analysis of the sociated geothermal waters, and fossil fuels, including
situation of arsenic contamination in Canada. Through coals and petroleum (Korte and Fernando, 1991; Smed-
examination of the available literature, screening and ley and Kinniburgh, 2002).

Mining

Smelting Atmosphere

Pesticides
es

Vo
iti

lat
tiv

ile

Fertilizers
Ac

et,
n

s,
tio
ial

Dr

M
os

Wood Preservatives
ob

icr
yD
ep
icr

o
yD

Discharge
bia
ep

Biota
M

Volcanoes
os

lA
Dr
s,

itio

Transport
ile

cti
et,
lat

Fossil Fuel Combustion

n
W

vit
Vo

ies

Sorption-Desorption
Industrial Process Soils Precipitaion-Dissolution
Municipal Wastes Sediments Waters
Rocks Oxidation-Reduction
Military Activities Microbial Activities

Waste Treament (Landfill)

Fig. 2. A simplified diagram of arsenic cycle.

704 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
Arsenic occurs naturally in a wide range of minerals
in soils in several forms of inorganic compounds. The
most common arsenic-containing minerals are arseno-
pyrite or mispickel (FeAsS), realgar (AsS), and orpi-
ment (As2S3). These minerals are usually associated
with sulfide ores or other metal ores and work as a
major starting point for the introduction of arsenic into
the environment. The average arsenic concentration in
the earth’s crust is about 2–5 mg/kg (USDHHS, 2000).
The global average concentration of arsenic in uncon-
taminated soil is 5–6 mg/kg (Peterson et al., 1981).
However, it varies among geographic regions. Amounts
of arsenic in uncontaminated soils up to 11 mg/kg were
reported in Canada (MacLean and Langille, 1981). The
arsenic levels in soil derived from arsenic-enriched
sedimentary rocks may attain a value of 20–30 mg/kg
(Zou, 1986). Bennett and Dudas (2003) reported an
acid sulfate soil that contained up to 37.9 mg/kg arsenic
in northwestern Alberta. Extremely high arsenic con-
centrations of 4600 mg/kg were detected in soils of the
A2 horizon (a mineral horizon, typically consisting of
fine sandy loam) near mineralized veins in British
Columbia (Warren et al., 1964).
Occurrence of arsenic in natural water is dependent
on the local geology, hydrogeology and geochemical
characteristics of the aquifer, and climate changes as
well as human activities. Natural sources of arsenic in
water has been attributed to several natural geochem-
ical processes, including oxidation of arsenic-bearing
sulfides, desorption of arsenic from (hydro)oxides
(e.g., iron, aluminum and manganese oxides), reduc-
tive dissolution of arsenic-bearing iron (hydro)oxides,
release of arsenic from geothermal water, and evapo-
rative concentration, as well as leaching of arsenic
from sulfides by carbonates (Kim et al., 2000; Bennett
and Dudas, 2003; Wang and Mulligan, in press).
Worldwide reported arsenic concentrations in natural
water vary from 0.00002 mg/L to greater than 5 mg/L
(Cullen and Reimer, 1989; Smith et al., 2002). Brooks
et al. (1982) reported elevated background arsenic
levels of 0.037 mg/L in Mitchell Brook near Halifax,
Nova Scotia.
2.2. Anthropogenic sources
The main anthropogenic activities that may release
arsenic into the environment include nonferrous metal
mining and smelting, fossil fuel processing and com-
bustion, wood preserving, pesticide production and
application, and disposal and incineration of munici-
pal and industrial wastes (Popovic et al., 2001; Prosun
et al., 2002). Most anthropogenic releases of arsenic
are to land or soil, primarily in the form of pesticides
or solid wastes. However, substantial amounts are also
released to air and water (USDHHS, 2000). Soluble
forms of arsenic are known to leach into the ground-
water and may enter surface waters from runoff.
Slimak and Charles (1984) estimated that 19% of
arsenic follows soil-related pathways via runoff and
leaching.
2.2.1. Mining residues
Mine tailings and effluents usually contain high
concentrations of arsenic and are of concern as potential
sources of environmental contamination. It was
reported that the annual total fluvial input of arsenic
to the Moira Lake in Ontario was approximately 3.5
tonnes due to local mining and mineral processing
(Azcue and Nriagu, 1995). Coumans (2003) estimated
that about 220 million tonnes of highly toxic arsenic
trioxide were buried underground which threatens
ground and surface water for kilometers around the
Giant Mine in Yellowknife, NWT.
In mine tailings, arsenic occurs in various forms
such as arsenopyrite (FeAsS), arsenian pyrite (As-
rich FeS2), arsenates, and associated with iron oxy-
hydroxides. Wang and Mulligan (2004a) measured
the arsenic contents of six mine tailings. ICP-MS
analyses indicated that the highest arsenic concentra-
tions reached 2200 mg/kg in tailings from a lead–
zinc mine at Bathurst, NB (Table 2). In Yellowknife,
both historical and recently deposited tailings were
found to contain high levels of arsenic, up to 25,000
mg/kg in Con Mine tailings, 4800 mg/kg in Giant
Mine tailings, and 12,500 mg/kg in the historical
Negus tailings (Ollson, 1999). In northern Saskatch-
ewan, total arsenic concentrations in the mine tail-
ings and their associated pore fluids from the Rabbit
Lake in-pit tailings management facility (RLITMF)
ranged from 56 to 9871 mg/kg and 0.00024 to 0.14
mg/L respectively (Moldovan et al., 2003). Donahue
and Hendry (2003) reported that dissolved arsenic
concentrations in 5 monitoring wells installed within
Table 2
Arsenic concentrations measured in six mine tailings
Type of tailings Location Concentration (mg/kg)
Copper mine Murdochville, QC 500
Gold mine Musselwhite, ON 63
Copper–zinc mine Val d’Or, QC 270
Iron mine Mont-Wright, QC b0.70
Lead–zinc mine Bathurst, NB 2200
Gold mine Marathon, ON 270
(Wang and Mulligan, 2004a).
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
the tailings body from RLITMF ranged from 9.6 to
71 mg/L.
2.2.2. Industrial emissions
Smelter and base-metal refinery facilities as well as
thermal and power generating stations are the principal
anthropogenic sources of arsenic in Canada. It was
estimated that Canadian base-metal smelters and refin-
eries released about 15 tonnes/year of arsenic in liquid
effluent, 310 tonnes/year into the atmosphere, and 770
tonnes/year as solid waste (MacLatchy, 1992). The on-
site, off-site and total releases of arsenic from 1994 to
2001 based on the Environment Canada’s National
Pollutant Release Inventory (NPRI) are illustrated in
Fig. 3. The decrease in 2000 is largely due to the
closure of a large gold mine in 2000 (Environment
Canada, 2002). However, the total release in 2002
was dramatically increased to 501.2 tonnes (310 tonnes
on-site, 191.2 tonnes off-site). Most of the release
(N90%) was from coal-fired power or thermal generat-
ing stations and smelter and metallurgical facilities.
Elevated arsenic concentrations have been detected in
the vicinity of these sources. Near a copper–zinc smelt-
er in Manitoba, Zoltai (1988) reported arsenic concen-
trations in surface peats of up to 280 mg/kg, compared
to an average background concentration of 4 mg/kg.
2.2.3. Wood preserving
Another important anthropogenic source of arsenic
is the extensive application of arsenical wood preserva-
tives. For the period of 1984 to 1988, annual Canadian
sales of arsenic (as arsenic pentoxide, As2O5) for use in
4500
4000
3500
Arsenic Release (kg)
3000
2500
2000
1500
1000
500
0
1994
Fig. 3. Arsenic release from NPRI reporting facilities, 1994–2001 (data sources: NPRI online database).
705
wood preservation oscillated between about 650 and
1300 tonnes (CEPA, 1993). Chromated copper arsenate
(CCA), a wood preservative containing 18.5% CuO,
34% As2O5, and 47.5% CrO3 (w/w) (Cooper, 1994),
was the overwhelmingly dominant preservative used in
Canada. Stephens et al. (1994) estimated 59 million kg
of CCA were used in 1992, and the used amount of
ammoniacal copper arsenate (ACA) was 88,000 kg.
The sale volume of CCA/ACA/ACZA (ammoniacal
copper zinc arsenate) treated wood products was
2,078,694 m3 in 1992, but in 1999 the amount jumped
to 3,117,328 m3, an increase of about 50% (Stephens et
al., 2001). Substantial amounts of CCA remain in the
treated wood, ranging from 7800 to 78,000 mg/kg
(Fields, 2001). Leaching of preservative components
from treated wood that is in-service therefore has
been a source of arsenic in the environment. Moreover,
the widespread arsenic contamination around the wood
preservation arises as a result of raw material handling,
spills, deposition of sludge and dripping from freshly
impregnated wood or due to leaching from the piles of
impregnated wood at these sites by rain water especial-
ly under low pH conditions (Lund and Fobian, 1991).
The important factors determining the leachability of
treated woods are the concentration and type of the
preservative, the drying and storage conditions, and
the wood species, as well as the weather conditions
(Lund and Fobian, 1991; Brooks, 1993). Exposure to
sunlight and other weathering activities will increase
the rates. Field trials demonstrated that the average
annual leaching rate of CCA were 1.8–17.3% of the
total active ingredients (Hingston et al., 2001). Leach-
On-site
Off-site
Total
1995 1996 1997 1998 1999 2000 2001
Year
706 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
ing rates of arsenic from freshly treated woods are
highly variable and decrease exponentially with time
(Brooks, 1993). Merkle et al. (1993) estimated that the
12-h and 90-day leaching rates of arsenic from CCA-
treated wood were 3.3–8.2 and 0.4–0.5 Ag/cm2/day,
respectively.
Consequently, elevated levels of arsenic have been
found in soils surrounding the treated woods (Bam-
woya et al., 1991; CED, 2003; Zagury et al., 2003).
Bamwoya et al. (1991) measured levels of 262 mg
arsenic/kg in the sediments downstream from an arsen-
ical wood preservation facility near Elmsdale, Nova
Scotia. The Canadian Council of Ministers of the En-
vironment (CCME, 1999/2002) collected 58 sand sam-
ples from playgrounds of 7 cities. The arsenic contents
varied from 0.5 to 147.0 mg/kg. 60% of the play-
grounds tested had arsenic levels above the federal
soil guideline (25 mg/kg) for the protection of human
health. The use of CCA was proposed as the main
source of the contamination (CED, 2003). Zagury et
al. (2003) reported high arsenic concentrations of
410 F 150 mg/kg on the ground and immediately adja-
cent to the CCA/polyethylene glycol (PEG)-treated
utility poles in Montreal, Quebec. Since December
31, 2003, arsenic-containing preservatives (e.g., CCA)
have no longer been used on wood for non-industrial
use (Health Canada, 2005).
2.2.4. Coal combustion
Arsenic is known to be concentrated in coals. Arse-
nic is released during coal processing and combustion.
Arsenic exceeding 6000 mg/kg (ash basis) was reported
in separate lithotypes of Kimberly coals in Westphalian
A Joggins Formation, Cumberland Basin, Nova Scotia
(Hower et al., 2000). Goodarzi and Huggins (2001)
investigated the concentration of arsenic in milled
coal, bottom ash and fly ash from a coal-fired power
plant in western Canada. The average arsenic concen-
trations were 1.6, 1.6, and 17.5 mg/kg, respectively.
Arsenic occurs in the forms of both arsenite and arse-
nate in the milled coal, while virtually all (N 90%) of the
bottom ash and fly ash appear to be arsenate. It has
been reported that the arsenic concentration in soil near
a steel plant and coke ovens in Sydney, Nova Scotia,
varied from 2 to 157 mg/kg (Lambert and Lane, 2004).
2.2.5. Arsenical pesticides
The use of arsenical pesticides presents a non-point
anthropogenic source of arsenic. The mainly used ar-
senical pesticides include lead arsenate [Pb3(AsO4)2],
calcium arsenate [Ca3(AsO4)2], magnesium arsenate
[Mg3(AsO4)2], zinc arsenate [Zn3(AsO4)2], zinc arse-
nite [Zn(AsO2)2], and Paris green [Cu(CH3C-
COO)2d 3Cu(AsO2)2]. They were used extensively in
orchards before the introduction of dichlorodiphenyltri-
chloroethane (DDT) in 1947 (Bishop and Chisholm,
1961). In Canada, the use of lead arsenate in apple
orchards was officially recommended in Ontario as
late as in 1975 (Frank et al., 1976). Consequently,
arsenic accumulation in treated orchard soil and adja-
cent sites has been reported (Bishop and Chisholm,
1961; Martin et al., 2000). Currently, the use of arsen-
ical pesticides (e.g., lead arsenate, calcium arsenate,
zinc arsenate, zinc arsenite, and magnesium arsenate)
in Canada has not been specifically allowed (PAN
Pesticides Database, 2005). Bishop and Chisholm
(1961) found that the use of arsenical pesticides had
resulted in the accumulation of 9.8–124 mg arsenic/kg
in the topsoils (0–15 cm) from 25 Annapolis Valley
orchards. At a site in Niagara (Ontario) that received
lead arsenate applied as a spray, the arsenic concentra-
tions in the top 5 cm of soil and the adjacent untreated
site (500 m apart) were 71.6 and 47.3 mg/kg, respec-
tively, while the provincial average is 7 mg/kg (Martin
et al., 2000). The authors postulated that the arsenic at
the untreated site might have drifted from the treated
site.
3. Arsenic in air
3.1. Reported concentrations
Arsenic is released into the atmosphere from both
natural and anthropogenic sources. Natural inputs are
originated from wind erosion, volcanic emissions, and
low-temperature volatilization from soil and water sur-
faces. The principal anthropogenic sources are the burn-
ing of fossil fuels (especially coal), metal production,
agricultural use and waste incineration. Global natural
arsenic emissions have been estimated to be around
7900 tonnes/year, while anthropogenic sources of at-
mospheric arsenic (about 18,800–23,600 tonnes/year)
amounted to around 75% of the global atmospheric
arsenic flux (Woolsan, 1983; Nriagu and Pacyna,
1988).
The concentrations of arsenic in the atmosphere are
usually low, but can be increased by emissions from
smelting and other industrial operations, fossil-fuel
combustion and volcanic activity (Table 3). The impact
on humans is mainly health-related and generally asso-
ciated with inhalation of particulate matter of less than
10 Am in diameter. Respirable particles (b 2.5 Am in
diameter) can reach the lung alveoli (Brewer and Bel-
zer, 2001). Although there is no national quality guide-
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721 707

