Environmental Pollution 145 (2007) 793e799 www.elsevier.

com/locate/envpol

n, Mexico Arsenic in the soils of Zimapa

Lois K. Ongley a,*,1, Leslie Sherman b, Aurora Armienta c, Amy Concilio d, Carrie Ferguson Salinas e,2
Oak Hill High School, P.O. Box 400, Sabattus, ME 04280, USA Department of Chemistry, Washington College, 300 Washington Avenue, Chestertown, MD 21620, USA c Instituto de Geof sica, UNAM, Me xico D.F. 04510, Mexico d Department of Earth, Ecological, and Environmental Sciences, University of Toledo, Toledo, OH 43606, USA e Department of Agronomy and Environmental Management, Louisiana State University, Baton Rouge, LA 70803, USA
b a

Received 15 December 2004; accepted 1 May 2006

Much of the arsenic is relatively immobile but presents long-term source of arsenic.
Abstract n Valley range from 4 to 14 700 mg As kg1. Soil arsenic conArsenic concentrations of 73 soil samples collected in the semi-arid Zimapa centrations decrease with distance from mines and tailings and slag heaps and exceed 400 mg kg1 only within 500 m of these arsenic sources. Soil arsenic concentrations correlate positively with Cu, Pb, and Zn concentrations, suggesting a strong association with ore minerals known to exist in the region. Some As was associated with Fe and Mn oxyhydroxides, this association is less for contaminated than for uncontaminated samples. Very little As was found in the mobile water-soluble or exchangeable fractions. The soils are not arsenic contaminated at depths greater than 100 cm below the surface. Although much of the arsenic in the soils is associated with relatively immobile solid phases, this represents a long-term source of arsenic to the environment. 2006 Elsevier Ltd. All rights reserved.
Keywords: Arsenic; Mining; Trace metals; Pollution; Smelter; Sequential extraction

1. Introduction 1.1. Arsenic in mining regions Elevated soil arsenic concentrations due to mining and smelting have been reported around the world (see for example, Davis et al., 1996; Filippi et al., 2004; Ghosh et al., 2004; La Force et al., 2000; Lombi et al., 2000; Matera et al., 2003; Moore et al., 1988; Nriagu, 1994; Razo et al., 2004; Stu ben et al., 2001). Soil arsenic concentrations in these

* Corresponding author. Tel.: +1 207 948 3131. E-mail address: loisongley@earthlink.net (L.K. Ongley). 1 Associate Professor of Chemistry, Unity College, Unity, ME 04988 USA; Formerly at Bates College, Lewiston, ME, USA. 2 Formerly at Department of Geology, Centenary College, Shreveport, LA, USA. 0269-7491/$ - see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.envpol.2006.05.014

contaminated locations range from 500 to 17 000 mg kg1. In most cases, arsenic concentrations decrease with increasing distance from tailings piles and impoundments and from a et al., 2001; Magalh~ active or retired smelters (Garc aes et al., 2001; Nriagu, 1994; Razo et al., 2004). Arsenic concentrations in uncontaminated soils average 5e6 mg kg1 with a range of 0.1e40 mg kg1 (NAS, 1977) although high naturally occurring arsenic concentrations have been reported (Hansen et al., 2001; Lalor et al., 1999). Arsenic is known to adsorb to iron and manganese oxyhydroxides, clays, carbonates and organic matter (Cheng et al., 1999; Dixit and Hering, 2003; Goldberg, 2002; Goldberg and Glaubig, 1988; Lin and Puls, 2000; Manning et al., 1998; Romero et al., 2004; Thanabalasingam and Pickering, 1986). In soils contaminated by mining activities, arsenic has been found to be primarily associated with amorphous iron oxyhydroxides in soils (Ahumada et al., 2004; Filippi et al., 2004;

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Ghosh et al., 2004; Lombi et al., 2000; Matera et al., 2003; Van Herreweghe et al., 2003). Arsenic can also form secondary minerals, such as scorodite and suldic minerals, or can co-precipitate with other minerals (Fendorf et al., 2004; Filippi et al., 2004; Moore et al., 1988; Reynolds et al., 1999).