Table 3 and 0.589 Ag/m3, while the several-year-averaged back-

Arsenic concentrations in Canadian air ground concentration was 0.00062 F 0.00028 Ag/m3.
Location As concentration References The annual average for total arsenic in air was 0.002
average (range)
Ag/m3 in Yellowknife in 2001, but the highest 24-h level
(Ag/m3)
reached 0.033 Ag/m3 (RWED, 2003). Due to copper
11 Canadian cities 0.001 Environmental
smelting, 24-h maximum concentrations between 1.0
and 1 rural site (b0.0005–0.017) Canada (1990)
Quebec b0.0005–0.002 ENVIRDOQ (1997) and 6.5 Ag/m3 were measured in Murdochville and
Canadian ambient air 0.00062 F 0.00028 Newhook et al. Rouyn-Noranda, Quebec, while the background con-
(2003) centrations were 0.001 and 0.002 Ag/m3, respectively
Alberta 0.006–0.0015 Alberta Environment (ENVIRDOQ, 1997). Atmospheric arsenic near such
(2003)
industrial sources is typically As2O3 in particulate form
0.0021–0.0048a Alberta Environment
(2003) (Cullen and Reimer, 1989).
Burnaby Lake, BC 0.023 (0.0012–0.28) Brewer and Belzer
(2001) 3.2. Arsenic species in air
Windsor, ON 0.001–0.002 IAQAB (2004)
0.003–0.016a IAQAB (2004)
Arsenic in the air is present mainly in inorganic
Near Cu smelter 0.007–0.589 Newhook et al.
and Zn plants (2003) particulate forms with a minor portion as methylated
Yellowknife, NT 0.002 RWED (2003) arsenic. However, the dominant species are variable
0.033a RWED (2003) depending on the emission sources. Arsenate is usually
Murdochville, QC 1.0a ENVIRDOQ (1997) the predominant inorganic species. As2O3 is likely to be
Rouyn-Noranda, QC 6.5a ENVIRDOQ (1997)
dominant near smelters and roasters, coal burning and
House dust , Ottawa 7.3 (1.7–79.5) Rasmussen et al.
(mg/kg) (2001) volcanic sources (Cullen and Reimer, 1989). Arsine
Street dust, Ottawa 1.3 ( 0.0–2.9) Rasmussen et al. (AsH3) may be derived from landfills and peats (Cullen
(mg/kg) (2001) and Reimer, 1989). Volatile organic species may escape
a
24-h maximum concentrations. through soil and water surfaces due to microbial activ-
ity (Challenger, 1945; Braman, 1975; Cullen and
line for arsenic in air, the province of Ontario developed Reimer, 1989). Reduced species, however, are likely
a standard of 0.3 Ag/m3 over 24-h for total arsenic to be oxidized by oxygen (O2) and react with sulfur
based on a general toxicity level. dioxide (SO2) or ozone (O3) in the atmosphere.
Levels of inhalable arsenic-containing particulates
(b10 Am in diameter) in ambient air in 11 Canadian 3.3. Atmospheric deposition of arsenic
cities and one rural site monitored from 1985 to 1990
ranged from less than 0.0005 to 0.017 Ag/m3 (24-h av- Arsenic is removed from the atmosphere either by
erage), while the mean level in most cities was 0.001 dry deposition or by rainfall. Some air-borne arsenic
Ag/m3 (Environment Canada, 1990). In northwest particles can condense onto dust particles which can be
Edmonton, from September 2001 to March 2002, the either inhaled or ingested. The total arsenic concentra-
maximum 24-h concentration of arsenic in total sus- tions in house dust of Ottawa residences varied from
pended particulates (TSP) varied from 0.0021 to 0.0048 1.7 to 79.5 mg/kg with an average of 7.3 mg/kg, while
Ag/m3, and the median concentration was 0.0006 to the average total arsenic concentration in street dust
0.0015 Ag/m3 (Alberta Environment, 2003). Brewer was 1.3 mg/kg with a maximum value of 2.9 mg/kg
and Belzer (2001) measured the mean arsenic concen- (Rasmussen et al., 2001).
tration in atmospheric particulates of 0.023 Ag/m3 at In rural areas, arsenic concentrations in rainfall and
Burnaby Lake, British Columbia, within a range of snow are typically less than 0.00003 mg/L (Andreae,
0.0012 to 0.28 Ag/m3. In Windsor, Ontario, the levels 1980; Barbaris and Betterton, 1996). In the vicinity of
of arsenic were observed to be rather constant at about smelting and coal burning industrial areas, arsenic con-
0.001 to 0.002 Ag/m3. The maximum 24-h values centrations in rainfall was found to be around 0.0005
ranged from 0.003 to 0.016 Ag/m3. Most of this arsenic mg/L (Andreae, 1980). Depending on the relative pro-
is probably inorganic (IAQAB, 2004). portions of wet and dry deposition, proximity to con-
Newhook et al. (2003) investigated the arsenic re- tamination sources, meteorological situations and size
lease from copper smelters and refineries and zinc distribution, total arsenic deposition rates have been
plants in Canada. Annual average concentration of calculated in the range b 1 to 1000 Ag/m2/yr (Schroeder
arsenic in ambient air nearby oscillated between 0.007 et al., 1987). By assuming a tropospheric burden of
708 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721

7.7  108 g arsenic and a global source strength of 5 mg/kg arsenic in soils from Alberta, while high con-
31  109 g arsenic/year, Walsh et al. (1979) estimated centrations ranging from 8 to 45 mg/kg were found in
that the global tropospheric residence time of arsenic acid sulfate soils derived from the weathering of pyrite-
was about 9 days. rich shales (Dudas, 1984, 1987; Bennett and Dudas,
2003). Concentrations in the overlying leached horizons
4. Arsenic in soil and sediments were low (1.5–8.0 mg/kg) due to volatilization or leach-
ing of arsenic to lower levels (Dudas, 1984).
4.1. Reported concentrations Arsenic levels are naturally much higher in areas
associated with mining operations as a result of the
4.1.1. Soil natural weathering of arsenic rich minerals (Table 4).
Across Canada, arsenic can be found naturally in soil The background arsenic concentration of soil in Yel-
at concentrations ranging from 4.8 to 13.6 mg/kg, and lowknife was found to vary from 4 to 150 mg/kg (ESG,
average urban and agricultural soil concentrations are 2000). Ollson (1999) found that soils from the Con
mostly between 4 and 6 mg/kg (Table 4) (CCME, 1999/ Mine property had a median concentration of 118 mg/
2002; CED, 2003). Total arsenic concentrations in the kg while soil samples collected in the city of Yellow-
garden soil of Ottawa residences varied from 1.7 to 9.9 knife had a median arsenic concentration of 31 mg/kg.
mg/kg, with an average of 3.0 mg/kg (Rasmussen et al., EBA (1998) reported that arsenic was present in soils in
2001). Acid sulfate soils generated by the oxidation of the Giant Mine Townsite (Yellowknife) at a concentra-
pyrite in sulfide-rich terrains are relatively enriched in tion between 754 and 9580 mg/kg. At the same loca-
arsenic. Dudas and Pawluk (1980) reported an average of tion, arsenic levels of 1174 F 519 mg/kg were found in
samples of crushed rocks, and much lower levels of 87
Table 4 mg/kg were found in samples which were organic or
Arsenic concentrations in Canadian soil clay in nature, well within the background concentra-
Location As concentration References tions of arsenic (7.1–127 mg/kg) (ESG, 2000).
average (range)
(mg/kg)
4.1.2. Sediments
Natural uncontaminated 4.8–13.6 CCME (1999/2002);
The typical concentration of arsenic in sedimentary
soils CED (2003)
11 MacLean and Langille rocks ranges from 5 to 10 mg/kg (Webster, 1999). The
(1981) uncontaminated sediment arsenic concentration is be-
Acid sulfate soils, AB 5 (1.5–45) Dudas and Pawluk tween 6 and 100 mg/kg, with a median concentration of
(1980); Dudas (1984); 68 mg/kg (Table 5) (Ollson, 1999). In the Fawnie Creek
Dudas et al. (1988);
area, Central British Columbia, Cook et al. (1995)
Bennett and Dudas
(2003) reported arsenic concentrations in lake sediments vary-
Resident garden soil, 3.0 (1.7–9.9) Rasmussen et al. ing from 0.9 to 44 mg/kg (median 5.5 mg/kg) and the
Ottawa (2001) highest concentrations were found a few kilometers
Surface peat, MB 4–280 Zoltai (1988) down-slope from mineralized areas (upper baseline,
Yellowknife 4–150 ESG (2000)
90th percentile, 13 mg/kg). Concentrations in glacial
32 (4–70) Ollson (1999)
Sydney, NS 2–157 Lambert and Lane till were from 1.9 to 170 mg/kg (median 9.2 mg/kg) and
(2004) reached highest levels down-ice of mineralized areas
Bowen Island, BC 2–172,000 Boyle et al. (1998) (upper baseline, 90th percentile, 22 mg/kg). Environ-
Montreal, QC 410 F 150 Zagury et al. (2003) ment Canada (1996) reported that concentrations of
Elmsdale, NS 262 Bamwoya et al. (1991)
arsenic in glacial till samples from a number of Cana-
Delora, ON 1023 F 15 Zheng et al. (2003)
Playgrounds, Vancouver 6.4–51.3 CED (2003) dian sites were in the range of 1 to 6590 mg/kg.
Playgrounds, Edmonton 8.6–52.3 CED (2003) Sediments from two popular recreational lakes in
Playgrounds, Winnipeg 2.8–21.3 CED (2003) Yellowknife, Rat Lake and Kam Lake, were found to
Playgrounds, Toronto 2.6–147.0 CED (2003) contain arsenic up to 820 mg/kg and up to 1570 mg/kg,
Playgrounds, Ottawa 3.1–17.4 CED (2003)
respectively (Ollson, 1999). Wagemann et al. (1978)
Playgrounds, Montreal 0.5–104.0 CED (2003)
Playgrounds, Halifax 9.4–69.4 CED (2003) reported arsenic concentrations ranged from 6 to 3500
Giant Mine Townsite, 754–9580 EBA (1998) mg/kg in bottom sediments of lakes in the vicinity of
Yellowknife 1174 F 519 EBA (1998) Yellowknife. In the case of Jack of Clubs Lake, British
(crushed rock) Columbia, arsenic was transported from abandoned
87 F 89 (clay) EBA (1998)
gold mine tailings to the lake, where it accumulated in
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721 709

Table 5 values close to 1000 mg/kg at depths of 23 to 27 cm

Arsenic concentrations in Canadian sediments below the sediment–water interface. The elevated arse-
Location As concentration References nic concentrations in bottom sediments represent a con-
average (range)
tinuous internal mining of arsenic towards the interface
(mg/kg)
all year around. The sediment porewater works as the
Natural uncontaminated 68 (6–100) Ollson (1999)
linking agent. The estimated annual upward diffusion
sediment
Rat Lake, Yellowknife 820 Ollson (1999) flux ranged from 0.8 to 3.8 Ag/cm2/year.
Kam Lake, Yellowknife 1570 Ollson (1999)
Flin Flon, MB 9–206 Franzin (1994) 4.2. Arsenic species in soil and sediments
Lake sediments, BC 5.5 (0.9–44) Cook et al. (1995)
(background)
The major proportion of arsenic compounds in soils
342 (80–1104) Azcue et al. (1994b,
1995) and sediments are usually As(III) and As(V). Under
Stream and lake silt 6 (b1–72) Boyle and Jonasson oxidizing conditions, inorganic arsenic is predominant-
(1973) ly present as As(V). H2AsO4 is the most stable species
Moira River, ON 1830 Owen and Galloway between pH 2 and 7, while HAsO42 is the most stable
(1969)
species above pH 7. As(V) can be reduced to As(III)
Moira Lake, ON 27 Mudroch and
Capobianco (1980) under moderately reducing conditions (Eh b 100 mV),
138–528 Zheng et al. (2003) which can be induced by flooding (Masscheleyn et al.,
408–1051 Azcue and Nriagu 1991; Reynolds et al., 1999). H3AsO3 is the predomi-
(1995) nant species within the normal soil pH range (pH 4 to 9)
Goldenville, NS 230–1980 Wong et al. (1999)
and is stable up to about pH 9 (Fig. 4).
Elmsdale, NS 262 Bamwoya et al. (1991)
Lakes near Yellowknife 6–3500 Wagemann et al. Gaseous arsine (AsH3) can be formed under ex-
(1978) tremely reduced conditions (Challenger, 1945; Cullen
Glacial till, BC 9.2 (1.9–170) Cook et al. (1995) and Reimer, 1989). Biotransformation and methylation
of arsenic occur naturally as a result of microbial
bottom sediments in concentrations up to 1104 mg/kg activity (Challenger, 1945; Braman, 1975; Cullen and
(Azcue et al., 1995). Azcue et al. (1994a) reported that Reimer, 1989; Abdullah et al., 1995). The methylated
the surficial sediments of Moira Lake, Ontario, arsenic species such as MMA(V), DMA(V) and TMAO
contained an average of 545 mg/kg of arsenic, and have been widely detected in soils (Braman, 1975;

0.75
H3AsO4
H2AsO4-
0.50

HAsO42-
0.25 H3AsO3

AsO43-
Eh (volts)

0 HAsS2
(AsS)
(As2S3) H2AsO3-
-0.25
AsS2-
HAsO32-
-0.50
AsH3(aq)
P AsH3 = 1 (As)
-0.75

-1
0 2 4 6 8 10 12 14
pH
Fig. 4. The Eh–pH diagram for arsenic at 25 8C and 101.3 kPa (modified from Ferguson and Gavis, 1972).
710 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
Cullen and Reimer, 1989). The trivalent methylated
intermediates such as MMA(III) and DMA(III) are
found to be readily oxidized chemically and biological-
ly (Sanders, 1979; Abdullah et al., 1995). Sanders
(1979) measured an average demethylation and oxida-
tion rate of DMA(III) acid to arsenate approximately 1
ng DMA(III)/L/day by mixed bacterial cultures isolated
from an estuarine system.
4.3. Arsenic association with solid phases
Arsenic in soils and sediments is usually found in
association with iron, aluminum, and manganese
(hydro)oxides, clays, and mineral oxyanions such as
sulfates, phosphates and carbonates, which may serve
as significant repositories of arsenic due to their ubiq-
uity in the environment (Foster, 2003). The grain sizes
of solid particles play an important role in controlling
the distribution and mobility of arsenic. Fine grains can
adsorb the bulk arsenic onto their surface because they
are of larger surface areas. Clay minerals and (hydro)-
oxides of iron, aluminum, and manganese occur ubiq-
uitously and are present as the main phase components
in the fine-particle fraction. They are, therefore, likely
the most important source/sink for arsenic. Iron hydro-
xides, such as goethite (a-FeOOH) and ferrihydrite (h-
FeOOH), are commonly found in soil and aquifer sedi-
ments and have shown an important role in influencing
the mobility behavior of arsenic (Sun and Doner, 1996;
Waychunas et al., 1993; Foster, 2003).
Results from selective sequential extraction showed
that most (approximately 60%) of the arsenic in a sed-
iment was retained by manganese oxides, amorphous
iron oxides and clay minerals (Shaw, 2004). The author
attributed this to the ligand exchange of the arsenate
oxyanion on the surfaces of the metal oxides and clay
minerals as well as the diffusion of arsenic into the metal
oxide minerals present in the sediment. Using extended
X-ray absorption fine structure (EXAFS) spectroscopy,
Waychunas et al. (1993) observed the formation of
inner-sphere bidentate arsenate complexes on the ferri-
hydrite surface and on the surfaces of the crystalline
FeOOH polymorphs. It has been reported that As(III)
also forms inner-sphere surface complexes on goethite
(Sun and Doner, 1996). The inner-sphere surface com-
plexes are formed through specific adsorption, involv-
ing the incorporation of anions (arsenic anions, in our
case) as a ligand in the coordination shell of an adsor-
bent. Since the inner-spherically adsorbed arsenic
anions are not considered to be readily exchangeable,
the formation of inner-sphere surface complexes will
inhibit the arsenic mobility. However, the adsorbed
arsenic may be remobilized when the environmental
conditions change (Fuller et al., 1993).
4.4. Mineral dissolution induced arsenic release
Arsenic-enriched soils and sediments are often pro-
posed to be the primary starting sources of arsenic in
waters. Oxidation of arsenic-bearing sulfides under ox-
ygenated conditions has been implicated as the cause of
arsenic contamination of surface and ground waters in
regions of active and historic mining as well as in non-
mined areas worldwide (Armienta et al., 1993; Chatter-
jee et al., 1995; Prior and Williams, 1996). It is postu-
lated that geochemical oxidation of exposed sulfide
minerals will release arsenic into surface and ground
waters. This process can be catalyzed by micro-organ-
isms such as Acidithiobacillus ferrooxidans and Lep-
tospirillum ferrooxidans (Rohwerder et al., 2003). The
exposure of potentially reactive surfaces to the atmo-
sphere and certain bacterial species has been attributed
to the seasonal lowering of water table. The extraction
of groundwater for irrigation and mining activities can
enhance the exposure and thus the oxidation process.
It is hypothesized that reductive dissolution of Fe(III)
oxides and hydroxides leads to high arsenic concentra-
tions in anoxic groundwater (Matisoff et al., 1982; Nick-
son et al., 2000; Harvey et al., 2002; Anawar et al., 2003;
McArthur et al., 2004). Microbially driven reductive
dissolution of arsenic-bearing iron oxyhydroxides
releases the sorbed arsenic. Microbial reduction of arse-
nate can occur even when arsenic is bound to iron oxides
(Langner and Inskeep, 2000). In a reducing environment,
the electron donor can be organic matter in sediments.
McArthur et al. (2004) suggested that the reduction is
driven by buried peat in the sediments. Ogden (1990)
proposed that the organic matter could be an anthropo-
genic input such as benzene, toluene, ethylbenzene, and
xylene (BTEX) and/or organic acids from landfill sites.
Harvey et al. (2002) found that young carbon sources
brought to the depth by recent irrigation pumping plays a
role in driving the reduction of FeOOH. The reduction of
FeOOH is governed by the available organic matter and
its reactivity to drive the reduction, which, in turn, will
affect the release of sorbed arsenic to solution.
5. Arsenic in water
5.1. Reported arsenic concentrations
5.1.1. Surface water
The ambient concentration of arsenic in surface and
ground waters in Canada usually ranges from 0.001 to
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721 711