(Armienta et al., 1997a; Ongley et al., 2001). Arsenic-related health impacts have been found in the region, including hypopigmentation, hyperpigmentation, and hyperkerathosis (Armienta et al., 1997b). 1.3. Scope of this study

1.2. Arsenic in Zimapa n, Mexico n, Pb, Zn, and Ag minerals have been extensively In Zimapa az, 1995). The ore at Zimapa n mined since about 1576 (D sometimes contains an appreciable amount of arsenic up to 16 wt% (Ongley et al., 2001). The dominant arsenic-bearing mineral is arsenopyrite, however, some ore bodies include tennantite, lead sulfosalts, and lollingite; the most common arsenic-bearing secondary mineral is scorodite (Armienta et al., 2001). Large tailings piles (up to 1.9 wt% As) dominate the land n River (Fig. 1). Fresh tailings are a dry scape along the Tolima gray powder ne enough to form aeolian ripples on the ank of the tailings. Weathered tailings are red-orange in color and often display white and yellow crystallization on the surface. While there are no smelters currently in operation in n, tall smokestacks and slag piles still mark a few of Zimapa the former smelter sites. n, elevated groundwater arsenic concentrations In Zimapa exceed the WHO drinking water standard more than 10-fold

The focus of this study was to determine the distribution of n. We hypothesize that arsenic in the surface soils of Zimapa soil arsenic concentrations will be highest in the immediate vicinity of mines, tailings and former smelter sites. Soil arsenic concentrations should decrease with depth reecting the historic record as well as indicating minor movement of arsenic down the proles. We also hypothesize that arsenic should be found primarily associated with metal oxyhydroxides or with refractory minerals such as arsenopyrite.
2. Materials and methods 2.1. Site description
n is located in the state of Hidalgo, Mexico, about 150 km north of Zimapa Mexico City at an elevation of about 1770 m. PbeZneAg ore is found as massive sulde skarn deposits in the limestones to the north and west of town and in occasional hydrothermal veins in the extreme eastern portion of the valley. The soils of the region are predominately regosols and lithosols developed from fresh alluvium and rock, respectively (INEGI, 2005). Soil thickness

n Valley, Mexico (Group A, open circles; Group B, open triangles; Group C, closed circles; Group D, closed Fig. 1. Soil arsenic concentration in the Zimapa triangles). The locations of sequential extraction (SE) and prole (P) samples are indicated. Mines are indicated by an asterisk, tailings by gray polygons.

L.K. Ongley et al. / Environmental Pollution 145 (2007) 793e799 ranges from <10 cm to about 100 cm but the soil is discontinuous and generally thin (INEGI, 2005). n River is the only large perennial stream in the region; most of The Tolima its discharge near the town consists of wastewater. Natural springs feed the river downstream of the mines to the west of town. The climate is semiarid, with an annual rainfall of 400 mm and annual evapotranspiration rates of 500e600 mm (INEGI, 2005).

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Table 1 Optimized procedure for sequential extraction of arsenic from various fractions of the soils and sediments (1 g sample) Fraction Water soluble Exchangeable Carbonate-bound Extraction uid 8 mL deionized water 8 mL 1 M MgCl2 8 mL 1 M sodium acetate adjusted to pH 5.0 with CH3COOH 20 mL 0.04 M NH2OH$HCl in 25% (v/v) CH3COOH Extraction time 30 min 60 min 10 h

2.2. Sample collection

During 1996e1999 soil samples were collected from 73 locations in the n region (Fig. 1) and brought back to the US for analysis. Sample loZimapa cations were plotted on base maps in the eld. Some locations were veried using real-time corrected GPS. Soil and tailings samples were taken by trowel or collected by a gloved hand. Prior to collecting a soil sample, any surface vegetation was cleared away. To sample soil near smelter slag piles, 16 samples were collected from a small area within 5e50 m of two large smelter slag piles. The averages of the data collected from these 16 samples are reported for each metal analyzed. A soil sample presumed to be weathered slag was collected from the top of the largest slag pile. Prole samples were taken from four areas to dene the changes in arsenic concentrations with depth (Fig. 1). Two soil proles were taken from outside the town, one to the east (San Juan, 60 cm depth) and one to the west (Barron, 60 cm depth). In addition, soil proles were taken from a construction site in the town center (Banamex, 120 cm depth) and from a trench dug for a water line along a road originally constructed in the 16th century (Via Real, 120 cm depth). The Banamex and Via Real sites are within 500 m of an arsenic source, either former smelters or tailings. All samples were placed into Whirl-pak bags and stored in a box while in Mexico, then stored in a 4  C cooler at Bates College, Lewiston, ME, USA until sent out for analysis. Prior to analysis samples were air dried, and pebbles and obvious rootlets were removed. Fe and Mn (hydro)oxide-bound Organic-bound/ suldes Step 1

6 h at 96  C

Step 2 Step3

Step 4 Residual

3 mL 0.02 M HNO3 and 5 mL of 30% H2O2 at pH 2 for 2 h at 85  C 3 mL 30% H2O2 adjusted to pH 2 for 3 h at 85  C 5 mL 3.2 M NH4OOCH3 in 20% (v/v) HNO3 at ambient temperature for 30 min diluted to 20 mL Calculated by difference between above and total As measured by ICP-AES (Activation Labs, Ancaster, Ontario)