0.002 mg/L (Table 6) (BCMWLAP, 2002). The levels of its untreated source water, which originated as ground-
arsenic in drinking water are generally less than 0.005 water from an aquifer (OSMONICS, 2002).
mg/L (Health Canada, 2003). Some creeks that are Elevated arsenic concentrations have been reported
recharged by groundwater with high levels of arsenic in waters near the vicinity of gold-mining or ore-
may also have high levels. In the town of Virden, Man- roasting operations. Influenced by tailings from gold-
itoba, arsenic levels ranged from 0.065 to 0.07 mg/L in mine workings, arsenic concentrations in the Moira
River, Ontario increased from 0.0007 mg/L (upstream)
to 0.023 mg/L (downstream) (Azcue and Nriagu,
Table 6
Arsenic concentrations in Canadian waters
1995). Azcue et al. (1994b) found concentrations up
to 0.556 mg/L (averaging 0.0175 mg/L) in streams
Location As concentration References
average (range)
adjacent to tailings deposits in British Columbia. The
(mg/L) arsenic content of the suspended particulates from
Surface water Gegogan Lake, Nova Scotia near an abandoned gold
British Columbia 0.00028 Azcue et al. (1994b, mine, ranged from 1500 to 5000 mg/kg, and the
(b0.0002–0.00042) 1995) arsenic content in filtered stream water varied from
Ontario 0.0007 Azcue and Nriagu 0.03 to 0.23 mg/L (Wong et al., 1999). In the vicinity
(1995) of Yellowknife, arsenic concentrations in water of
Saanich Inlet, BC 0.0012–0.0025 Peterson and
Carpenter (1983)
lakes ranged from 0.7 to 5.5 mg/L (Wagemann et
Mitchell Brook, NS 0.037–0.19 Brooks et al. (1982) al., 1978). Coumans (2003) estimated that the surface
Meager Creek, BC 0.0056 (cold) Koch et al. (1999) water in the Kam Lake, Yellowknife, contained up to
0.28 (0.237–0.303) 1570 mg/L of arsenic. The dominant species were
(hot) arsenate anions (Ollson, 1999).
Moira Lake, ON 0.022 (winter)–0.062 Azcue and Nriagu
(summer) (1995)
0.04–0.05 Zheng et al. (2003) 5.1.2. Groundwater
Moira River, ON 0.002–0.14 Zheng et al. (2003) Arsenic concentrations in groundwater are often
37.5 Owen and Galloway higher than those measured in surface waters (Table
(1969) 6). White et al. (1963) reported a dissolved arsenic
Gegogan Brook, NS 0.03–0.23 Wong et al. (1999)
Kam Lake, Yellowknife 1570 Coumans (2003) concentration of 0.23 mg/L in a NaHCO3 groundwater
British Columbia 0.0175 Azcue et al. (1994b) from a 1000 m deep oilfield well from Ellis Pool,
(b0.0002–0.556) Alberta. Boyle et al. (1998) measured concentrations
Northwest Territories 0.27 (0.064–0.53) Bright et al. (1996) up to 0.58 mg/L in groundwater from an area of sulfide
Ontario 0.035–0.1 Azcue and Nriagu
mineralization in Bowen Island, British Columbia. High
(1995)
Lakes near Yellowknife 0.7–5.5 Wagemann et al.
arsenic concentrations up to 11 mg/L were reported in
(1978) the groundwater in the vicinity of an abandoned arsen-
ical wood preservative facility near Vancouver, British
Groundwater Columbia (Henning and Konasewich, 1984).
Ellis Pool, Alberta 0.23 White et al. (1963)
Virden, MB 0.065–0.07 OSMONICS (2002)
Vancouver, BC 11 Henning and 5.1.3. Porewater
Konasewich (1984) High concentrations of arsenic have been found in
Bowen Island, BC 0.0005–0.58 Boyle et al. (1998) the porewater extracted from unconsolidated sediments
(Table 6). Inorganic arsenic species were measured in
Sediment porewater the porewaters collected from eighteen piezometers
Baseline, clays, 0.0032–0.098 Yan et al. (2000)
Saskatchewan
installed in a thick till and clay-rich aquitard sequence
Mining contaminated, 0.05–0.36 Azcue et al. (1994b) located in southern Saskatchewan. The aqueous con-
BC centrations of arsenate, arsenite and total arsenic are in
Tailing impoundment, 0.3–100 McCreadie et al. the range of 0.00031 to 0.097, 0.00071 to 0.021 and
ON (2000) 0.0032 to 0.098 mg/L, respectively (Yan et al., 2000).
Suspended particulates Even higher concentrations can be found in the pore-
Gegogan Lake, NS 1500–5000 (mg/kg) Wong et al. (1999) water from sediments affected by mining contamination
Moira Lake, ON 495–1565 (mg/kg) Azcue and Nriagu (tailings, mineral-rich deposit). McCreadie et al. (2000)
(1995) found arsenic concentrations up to 100 mg/L in pore-
Gegogan Brook, NS 170–2000 (mg/kg) Wong et al. (1999) water extracted from tailings in the province of Ontario.
712 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
The arsenic content in porewater is often higher than
in the overlying surface water (Table 6). Contaminated
from historic gold mine operations, high concentrations
of arsenic (N 0.3 mg/L), mainly present as As(III), were
detected in sediment porewater, Moira watershed,
Ontario, while arsenic concentrations in the surface
water of Moira River and Moira Lake are up to 0.075
and 0.05 mg/L respectively. 98% of them were present
as As(V) (Zheng et al., 2003). This may be the result of
the reducing conditions below the sediment–water in-
terface, which promotes the reduction of As(V) to
As(III) and the reductive dissolution of sorbed arsenic
from Fe and Mn oxides.
5.1.4. Geothermal fluid
Arsenic concentrations in geothermal fluid are usu-
ally two or three orders of magnitude greater than those
in uncontaminated surface and groundwater (Webster
and Nordstrom, 2003). Levels of arsenic in water from
Meager Creek hot springs, British Columbia, were
found to be naturally elevated (Koch et al., 1999).
The average concentration in the hot springs water
was 0.28 mg/L, with levels ranging from 0.237 to
0.303 mg/L. It was two orders of magnitude higher
than that in the cold Meager Creek water (0.0054 mg/
L). Only arsenate was detected in the hot water. The
elevated concentrations of arsenic result from the en-
hanced dissolution of arsenic-containing minerals by
hot water. Hot water usually has a high dielectric
constant, which enables it to dissolve ionic crystalline
minerals and form new hydrated minerals (Webster and
Nordstrom, 2003). Arsenic, initially as As(III), is then
released from the host rock. Oxidation of As(III) to
As(V) occurs immediately once the fluid is exposed to
oxygenated conditions. The estimated half-life is
around 20 min for As(III) oxidation to As(V) in Hot
Creek, Sierra Nevada Mountains of California, US
(Wilke and Hering, 1998). This process can be micro-
bially mediated. Through field investigations at a hot
spring in Yellowstone National Park and laboratory
experiments, Gihring et al. (2001) proposed that Ther-
mus aquaticus and Thermus thermophilus might play
an important role in determining arsenic speciation and
bioavailability in thermal environments.
5.1.5. Seasonal variation
Significant seasonal variations in speciation and ab-
solute concentration of arsenic in lake water have been
also reported. Azcue and Nriagu (1995) found that the
dissolved arsenic concentrations in the water of Moira
Lake in Ontario showed seasonal differences, with an
average concentration of 0.062 mg/L in summer and
0.022 mg/L in winter. In the summer, 60% of the
arsenic in the hypolimnion is largely present as
As(III). Some As(III) (25%) can even be detected in
the surface water. McLaren and Kim (1995) attributed
the seasonal variation to the seasonal changes in the
microbial activity of As(V) reducing bacteria such as
Anabena oscillaroides, which increases in high water
temperature during summer months thus leading to the
formation and release of the more soluble As(III) spe-
cies. Another possible reason is the lower dissolved
oxygen levels in water in summer due to the high
temperature. This condition favors the presence of
As(III) and may induce the reductive dissolution of
iron hydroxides to release adsorbed arsenic.
5.2. Main arsenic species in water
As(III) and As(V) are usually the main soluble
species in waters. Relative proportions of As(V) and
As(III), however, vary following changes in the
sources, pH and redox conditions, and microbial activ-
ities. Aggett and Brien (1985) found stratification of
arsenic concentrations in some lake waters due to vary-
ing redox conditions. Kim and Nriagu (2000) estimated
half-lives of As(III) in water saturated with air to be 4–9
days. Azcue and Nriagu (1995) reported an increase in
the ratio of As(III) / As(V) with depth. This can be
explained by the depleted oxygen levels at the bottom
of lake waters as a result of biological activities and the
resuspension of sediment porewaters near sediment–
water interface. Estimated upward diffusion flux of
arsenic from the sediments was 0.81–7.09 Ag/cm2/yr
(Azcue, 1992).
Concentrations of organoarsenic compounds are
generally low or negligible (Chen et al., 1995). For
example, in waters of Moira Lake, Ontario, Azcue
and Nriagu (1995) found As(III) concentrations of
0.007 to 0.075 mg/L, As(V) of 0.019 to 0.058 mg/L,
and only 0.00001 to 0.0015 mg/L of organic arsenic.
The concentrations of the methylated species, however,
may increase in the summer due to increased microbial
activity (Hasegawa, 1997).
5.3. Arsenic sorption behavior in water
Adsorption of arsenic onto mineral surfaces is gen-
erally the principal control on the dissolved arsenic
concentrations in waters. It has been found that arsenic
adsorption onto Fe oxides under neutral or mildly
acidic conditions may effectively decrease arsenic con-
centrations in mining affected lake water. In Jack of
Clubs Lake, British Columbia, Azcue et al. (1994b)
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
found arsenic concentrations affected by mining efflu-
ent were similar to those not affected by mining
effluent, at around 0.0003 mg/L in each case. The
greatest proportion of arsenic in the sediment cores
was associated with iron oxides and sulfides. The
tendency for iron solid surfaces to adsorb arsenic has
become the basis for removing arsenic from contami-
nated waters. Iron and manganese oxides have been
used for coating sand to remove arsenic from ground-
water (Joshi and Chaudhuri, 1996; Bajpai and Chaud-
huri, 1999).
The adsorption of arsenic onto minerals in aquifers,
however, is pH-dependent and is affected by the surface
characteristics of the minerals (Pierce and Moore, 1980,
1982; Xu et al., 1988; Bowell, 1994; Grossl et al.,
1997; Lin and Puls, 2000). The change of pH can affect
the aqueous arsenic speciation and the composition of
surface functional groups through protonation and
deprotonation reactions. Pierce and Moore (1980,
1982) reported that the preferential pH for As(V) ab-
sorption on hydroxides was from 4 to 7 whereas that for
As(III) was from 7 to 10. Bowell (1994) found that
amorphous iron oxyhydroxides could absorb much
more arsenic than crystalline iron oxyhydroxides and
oxide minerals. However, most experiments have been
carried out in the laboratory and are commonly for pure
minerals. Field-based investigations based on natural
environments, therefore, are preferred to determine the
effects directly.
Competition between arsenic and other sorbates (i.e.,
PO43 , SO42 , MoO42 ) on clay and oxide minerals has
also been demonstrated (Manning and Goldberg,
1996a,b; Anawar et al., 2003). Manning and Goldberg
(1996a,b) found that As(V) adsorption was slightly less
at equal concentrations of PO43 and As(V), but it was
greatly reduced when PO43 was present at 10 times the
concentration of As(V). Also, MoO42 inhibited As(V)
adsorption only at a pH value less than 4. Anawar et al.
(2003) reported that the bicarbonate ion is effective in
arsenic leaching from sediment samples. The increase
of arsenic concentrations extracted by NaHCO3 is lin-
early correlated with the concentration of NaHCO3.
Especially, natural organic matter may have signifi-
cant potential for influencing arsenic biochemistry in
aquifers (Redman et al., 2002; McArthur et al., 2004;
Wang and Mulligan, in press). Positive and significant
correlation of arsenic with the organic matter concen-
trations has been demonstrated in several areas world-
wide (Tseng et al., 1968; Kalbitz and Wennrich, 1998).
The presence of natural organic matter may enhance
arsenic release from soil and sediments into water
column through competition for available adsorption
713
sites, forming aqueous complexes and/or changing the
redox chemistry of site surface and arsenic species.
They could also inhibit arsenic release by serving as a
binding agent and/or by forming insoluble complexes
(Wang and Mulligan, in press).
6. Arsenic in biota
6.1. Arsenic uptake
All living organisms have the ability to extract arse-
nic from the ambient environment. Bioavailability, up-
take and phytotoxicity of arsenic to living organisms
are influenced by factors such as arsenic concentration
and species, living organism species, environmental
properties, and concentrations of competing ions (e.g.,
phosphate and sulfate). Since arsenate behaves as a
phosphate analogue (Yong and Mulligan, 2004), it is
taken up by phosphate transporters, e.g., Pit and Pst in
the prokaryote Escherichia coli (Rosenberg et al.,
1977). The uptake of arsenite is accomplished by aqua-
glyceroporins. Arsenate is then reduced to arsenite by
arsenate reductase. Arsenite is either extruded from
cells or form conjugates with thiol groups (Oden et
al., 1994; Pickering et al., 2000; Wysocki et al., 2001;
Rosen, 2002). Arsenic species can also be methylated
(Bentely and Chasteen, 2002). There is evidence that
bioaccumulation of arsenic can occur in organisms
(Meharg et al., 1998; Ebsuda et al., 2002).
6.2. Reported arsenic concentrations
Background arsenic concentrations in freshwater and
terrestrial biota are usually less than 1 mg/kg (fresh
weight) (Stoeppler and Nurnberg, 1979). Commonly
observed arsenic concentrations in plants range from
0.2 to 2.0 mg/kg (dry weight) (Bowen, 1979). They,
however, can be much higher near anthropogenic
sources or in areas with geothermal activity. Franzin
(1994) found arsenic concentrations varied from 4 to
263 mg/kg (dry weight) in Myriophyllum exalbescens,
a common pond weed in the lakes in the vicinity of the
base metal smelter at Flin Flon, Manitoba. Gamberg
and Braune (1999) reported that arsenic residues in the
kidney of male Yukon wolves were 0.51 (b18 months)
and 0.21 mg/kg (dry weight) (19–36 months). Values
were slighter higher for females, 0.57 and 0.25 mg/kg,
respectively. Arsenic residues in the liver of male
wolves were 0.31 (b 18 months) and 0.21 mg/kg (dry
weight) (19–36 months), whereas the values were 0.17
and 0.14 mg/kg for female wolves. Brooks et al. (1982)
measured the arsenic contents of aquatic organisms in a
714 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
stream in a gold-mining district in Nova Scotia. The
arsenic content ranged from 0.002 to 0.059 mg/kg (dry
weight) for mayfly larvae, 0.002 to 0.18 mg/kg (dry
weight) for caddisfly larvae, and 0.63 to 3.2 mg/kg (wet
weight) for the banded killifish (minnow).
In the coastal area of British Columbia, an average
arsenic concentration of 1.4 F 1.2 mg/kg was found in
the ooligan grease, a marine food fat rich with vitamin
A and omega-3 fatty acids (Kuhnlein et al., 1996).
Ebsuda et al. (2002) examined the total arsenic concen-
tration in ringed seals from Pangnirtung. Arsenic con-
centrations ranged from 0.11 F 0.04 mg/kg (dry weight)
in the hair to 1.14 F 0.37 mg/kg (wet weight) in the
blubber. The predominant arsenic specie (N 70%) was
arsenobetaine, an organoarsenic species common to
marine mammals. Notable high accumulation of arsenic
in the blubber was measured, accounting for about 90%
of the total arsenic.
In Meager Creek hot springs, British Columbia, the
highest arsenic concentrations were found in microbial
mats, algae and moss, ranging from 56 to 350 mg/kg
(dry weight). Arsenic concentrations in plants ranged
from 0.96 to 14 mg/kg (dry weight). Low levels of
arsenic were found in lichens and fungi, from b 0.07 to
4.8 mg/kg (dry weight). The arsenic concentrations in
the oyster tissue and the fucus were 4.0 F 0.5 and
41.4 F 1.2 mg/kg, respectively. At least 13–67% of
the total arsenic in vascular plants was in inorganic
forms and significant amounts of arsenite were present
in almost all plant samples (Koch et al., 1999).
In the vicinity of Yellowknife, elevated arsenic con-
centrations have been reported in plants, aquatic and
terrestrial biota due to the mining activity. In contam-
inated lakes, arsenic concentrations were found in the
range from 150 to 3700 mg/kg in macrophytes, 700 to
2400 mg/kg in zooplankton, and b 1 to 1300 mg/kg in
other invertebrates (Wagemann et al., 1978). Koch et al.
(2000a) analyzed the arsenic levels in a variety of plants
from Yellowknife. The arsenic levels varied between
3.6 and 1220 mg/kg (dry weight) and mosses contained
the highest levels of arsenic (490–1220 mg/kg dry
weight). The predominant arsenic species were in inor-
ganic forms. Arsenic concentrations in terrestrial
lichens and fungi ranged from 6.4 to 2300 mg/kg (dry
weight) (Koch et al., 2000b).
6.3. Implications for arsenic remediation technologies
6.3.1. Hyperaccumulation
Accumulation of arsenic was observed in submerged
plants in Moria River and Moria Lake in Ontario.
Arsenic concentrations in freshwater plants ranged
from 2.6 to 117 mg/kg (dry weight), and most of this
arsenic (70–93%) was inorganic arsenic (Zheng et al.,
2003). These may give some indications of the hyper-
accumulation technology for arsenic removal. Mkanda-
wire and Dudel (2005) demonstrated the potential of
using Lemna gibba L. for arsenic phytoremediation of
mine tailing waters. The authors proposed that L. gibba
L. could be a preliminary bioindicator for arsenic trans-
fer from substrate to plants and might be used to
monitor the transfer of arsenic from lower to higher
trophic levels in the abandoned mine sites. Moreover,
the brake fern Pteris vittata has been found recently the
capable of hyperaccumulating arsenic from soil (Ma et
al., 2001). The fern can accumulate levels up to 22,630
mg arsenic/kg (dry weight) in the shoot. The biocon-
centration factor (the ratio of shoot arsenic concentra-
tion to soil arsenic concentration) was greater than 10.
Sidoli O’Connor et al. (2003) found that the combina-
tion of electrokinetics and phytoremediation could re-
move 230 Ag/g of arsenic.
Hyperaccumulation of arsenic, however, is low for
most plant species, due to the high phytotoxicity of
arsenic and the limited uptake and translocation capa-
bilities of plants. These capacities can be significantly
increased by the overexpression of proteins involved in
intracellular arsenic sequestration. Dhankher et al.
(2002) demonstrated that engineering tolerance and
hyperaccumulation of arsenic in plants might be en-
hanced by combining arsenate reductase and g-gluta-
mylcysteine synthetase expression. After harvesting,
the hyperaccumulating plants can be either disposed
of as hazardous waste or, preferably, subjected to pro-
cesses to extract the arsenic from the plant issue for
industrial use (Ma et al., 2001; Mkandawire and Dudel,
2005).
6.3.2. Microbially mediated mobilization
Although arsenic is known to be toxic, some organ-
isms have evolved biochemical mechanisms to exploit
arsenic oxyanions, either as an electron acceptor (ar-
senate) for anaerobic respiration, or as an electron
donor (arsenite) to support chemoautotrophic fixation
of carbon dioxide into cell carbon (Santini et al.,
2000; Zobrist, 2000). Zobrist (2000) reported that
the cell suspension of Sulfurospirillium barnesii was
able to reduce arsenate to arsenite. The reduction of
Fe(III) in ferrihydrite to soluble Fe(II) occurred with
the cultured cells. The adsorption of arsenite onto the
ferrihydrite or alumina phase controlled the extent of
its release. The authors pointed out that the results are
significant in contributing to the understanding of the
mobilization of arsenic in large alluvia aquifers and in
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
the hyporheic zones of contaminated streams. As ar-
senite is much more toxic than arsenate. The reduction
process, however, cannot contribute to the detoxifica-
tion of arsenic and thus may limit the effectiveness of
bioremediation. Santini et al. (2000) discovered that
Pseudomonas arsenitoxidans NT-26 grew chemo-
lithoautrophically with arsenite as the electron donor,
oxygen as the electron acceptor, and carbon dioxide or
bicarbonate as the carbon sources. Results suggested
that this microorganism gains energy from the oxida-
tion of arsenite.
6.3.3. Natural attenuation
Several indigenous microorganisms are able to cat-
alyze the iron oxidation and, therefore, can enhance the
removal of arsenic. As a result of the biological oxida-
tion of iron, the intermixing of iron oxides, organic
material, and bacterial presence can enhance arsenic
removal by direct adsorption and/or co-precipitation
(Ferris et al., 2000; Fukushi et al., 2003; Katsoyiannis
and Zouboulis, 2004). Katsoyiannis and Zouboulis
(2004) found that the biotic oxidation of iron by micro-
organisms Gallionella ferruginea and Leptothrix ochra-
cea was effective for removal of arsenic from
groundwater. Fukushi et al. (2003) reported a natural
attenuation process of arsenic in an abandoned mining
area in Nishinomaki, Japan. The oxidation from Fe(II)
to Fe(III), catalyzed by the activity of Acidithiobacillus
ferrooxidans, facilitated the formation of schwertman-
nite under acidic and high SO42 conditions. The
arsenic concentration in the drainage decreased to back-
ground level by sorption onto schwertmannite, which
concentrated arsenic up to 10,000 mg/kg due to incor-
poration into the structure. The authors postulated that
the attenuation of arsenic in the drainage and the reten-
tion of arsenic by schwertmannite might be maintained
for a long term, since the transformation of schwert-
mannite to goethite might be retarded by the presence
of absorbed arsenate in the structure.
However, natural attenuation will be effective only
at sites with special environmental conditions, desorp-
tion and remobilization of sorbed arsenic from the solid
phases can occur when the conditions change with time.
It has been reported that significant arsenate desorption
from iron hydroxides could occur at pH values of
approximately pH 8 and higher (Fuller et al., 1993;
Lumston et al., 2001). Microbial activity can also en-
hance the remobilization processes (Zobrist, 2000).
Therefore, long-term monitoring of the subsurface en-
vironment in the contaminated site and in the region
surrounding the site is required (Mulligan and Yong,
2004).
715
6.3.4. Other technologies
Remediation technologies for arsenic-contaminated
soils can be divided into in situ and ex situ technologies.
Washing is a method for remediating arsenic-contami-
nated soils by using solutions to extract the arsenic from
the soil. Washing with alkali or acidic solutions en-
hanced arsenic removal but can destroy the soil iron
oxides at the extreme pH used or leach organic matter
(Legiec et al., 1997). However, reducing the acid treat-
ment time to less than 2 h reduced damage to the soil
(Tokunuga and Hakuta, 2002). 0.9 M phosphate is a
more inexpensive and environmental friendly method
of extracting arsenic from Al- and Fe-bound forms as
shown by sequential extraction (Alam et al., 2001).
Most in situ remediation techniques are potentially
less expensive and disruptive than ex situ ones, partic-
ularly for large contaminated areas. Natural or synthetic
additives can be utilized to enhance precipitation, ion
exchange, sorption and redox reactions (Mench et al.,
2000). The sustainability of reducing and maintaining
the reduced solubility conditions is key to the long term
success of the treatment. Ex situ techniques are expen-
sive and can disrupt the ecosystem and the landscape.
For shallow contamination, remediation costs, worker
exposure and environmental disruption can be reduced
by using in situ remediation techniques.
Various field trials have been performed to evaluate
steel shots and beringite to reduce arsenic solubility
(Verkleij et al., 1999). The corrosion of the steel shots
enhances the formation of Fe/Mn oxides while beringite
affects soil pH (Vangronsveld et al., 1999). Boisson et
al. (1999) amended soil with various additives and
determined that 1% steel shot with 5% beringite was
the most effective for reducing arsenic mobility due to
adsorption and precipitation with iron oxides. However,
hydroxyapetite addition could enhance mobility due to
competition with phosphate. Warren et al. (2003) also
evaluated addition of ferrous sulfate and lime in solu-
tion to produce ferrous oxides. Significant reductions in
arsenic bioavailability were achieved. Mench et al.
(2003) evaluated the long term sustainability of various
amendments at a former gold mine including 5% com-
post with steel shot (CSS), 5% compost with 5% ber-
ingite and 1% steelshot (CBSS), 5% compost (C) and
others. The CBSS and CS treatments were very suc-
cessful in terms of revegetation and decreased leaching
compared to compost only. Addition of immobilizing
agents that are insoluble such as hydroxyapetite, zeo-
lites or illitic clays can be problematic, particularly to
depths below 50 cm.
Vitrification is applicable for arsenic-contaminated
soils since arsenic is of low volatility. Melting ability
716 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
depends on the soil’s silica content. The maximum
allowable oxide content for arsenic is 5% (Smith et
al., 1995). It is the best demonstrated available technol-
ogy (BDATs) for RCRA wastes.
7. Conclusions and recommendations
This study examined the current available informa-
tion on the occurrence and distribution of arsenic con-
tamination in Canada. It has also been related to the fate
and transport cycle of arsenic in the environment and
their implications on arsenic remediation technologies.
The current situation of arsenic contamination in
Canada appears alarming and requires commensurate
attention to the gravity of the consequent situation.
Main sources of arsenic in Canada have been attributed
to the release from natural enrichments and human
activities such as mining and metal smelting, and
wood preservation as well as coal-fired thermal and
power generation. Elevated concentrations have been
reported. Most of the arsenic is present in highly toxic
inorganic forms. It may cause severe adverse effects on
the environment and public health, especially for those
living in the vicinity of point sources.
Previous investigations of a number of contaminated
sites have led to a better understanding of this particular
problem. However, research focused only on heavily
contaminated sites. Uncertainties still remain and much
is unknown beyond these areas. A national-scale survey
is required to gain a full picture, and to identify areas of
groundwater with low concentrations of arsenic for fu-
ture use. It is critical to assess arsenic exposure in people,
especially in populations living near point sources such
as mining areas and in rural areas. It may be helpful to
increase the public awareness of the toxicity and the
environmental impact of arsenic contamination.
The implementation of new guidelines and regula-
tions should be considered in order to protect public
health. For example, the Interim Maximum Concentra-
tion Level (IMCL) for drinking water (0.025 mg/L)
should be reduced to the WHO standard of 0.01 mg/L
or even lower to 0.005 mg/L or less. National quality
guidelines for arsenic in air should be built since ele-
vated levels have been detected. Source reduction is of
principle significance for preventing future contamina-
tion. Mining and smelting industries should be encour-
aged to develop new technologies for reducing arsenic
release to achieve the arsenic discharge limits set by the
government.
Knowledge of the occurrence, origin and distribu-
tion of arsenic is necessary for reducing and avoiding
arsenic related problems. Especially, information on the
speciation of arsenic is gaining increasing importance
as the bioavailability and the physiological and toxico-
logical effects of arsenic are connected to its chemical
form and oxidation state. However, in most cases the
analyses are restricted to the determination of total
arsenic, which is insufficient for environmental consid-
erations. The quantitative determination of individual
species rather than the total arsenic determination is
therefore mandatory to obtain an appropriate measure-
ment for accurate assessments of environmental impact
and health risks.
Effective remediation technologies are required. Bi-
ological processes have demonstrated potential for the
treatment of contaminated sites, since they are cost
effective, promising, and environmentally friendly
(Mulligan, 2002; Wang and Mulligan, 2004b). Pretreat-
ments may be required to reduce the arsenic concentra-
tion to a tolerable level for microorganisms. The use of
plants to remediate arsenic contaminated sites is emerg-
ing. Genetics-based strategies may be used to improve
the engineering tolerance and hyperaccumulating ca-
pacity of plants. Natural attenuation may be a cost-
effective in situ remedial option. Sufficient site charac-
terization is the key to assess the site natural attenuation
capacity. More research studies are needed to elucidate
the mechanisms controlling the rate of microbially
mediated As(V)/As(III) cycling in soils and natural
waters. However, natural attenuation is subject to
changes of site geological conditions. Long-term mon-
itoring is required and engineering methods may be
used to reduce risk and increase remediation rates.
Naturally occurring organic matter such as humic and
fulvic acids has demonstrated potential in influencing
the arsenic mobility. Further research is needed to
investigate their roles in the remedial strategies for
arsenic contaminated sites.
References
Abdullah MI, Zhou S, Mosgren K. Arsenic and selenium species in
the oxic and anoxic waters of the Oslofjord, Norway. Mar Pollut
Bull 1995;31:116 – 26.
Aggett J, Brien OGA. Detailed model for the mobility of arsenic in
lacustrine sediments based on measurements in Lake Ohakuri.
Environ Sci Technol 1985;19:231 – 8.
Alam MGM, Tokunaga S, Maekawa T. Extraction of arsenic in a
synthetic arsenic-contaminated phosphate. Chemosphere 2001;43:
1035 – 41.
Alberta Environment. Air quality monitoring, Northwest Edmonton,
June 2001 to March 2002, interim report. Edmonton7 AB; 2003.
Anawar HM, Akai J, Komaki K, Terao H, Yoshioka T, Ishizuka T, et al.
Geochemical occurrence of arsenic in groundwater of Bangladesh:
source and mobilization processes. J Geochem Explor 2003;
77:109 – 31.
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
Andreae MO. Arsenic in rain and the atmospheric mass balance of
arsenic. J Geophys Res 1980;85:4512 – 8.
Armienta MA, Villasenor G, Rodriguez R, Ongley LK, Mango H.
The role of arsenic-bearing rocks in groundwater pollution at
Zimapán Valley, México. Environ Geol 1993;40:571 – 81.
Azcue JM. Geochemistry of arsenic in Moira Lake. PhD Thesis,
University of Waterloo, Canada; 1992.
Azcue JM, Nriagu JO. Impact of abandoned mine tailings on the
arsenic concentrations in Moira Lake, Ontario. J Geochem Explor
1995;52:81 – 9.
Azcue JM, Nriagu JP, Schiff S. Role of sediment porewater in the
cycling of arsenic in a mine-polluted lake. Environ Int 1994a;20:
517 – 27.
Azcue JM, Murdoch A, Rosa F, Hall GEM. Effects of abandoned
gold mine tailings on the arsenic concentrations in water and
sediments of Jack of Clubs Lake, BC. Environ Technol 1994b;15:
669 – 78.
Azcue JM, Jackson TA, Reynoldson T, Mudroch A, Rosa F, Hall
GEM. Trace elements in water, sediments, porewater, and biota
polluted by tailings from an abandoned gold mine in British
Columbia, Canada. J Geochem Explor 1995;52:25 – 34.
Bajpai S, Chaudhuri M. Removal of arsenic from groundwater by
manganese dioxide-coated sand. J Environ Eng 1999;125:782 – 4.
Bamwoya JJ, Rutherford LA, Henninger PA, Horne WH. Toxic
contaminants in soils and sediments at four wood preservation
facilities in Atlantic Canada EPS-5-AR-91-2. Dartmouth, Nova
Scotia, Canada7 Environment Canada, Environmental Protection;
1991.
Barbaris B, Betterton EA. Initial snow chemistry survey of the
Mogollon Rim in Arizona. Atmos Environ 1996;30:3093 – 103.
BCMWLAP (Ministry of Water, Land, and Air Protection, Province
of British Columbia). Arsenic in groundwater Well stewardship
information series, BC; 2002.
Bennett B, Dudas MJ. Release of arsenic and molybdenum by reduc-
tive dissolution of iron oxides in a soil with enriched levels of
native arsenic. J Environ Eng Sci 2003;2:265 – 72.
Bentely R, Chasteen TG. Microbial methylation of metalloid: arse-
nic, antimony, and bismuth. Microbiol Mol Biol Rev 2002;66:
250 – 71.
Bishop RF, Chisholm D. Arsenic accumulation in Annapolis Valley
orchards. Can J Soil Sci 1961;42:77 – 80.
Boisson J, Mench M, Vanqronsveld J, Ruttens A, Kopponen P, De
Koe T. Immobilization of trace metals and arsenic by different soil
additives: Evaluation by means of chemical extractions. Commun
Soil Sci Plant Anal 1999;30:365 – 87.
Boyle RW, Jonasson IR. The geochemistry of As and its use as an
indicator element in geochemical prospecting. J Geochem Explor
1973;2:251 – 96.
Boyle DR, Turner RJW, Hall GEM. Anomalous arsenic concen-
trations in groundwaters of an island community, Bowen
Island, British Columbia. Environ Geochem Health 1998;20:
199 – 212.
Bowell RJ. Sorption of arsenic by iron oxides and oxyhydroxides in
soils. Appl Geochem 1994;9:279 – 86.
Bowen HJM. Environmental chemistry of the elements. London7
Academic; 1979.
Braman RS. Arsenic in the environment. In: Woolson EA, editor.
Arsenical pesticides. Washington, DC7 Am Chem Soc; 1975.
p. 108 – 23.
Brewer R, Belzer W. Assessment of metal concentrations in atmo-
spheric particles from Burnaby Lake, British Columbia, Canada.
Atmos Environ 2001;35:5223 – 33.
717
Bright DA, Dodd M, Reimer KJ. Arsenic in sub-Arctic lakes influ-
enced by gold mine effluent: the occurrence of organoarsenicals
and dhiddenT arsenic. Sci Total Environ 1996;180:165 – 82.
Brooks KM. Literature review and assessment of the environmental
risks associated with the use of CCA and ACZA treated wood
products in aquatic environments Prepared for western wood
preservative institute, Vancouver, BC; 1993.
Brooks RR, Fergusson JE, Holzbecher J, Ryan DE, Zhang HF, Dale
JM, et al. Pollution by arsenic in a gold-mining district in Nova
Scotia. Environ Pollut (B) 1982;4:109 – 17.
CCME (Canadian Council of Ministers of the Environment). Cana-
dian environmental quality guidelines. MB, Canada7 Winnipeg;
1999/2002. updated.
CED (Environmental Defence Canada). Arsenic lurks in Canadian
playgrounds: Is your child safe? Toronto, ON, Canada7 Environ-
mental Defence Canada; 2003.
CEPA (Canadian Environmental Protection Act). Arsenic and its
compounds Priority substances list assessment report. Ottawa,
Canada7 Government of Canada; 1993.
Challenger F. Biological methylation. Chem Rev 1945;36:315 – 61.
Chatterjee A, Das D, Mandal BK, Chowdhury TR, Samanta G,
Chakraborti D. Arsenic in groundwater in 6 districts of West
Bengal, India — the biggest arsenic calamity in the world 1
Arsenic species in drinking water and urine of the affected people.
Anal 1995;120:643 – 50.
Chen SL, Yeh SJ, Yang MH, Lin TH. Trace element concentration
and arsenic speciation in the well water of a Taiwan area with
endemic Blackfoot disease. Trace Elem Res 1995;48:263 – 74.
Cook SJ, Levson VM, Giles TR, Jackaman W. A comparison of
regional lake sediment and till geochemistry surveys, a case-
study from the Fawnie Creek area, central British Columbia.
Explor Min Geol 1995;4:93 – 110.
Cooper PA. Leaching of CCA: is it a problem? Environmental con-
siderations in the manufacture, use and disposal of preservative-
treated wood. Madison, Wisconsin7 Forest Products Society;
1994. p. 45 – 57.
Coumans C. Mining in Canada: the bigger picture Presentation for
Philippine delegation to Ottawa, Canada; 2003.
Cranstone D. Canada’s historical mineral production. Canadian min-
eral yearbook, 2001 Minerals and metals sector (MMS), natural
resources Canada; 2001.
Cullen WR, Reimer KJ. Arsenic speciation in the environment. Chem
Rev 1989;89:713 – 64.
Dhankher OP, Li Y, Rosen BP, Shi J, Salt D, Senecoff JF, et al.
Engineering tolerance and hyperaccumulation of arsenic in plants
by combining arsenate reductase and g-glutamylcysteine synthe-
tase expression. Nat Biotechnol 2002;20:1140 – 5.
Donahue R, Hendry MJ. Geochemistry of arsenic in uranium mine
mill tailings, Saskatchewan, Canada. Appl Geochem 2003;18:
1733 – 50.
Dopp E, Hartmann LM, Florea AM, van Recklinghausen U, Pieper R,
Shokouhi B, et al. Uptake of inorganic and organic derivatives of
arsenic associated with induced cytotoxic and genotoxic effects in
Chinese hamster ovary (CHO) cells. Toxicol Appl Pharmacol
2004;201:156 – 65.
Dudas MJ. Enriched levels of arsenic in post-active acid sulfate soils
in Alberta. Soil Sci Soc Am J 1984;48:1451 – 2.
Dudas MJ. Accumulation of native arsenic in acid sulphate soils in
Alberta. Can J Soil Sci 1987;67:317 – 31.
Dudas MJ, Pawluk S. Natural abundances and mineralogical parti-
tioning of trace elements in selected Alberta soils. Can J Soil Sci
1980;60:763 – 71.
718 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
Dudas MJ, Warren CJ, Spiers GA. Chemistry of arsenic in acid sulfate
soils of northern Alberta. Commun Soil Sci Plant Anal 1988;19:
887 – 95.
EBA Engineering Consultant Ltd. Surface contaminant study Giant
Mine site, Yellowknife, NWT. Yellowknife, NWT, Canada7 EBA
Engineering Consultants Limited; 1998.
Ebsuda K, Kunito T, Kubota R, Tanabe S. Arsenic concentrations
and speciation in the tissues of ringed seals (Phoca hispida)
from Pangnirtung, Canada. Appl Organomet Chem 2002;16:
451 – 7.
ENVIRDOQ. Air quality in Quebec, 1975–1994. Quebec, Canada7
Ministère de l’Environnement et de la Faune Direction du milieu
atmosphérique and Direction des politiques du secteur industriel;
1997.
Environment Canada. Results from inhalable particulate matter (PM10)
sampling network (1984–1987) PMD-90-3 Ottawa, Canada; 1990.
Environment Canada. Canadian soil quality guidelines for arsenic:
environmental and human health Supporting document, Final
draft Ottawa, Canada; 1996.
Environment Canada. Informing Canadians on pollution: highlights
of the 2000 national pollutant release inventory (NPRI) Ottawa,
Canada; 2002.
ESG (Environmental Sciences Group). Environmental study of arse-
nic contamination from the Giant Mine, Yellowknife, NWT, part I
Prepared for Indian and Northern Affairs Canada RMC-CCE-ES-
00-024. Kingston, Canada7 Royal Military College of Canada;
2000.
Ferguson JF, Gavis J. A review of the arsenic cycle in natural waters.
Water Res 1972;6:1259 – 74.
Ferris FG, Hallberg RO, Lyven B, Pedersen K. Retention of
strontium, cesium, lead and uranium by bacterial iron oxides
from a subterranean environment. Appl Geochem 2000;15:
1035 – 1042.
Fields S. Caution—children at play: how dangerous is CCA? Environ
Health Perspect 2001;109:262 – 9.
Foster AL. Spectroscopic investigation of arsenic species in solid
phases. In: Welch AH, Stollenwerk KG, editors. Arsenic in
ground water: geochemistry and occurrence. Boston7 Kluwer
Academic Publishers; 2003. p. 27 – 65.
Frank R, Braun HE, Ishida K, Suda P. Persistent organic and inor-
ganic pesticide residues in orchard soils and vineyards of southern
Ontario. Can J Soil Sci 1976;56:463 – 84.
Franzin WG. Aquatic contamination in the vicinity of the base metal
smelter at Flin Flon, Manitoba, Canada: a case history. In: Nriagu
JO, editor. Environmental impacts of smelters, vol. 15. Advances
in environmental science and technology. New York7 John Wiley
& Sons; 1994. p. 523 – 50.
Fukushi K, Sasaki M, Sato T, Yanase N, Amando H, Ikeda H. A
natural attenuation of arsenic in drainage from an abandoned
arsenic dump. Appl Geochem 2003;18:1267 – 78.
Fuller CC, Davis JA, Waychunas GA. Surface-chemistry of ferrihy-
drite 2 Kinetics of arsenate adsorption and coprecipitation. Geo-
chim Cosmochim Acta 1993;57:2271 – 82.
Gamberg M, Braune BM. Contaminant residue levels in arctic wolves
(Canis lupus) from Yukon Territory, Canada. Sci Total Environ
1999;243/244:329 – 38.
Gihring TM, Druschel GK, McCleskey RB, Hamers RJ, Banfield JF.
Rapid arsenite oxidation by Thermus aquaticus and Thermus
thermophilus: field and laboratory investigations. Environ Sci
Technol 2001;35:3857 – 62.
Goodarzi F, Huggins FE. Monitoring the species of arsenic, chromium
and nickel in milled coal bottom ash and fly ash from a pulverized
coal-fired power plant in western Canada. J Environ Monit
2001;3:1 – 6.
Gorby MS. Arsenic in human medicine. In: Nriagu JO, editor. Arsenic
in the environment, part II, human health and ecosystem effects.
NY7 John Wiley & Sons, INC; 1994. p. 1 – 16.
Gray JR, Khalil A, Prior JC. Acute arsenic toxicity: an opaque poison.
Can Assoc Radiol J 1989;40:226 – 7.
Grossl PR, Eick M, Sparks DL, Goldberg S, Ainsworth CC. Arsenate
and chromate retention mechanisms on goethite 2 Kinetic evalu-
ation using a pressure-jump relaxation technique. Environ Sci
Technol 1997;31:321 – 6.
Gulens J, Champ DR, Jackson RE. Influence of redox environments
on the mobility of arsenic in ground water. In: Jenne EA, editor.
Chemical modeling in aqueous systems, ACS Symposium Series
93. Washington, DC7 Am Chem Soc; 1979. p. 81 – 95.
Harvey CF, Swartz CH, Badruzzaman ABM, Keon-Blute N, Yu W,
Ali MA, et al. Arsenic mobility and groundwater extraction in
Bangladesh. Science 2002;298:1602 – 6.
Hasegawa H. The behavior of trivalent and pentavalent methylarse-
nicals in Lake Biwa. Appl Organomet Chem 1997;11:305 – 11.
Health Canada. It’s your health: arsenic in drinking water. Ottawa,
Canada7 Health Canada; 2003.
Health Canada. Fact sheet on chromated copper arsenate (CCA)
treated wood. Ottawa7 Pest Management Regulation Agency;
2005.
Henning FA, Konasewich DE. Characterization and assessment of
wood preservation facilities in British Columbia. West Vancouver,
BC, Canada7 Environmental Protection Services, Pacific region,
Environment Canada,; 1984.
Hingston JA, Collins CD, Murphy RJ, Lester JN. Leaching of chro-
mated copper arsenate wood preservatives: a review. Environ
Pollut 2001;111:53 – 66.
Hower JC, Calder JH, Eble CF, Scott AC, Robertson JD, Blanchard
LJ. Metalliferous coals of the Westphalian A Joggins Formation,
Cumberland Basin, Nova Scotia, Canada: petrology, geochemis-
try, and palynology. Int J Coal Geol 2000;42:185 – 206.
IAQAB (International Air Quality Advisory Broad). Air quality in
selected binational Great Lakes urban regions (Detroit–Windsor,
port Huron-Sarnia, and Sault Ste Maries) Reported to the Inter-
national Joint Commission Ontario, Canada; 2004.
Joshi A, Chaudhuri M. Removal of arsenic from groundwater by iron
oxide-coated sand. J Environ Eng 1996;122:769 – 71.
Kalbitz K, Wennrich R. Mobilization of heavy metals and arsenic in
polluted wetland soils and its dependence on dissolved organic
matter. Sci Total Environ 1998;209:27 – 39.
Katsoyiannis IA, Zouboulis AI. Application of biological processes
for the removal of arsenic from groundwaters. Water Res
2004;38:17 – 26.
Kim MJ, Nriagu JO. Oxidation of arsenite in groundwater using
ozone and oxygen. Sci Total Environ 2000;247:71 – 9.
Kim MJ, Nriagu JO, Haack SK. Carbonate ions and arsenic dissolu-
tion by groundwater. Environ Sci Technol 2000;34:3094 – 100.
Koch I, Feldmann J, Wang L, Andrewes P, Reimer KJ, Cullen WR.
Arsenic in the Meager Creek hot springs environment, British
Columbia, Canada. Sci Total Environ 1999;236:101 – 17.
Koch I, Wang L, Ollson CA, Cullen WR, Reimer KJ. The predom-
inant of inorganic arsenic species in plants from Yellowknife,
Northwest Territories, Canada. Environ Sci Technol 2000;34:
22 – 6.
Koch I, Wang L, Reimer KJ, Cullen WR. Arsenic species in terrestrial
fungi and lichens from Yellowknife, NWT, Canada. Appl Orga-
nomet Chem 2000;14:245 – 52.
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
Korte NE, Fernando Q. A review of arsenic (III) in groundwater. Crit
Rev Environ Control 1991;21:1 – 39.
Kuhnlein HV, Yeboah F, Sedgemore M, Sedgemore S, Chan HM.
Nutritional qualities of ooligan grease: a traditional food fat of
food fat of British Columbia First Nations. J Food Compos Anal
1996;9:18 – 31.
Lamble KJ, Hill SJ. Arsenic speciation in biological samples by on-
line high performance liquid chromatography-microwave diges-
tion-hydride generation-atomic absorption spectrometry. Anal
Chim Acta 1996;334:261 – 70.
Lambert TW, Lane S. Lead, arsenic and polycyclic aromatic hydro-
carbons in soil and house dust in the communities surrounding the
Sydney, Nova Scotia, tar ponds. Environ Health Perspect
2004;112:35 – 41.
Langner HW, Inskeep WP. Microbial reduction of arsenate in the
presence of ferrihydrite. Environ Sci Technol 2000;34:3131 – 6.
Legiec IA, Grifin LP, Walling, Breske MS, Angelo RS, Issacson M,
et al. DuPont soil washing technology program and treatment of
arsenic contaminated soils. Environ Prog 1997;16(1):29 – 34.
Lin Z, Puls RW. Adsorption, desorption and oxidation of arsenic
affected by clay minerals and aging process. Environ Geol
2000;39:753 – 9.
Lumston DG, Meeussen JCL, Paterson E, Garden LM, Abderson P.
Use of solid phase characterization and chemical modeling for
assessing the behavior of arsenic in contaminated soils. Appl
Geochem 2001;16:571 – 81.
Lund U, Fobian A. Pollution of two soils by arsenic, chromium and
copper, Denmark. Geoderma 1991;49:83 – 103.
Ma LQ, Komar KM, Tu C, Zhang WH, Cai Y, Kennelley ED. A fern
that hyperaccumulates arsenic—a hardy, versatile, fast-growing
plant helps to remove arsenic from contaminated soils. Nature
2001;409:579–79.
Mackenzie FT, Lantzy RJ, Paterson V. Global trace metal cycles and
predictions. J Int Assoc Math Geol 1979;11:99 – 142.
MacLatchy I. Metals data from base metal smelters and refineries.
Ottawa, Canada7 Environment Canada, Industrial Programs
Branch; 1992.
MacLean KS, Langille WM. Arsenic in orchard and potato soils and
plant tissue. Plant Soil 1981;61:413 – 8.
Manning BA, Goldberg S. Modeling arsenate competitive adsorption
on kaolinite, montmorillonite, and illite. Clays Clay Miner
1996;44:609 – 23.
Manning BA, Goldberg S. Modeling competitive adsorption of arse-
nate with phosphate and molybdate on oxide minerals. Soil Sci
Soc Am J 1996;60:121 – 31.
Martin RR, Tomlin A, Marsello B. Arsenic uptake in orchard
trees: implications for dendroanalysis. Chemosphere 2000;41:
635 – 7.
Masscheleyn PH, Delaune RD, Patrick WH Jr. Effect of redox po-
tential and pH on arsenic speciation and solubility in a contam-
inated soil. Environ Sci Technol 1991;25:1414 – 9.
Matisoff GC, Khourey CJ, Hall JF, Varnes AW, Strain WH. The
nature and source of arsenic in northeastern Ohio groundwater.
Ground Water 1982;20:446 – 56.
McArthur JM, Banerjee DM, Hudson-Edwards KA, Mishra R, Purohit
R, Ravenscroft P, et al. Natural organic matter in sedimentary basins
and its relation to arsenic in anoxic ground water: the example of
West Bengal and its worldwide implications. Appl Geochem
2004;19:1255 – 93.
McCreadie H, Blowes DW, Ptacek CJ, Jambor JL. Influence of
reduction reactions and solid-phase composition on porewater
concentrations of arsenic. Environ Sci Technol 2000;34:3159 – 66.
719
McLaren MA, Kim ND. Evidence for a seasonal fluctuation of As in
NZ’s longest river and the effect of treatment on concentrations in
drinking water. Environ Pollut 1995;90:67 – 73.
Meharg AA, Shore RF, Broadgate K. Edaphic factors affecting the
toxicity and accumulation of arsenate in the earthworm Lumbricus
terrestris. Environ Toxicol Chem 1998;17:1124 – 31.
Mench M, Vangronsveld J, Clijsters H, Lepp NW, Edwards R. In situ
metal immobilization and phytostabilization of contaminated
soils. In: Terry N, Bauelos G, editors. Phytoremediation of con-
taminated soil and water. Boca Raton, FL7 Lewis Publishers;
2000. p. 323 – 58.
Mench M, Bussiere S, Boisson J, Castaing E, Vangronsveld J, Ruttens
A, et al. Progress in remediation and revegetation of the barren
Jales gold mine spoil after in situ treatments. Plant Soil
2003;249:187 – 202.
Merkle P, Gallagher DL, Soldberg TN. Leaching rates, metals distri-
bution and chemistry of CCA treated lumber: implications for
water quality monitoring. Forest product society’s symposium,
environmental considerations in the use of pressure treated
wood. Madison, WI7 Forest Products Society; 1993. p. 69 – 78.
Mkandawire M, Dudel EG. Accumulation of arsenic in Lemna gibba
L. (duckweed) in tailing waters of two abandoned uranium mining
sites in Saxony, Germany. Sci Total Environ 2005;336:81 – 9.
Moldovan B, Hendry MJ, Jiang DT. Geochemical and mineralogical
controls on arsenic release from uranium mine tailings. Geophys
Res Abstr 2003;5:12538.
Mudroch A, Capobianco JA. Impact of past mining activities on
aquatic sediments in Moira River Basin, Ontario. J Great Lakes
Res 1980;6:121 – 8.
Mulligan CN. Environmental biotreatment: technologies for air, water,
soil and wastes. Rockville, MD7 Government Institutes; 2002.
Mulligan CN, Yong RN. Natural attenuation of contaminated soils.
Environ Int 2004;30:587 – 601.
Newhookm R, Hirtle H, Byrne K, Meek ME. Release from copper
smelters and refineries and zinc plants in Canada: human health
exposure and risk characterization. Sci Total Environ
2003;301:23 – 41.
Nickson RT, McArthur JM, Ravenscroft P, Burgess WG, Ahmed KM.
Mechanism of arsenic release to groundwater, Bangladesh and
West Bengal. Appl Geochem 2000;15:403 – 13.
NRC (National Research Council). Arsenic in drinking water.
Washington, DC7 National Academy Press; 1999.
Nriagu JO, Pacyna JM. Quantitative assessment of the world contam-
ination of air, water, and soils by trace metals. Nature 1988;333:
134 – 9.
Oden KL, Gladysheva TB, Rosen BP. Arsenate reduction mediated by
the plasmid-encoded ArsC protein is coupled to glutathione. Mol
Microbiol 1994;12:301 – 6.
Ogden PR. Arsenic behavior in soil and groundwater at a Superfund
site. Superfund ’90. Silver Spring, MD7 Hazardous Materials
Control Research Institute; 1990. p. 123 – 7.
Ollson CC. Arsenic contamination of the terrestrial and freshwater
environment impacted by gold mining operations Yellowknife,
NWT. MEng. Thesis, Royal Military College of Canada, King-
ston, Canada; 1999.
OSMONICS. Virden, Manitoba, Canada case study: arsenic. OSMO-
NICS profiles of winning solutions, Minnetonka, MN, Canada;
2002.
Owen GE, Galloway DL. Biological survey of the Moira River.
Canada7 Ontario Ministry of the Environment; 1969.
PAN Pesticides Database (2005). Pesticide registration status. http://
www.pesticideinfo.org/. Updated on April 8, 2005.
720 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
Peterson ML, Carpenter R. Biogeochemical processes affecting total
arsenic and arsenic species distributions in an intermittently an-
oxic fjord. Mar Chem 1983;12:295 – 321.
Peterson PJ, Benson LM, Zieve R. Metalloids, sec 3 — arsenic. In:
Lepp NW, editor. Effect of heavy metal pollution on plants.
London7 Applied Science Publishers; 1981. p. 299 – 322.
Pierce ML, Moore CB. Adsorption of arsenite on amorphous iron
hydroxide from dilute aqueous solution. Environ Sci Technol
1980;14:214 – 6.
Pierce ML, Moore CB. Adsorption of arsenite and arsenate on amor-
phous iron hydroxide. Water Res 1982;16:1247 – 53.
Pickering IJ, Prince RC, George MJ, Smith RD, George GN, Salt DE.
Reduction and coordination of arsenic in Indian mustard. Plant
Physiol 2000;122:1171 – 8.
Popovic A, Djordjevic D, Polic P. Trace and major element pollution
originating from coal ash suspension and transport processes.
Environ Int 2001;26:251 – 5.
Prior HL, Williams GA. Some mines and minerals of Morgan County,
Missouri. Rocks Miner 1996;71:102 – 10.
Prosun B, Mukherjee AB, Gunnar J, Nordqvist S. Metal contamina-
tion at a wood preservation site: characterization and experimental
studies on remediation. Sci Total Environ 2002;290:165 – 80.
Rasmussen PE, Subramanian KS, Jessiman BJ. A multi-element
profile of housedust in relation to exterior dust and soils in the
city of Ottawa, Canada. Sci Total Environ 2001;267:125 – 40.
Redman AD, Macalady D, Ahmann D. Natural organic matter affects
arsenic speciation and sorption onto hematite. Environ Sci Technol
2002;36:2889 – 96.
Reynolds JG, Naylor DV, Fendorf SE. Arsenic sorption in phosphate-
amended soils during flooding and subsequent aeration. Soil Sci
Soc Am J 1999;63:1149 – 56.
Rohwerder T, Gehrke T, Kinzler K, Sand W. Bioleaching review part
A: progress in bioleaching: fundamental and mechanisms of
bacterial metal sulfide oxidation. Appl Microbiol Biotechnol
2003;63:148 – 239.
Rosen BP. Biochemistry of arsenic detoxification. FEBS Lett
2002;529:86 – 92.
Rosenberg H, Gerdes RG, Chegwidden K. Two systems for the
uptake of phosphate in Escherichia Coli. J Bacteriol 1977;
131:505 – 11.
RWED (Department of Resources, Wildlife and Economic Develop-
ment). 2001/2002 Northwest territories air quality report. Yellow-
knife, NT, Canada7 Environmental Protection Service; 2003.
Saha KC. Review of arsenicosis in West Bengal, India: a clinical
perspective. Crit Rev Environ Sci Technol 2003;30:127 – 63.
Sanders JG. Microbial role in the demethylation and oxidation of
methylated arsenicals in sea water. Chemosphere 1979;8:135 – 7.
Santini JM, Sly LI, Schnagl RD, Macy JM. A new chemolithoauto-
trophic arsenite-oxidizing bacterium isolated from a gold mine:
phylogenetic, physiological, and preliminary biochemical studies.
Appl Environ Microbiol 2000;66:92 – 7.
Schroeder WH, Dobson M, Kane DM, Johnson ND. Toxic trace-
elements associated with airborne particulate matter, a review. Int
J Air Pollut Control Hazard Waste Manag 1987;37:1267 – 85.
Senesse P, Justrabo E, Boschi F, Goegebeur G, Collet E, Boutron MC,
et al. Cronkhite–Canada syndrome and arsenic poisoning: fortu-
itous association or new etiological hypothesis? Gastroentérol
Clin Biol 1999;23:399 – 402.
Shaw D. Mobility of arsenic in saturated, laboratory test sediments
under varying pH conditions. In: Yong YN, Thomas HR, editors.
Geoenvironmental engineering: integrated management of
groundwater and contaminated land Proceedings of the 4th
BGA geoenvironmental engineering conference, Stratford-on-
Avon, UK June 2004. London7 Thomas Telford; 2004. p. 142 – 50.
Sheppard SC. Summary of phytotoxic levels of soil arsenic. Water Air
Soil Pollut 1992;64:539 – 50.
Sidoli O’Connor C, Lepp NW, Edwards R, Sunderland G. The
combination of electrokinetic remediation and phytoremediation
to decontamination metal-polluted soils: A laboratory-scale feasi-
bility study. Environ Monit Assess 2003;84:141 – 85.
Slimak M, Charles D. Environmental pathways of exposure to 129
priority pollutants. J Toxicol Clin Toxicol 1984;21:39 – 63.
Smedley PL, Kinniburgh DG. A review of the source, behavior and
distribution of arsenic in natural waters. Appl Geochem
2002;17:517 – 68.
Smith LA, Means JL, Chen A, Alleman B, Chapman CC, Tixier JS Jr,
et al. Remedial options for metals-contaminated sites. Boca Raton,
FL7 Lewis Publishers; 1995.
Smith AL, Lopipero PA, Bates MN, Steinmaus CM. Arsenic
epidemiology and drinking water standards. Science 2002;
296:2145 – 6.
Squibb KS, Fowler BA. The toxicity of arsenic and its compounds.
In: Fowler BA, editor. Biological and environmental effects of
arsenic. Amsterdam7 Elsevier; 1983. p. 233 – 69.
Stephens RW, Brudermann GE, Morris PI, Hollick MS, Chalmers JD.
Value assessment of the Canadian pressure treated wood industry
Report to Canadian Forest Service; 1994.
Stephens RW, Brudermann GE, Konasewich DE. Summary of the
results of Environment Canada’s 2000 program for the Canadian
wood preservation industry Final report Prepared for Environment
Canada; 2001.
Stoeppler M, Nurnberg HW. Comparative studies on trace metal
levels in marine biota III Typical levels and accumulation of
toxic trace metals in muscle tissue and organs of marine organisms
from different European seas. Ecotoxicol Environ Saf 1979;3:
335 – 51.
Styblo M, Razo LMD, Vega L, Germolec DR, LeCluyse EL, Hamil-
ton GA, et al. Comparative toxicity of trivalent and pentavalent
inorganic and methylated arsenicals in rat and human cells. Arch
Toxicol 2000;74:289 – 99.
Sun X, Doner HE. An investigation of arsenate and arsenite bonding
structures on goethite by FTIR. Soil Sci 1996;161:865 – 72.
Thomas DJ, Styblo M, Lin S. The cellular metabolism and systemic
toxicity of arsenic. Appl Pharmacol 2001;176:127 – 44.
Tokunuga S, Hakuta T. Acid washing and stabilization of an artificial
arsenic-contaminated soil. Chemosphere 2002;46:31 – 8.
Tseng WP, Chu HM, How SW, Fong JM, Lin CS, Yeh S. Prevalence
of skin cancer in an endemic area of chronic arsenicism in Taiwan.
J Natl Cancer Inst 1968;40:453 – 63.
USDHHS (US Department of Health and Human Services). Toxico-
logical profile for arsenic. Atlanta7 Public Health Service, Agency
for Toxic Substances and Disease Registry; 2000.
Vangronsveld J, Ruttens A, Clijsters H. The use of cyclonic ashes of
fluidized bed burning of coal mine refuse for long term immobi-
lization of metals in soils. In: Sajwan KS, Alva AK, Keefer RF,
editors. Biogeochemistry of trace elements in coal and coal com-
bustion by-products. New York7 Plenum/Kluwer Academic Pub-
lishing; 1999. p. 223 – 33.
Verkleij JAC, Karenlampi S, De Koe T, Mench M, Vangronsveld J.
Strategies for rehabilitation of metal polluted soils: in situ phytor-
emediation, immobilization and revegetation, a comparative study
(PHYTOREHAB), final report ENV4-CT95-083, EU DGXII en-
vironment and climate programme. Amsterdam7 Vrije Universi-
teit; 1999.
 S. Wang, C.N. Mulligan / Science of the Total Environment 366 (2006) 701–721
Wagemann R, Snow NB, Rosenberg DM, Lutz A. Arsenic in sedi-
ments, water and aquatic biota from lakes in the vicinity of
Yellowknife, Northwest Territories Canada. Arch Environ Contam
Toxicol 1978;7:169 – 91.
Walsh PR, Duce RA, Fasching JL. Considerations of the enrichment
sources and flux of arsenic in the troposphere. J Geophys Res
1979;84:1719 – 26.
Wang S, Mulligan CN. Arsenic in Canada. Proceedings of the 57th
Canadian geotechnical conference and 5th joint-IAH-CNS/CGS
conference, Quebec City, Canada Session 1D, environmental
geotechnology I; 2004a. p. 1 – 8 October.
Wang S, Mulligan CN. Rhamnolipid foam enhanced remediation of
cadmium and nickel contaminated soil. Water Air Soil Pollut
2004b;157:315 – 30.
Wang S, Mulligan CN. Effect of natural organic matter on arsenic
release from soils and sediments into groundwater. Environ Geo-
chem Health, in press.
Warren HV, Delavault RE, Barakso J. The role of arsenic as a
pathfinder in biogeochemical prospecting. Econ Geol Bull Soc
Econ Geol 1964;59:1381 – 6.
Warren GP, Alloway BJ, Lepp NW, Singh B, Bochereau FJM, Penny
C. Field trials to assess the uptake of arsenic by vegetables from
contaminated soils and soil remediation with iron oxides. Sci Total
Environ 2003;311:19 – 33.
Waychunas GA, Rea BA, Fuller CC, Davis JA. Surface chemistry of
ferrihydrite: part 1 EXAFS studies of the geometry of coprecipi-
tated and absorbed arsenate. Geochim Cosmochim Acta
1993;57:2251 – 69.
Webster JG. Arsenic. In: Marshall CP, Fairbridge RW, editors.
Encyclopaedia of geochemistry. London7 Chapman Hall; 1999.
p. 21 – 2.
Webster JG, Nordstrom DK. Geothermal arsenic: the sources, trans-
port and fate of arsenic in geothermal systems. In: Welch AH,
Stollenwerk KG, editors. Arsenic in ground water: geochemistry
and occurrence. Boston7 Kluwer Academic Publishers; 2003.
p. 101 – 25.
White DE, Hem JD, Waring GA. Chemical composition of sub-
surface waters. In: Fleisher M, editor. Data of geochemistry, 6th
ed. Paper. US Geological Survey Professional; 1963.
721
WHO. Guidelines for drinking water quality, 2nd ed. Recommenda-
tions. World Health Organization; 1993.
Wilke JA, Hering JG. Rapid oxidation of geothermal arsenic(III) in
stream waters of the eastern Sierra Nevada. Environ Sci Technol
1998;32:657 – 62.
Wong HKT, Gauthier A, Nriagu JO. Dispersion and toxicity of metals
from abandoned gold mine tailings at Goldenville, Nova Scotia,
Canada. Sci Total Environ 1999;228:35 – 47.
Woolsan EA. Man’s perturbation of the arsenic cycle. In: Lederer
RJ, Fensterheim RJ, editors. Arsenic: industrial, biomedical and
environmental perspectives Proceedings of the arsenic sympo-
sium, Gaithersburg, MD. New York7 Van Nostrand Reinhold;
1983.
Wysocki R, Chery CC, Wawrzycka D, van Hulle M, Cornelis R,
Thevelein JM, et al. The glycerol channel Fps1p mediates the
uptake of arsenite and antimonite in Saccharomyces cerevisiae.
Mol Microbiol 2001;40:1391 – 401.
Xu H, Allard B, Grimvall A. Influence of pH and organic substance
on adsorption of As(V) on geologic materials. Water Air Soil
Pollut 1988;40:293 – 305.
Yan XP, Kerrich R, Hendry MJ. Distribution of arsenic(III),
arsenic(V) and total inorganic arsenic in porewaters from a thick
till and clay-rich aquitard sequence, Saskatchewan, Canada. Geo-
chim Cosmochim Acta 2000;64:2637 – 48.
Yong RN, Mulligan CN. Natural attenuation of contaminants in soils.
Boca Raton7 CRC Press; 2004.
Zagury GJ, Samson R, Louise D. Occurrence of metals in soil and
ground water near chromated copper arsenate-treated utility poles.
J Environ Qual 2003;32:507 – 14.
Zheng J, Holger H, Brian D, Stephen DM. Speciation of arsenic in
water, sediment, and plants of the Moira watershed, Canada, using
HPLC coupled to high resolution ICP-MS. Anal Bioanal Chem
2003;377:14 – 24.
Zobrist J. Mobilization of arsenite by dissimilatory reduction of
adsorbed arsenate. Environ Sci Technol 2000;34:4747 – 53.
Zoltai SC. Distribution of base metals in peat near a smelter at Flin
Flon, Manitoba. Water Air Soil Pollut 1988;37:217 – 28.
Zou BJ. Arsenic in soil. Turangxue Jinzhan 1986;14:8 – 13 [in
Chinese].