3. Results and discussion This study uses the following categorization scheme for total As concentrations: uncontaminated (Group A, As < 40 mg kg1), slightly contaminated (Group B, 41 < As < 400 mg kg1), contaminated (Group C, 401 < As < 4000 mg kg1) and very contaminated (Group D, As > 4001 mg kg1). The cut-off for uncontaminated samples, Group A samples, is based on the soils guideline of 40 mg kg1 suggested by (Dudka and Miller (1999)). 3.1. Total arsenic in soils The total arsenic in the soil surface samples ranged from 4 to 14 700 mg As kg1. The majority of soil samples were either uncontaminated (42%) or slightly contaminated (41%) with arsenic; the median arsenic concentration in the soils was 52 mg kg1. Sixteen percent of soils fell into Groups C and D, the most contaminated soil was the developing soil on top of the slag heap. Soil arsenic was signicantly negatively correlated with distance from known arsenic sources ( p < 0.01; Table 2). Uncontaminated or slightly contaminated soils, with a few exceptions, were at least 1000 m from tailings, slag piles and the massive sulde ore deposits. Uncontaminated soils dominate the eastern third of the basin, where the bedrock is composed of igneous rocks and where arsenic concentrations are low in water samples (Armienta et al., 1997a). Signicant particulate deposition from wind-blown tailings material and/or dry deposition from former smelters apparently did not reach these soils. Most Group B soils were found more than 500 m and

2.3. Chemical analysis

Major and minor metals in the samples were measured either by instrumental neutron activation analysis (INAA) at Activation Laboratories, Ancaster, Ontario, Canada and/or by inductively coupled plasma-optical emission spectrometry (ICP-OES) analyses of strong acid soil digests at the same lab. There were 58 soil samples with complete data sets including the surface sample from each prole. A sequential extraction was conducted on six surcial soil samples representative of the various geographical regions of the area and on a soil prole (Banamex). A tailings sample was run for comparison. Each sample was initially sieved (<2.36 mm) in order to remove the largest particles. The arsenic was separated into the following operationally dened fractions: water soluble, exchangeable, bound to carbonates, bound to iron and manganese oxyhydroxides, and bound to organic matter/associated with non-refractory suldes. The extraction is based on the method of Tessier et al. (1979), with slight deviations to optimize the extraction times (Table 1). Three 1 g replicates of each sample were extracted as listed in Table 1. After each extraction, the solution was separated from the solid by centrifuge at 10 000 rpm (12 000 g) for 30 min. The supernatant was ltered using Cameo 25AS Acetate lters with a pore size of 0.45 mm. The residue from each extraction was washed with 8 mL of deionized water. All extracts were stored at 4  C in polyethylene centrifuge tubes. Each extract solution was analyzed by ICP-OES at Bates College or at Rhode Island Analytical Laboratory, or by graphite furnace Atomic Absorption (AA) at A&L Laboratories (Auburn, Maine). Apparent sample and/or analytical variability caused differences in some of the replicates of the sequential extractions. To minimize the impact of outliers, the median rather than the mean was used as a measure of central tendency. The percentages of each fraction were calculated using the total arsenic concentrations for the soil obtained by INAA at Activation Laboratories. Total organic matter was measured on these soils by loss on ignition at 450  C (Nelson and Sommers, 1996).

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Table 2 n Rank correlation coefcients for metals in the soils (n 58) of the Zimapa Valley As Pb Zn Cu Ca Fe Mn

As 1 Pb 0.806 1 Zn 0.705 0.785 1 Cu 0.485 0.785 0.578 1 Ca 0.318 0.205 0.105 0.070 1 Fe 0.088 0.082 0.094 0.422 L0.606 1 Mn 0.126 0.254 0.349 0.438 L0.447 0.555 1 Distance L0.606 L0.452 L0.349 0.215 0.129 0.215 0.139 Coefcients in bold are signicant at the 0.01 level, those underlined are signicant at the 0.05 level. The coefcients were calculated using web-based statistical tools (Boersma, 2005).

less than 3500 m from tailings, mines and smelters. These soils appear to have received some particulate deposition from smelters and tailings. Soil arsenic concentrations exceeding 400 mg kg1 were concentrated in a radius of about 500 m around mines, tailings heaps, and former smelters. The very contaminated soils were taken in the vicinity of the slag heaps or from an arroyo (Arroyo Santa Maria) that drains a process wastewater reservoir from the San Miguel Nuevo tailings, where the aqueous arsenic concentration is about 0.4 mg l1; the ne gray windblown tailings particles are evident around the arroyo. Indeed one of the samples was originally taken because of its similar appearance to the nearby tailings, 400 m away; it had an arsenic concentration of 30 000 mg kg1. (This sample was not included in the correlations.) The developing soil on top of one slag heap was extremely arsenic rich (14 700 mg kg1). 3.2. Arsenic correlation to other metals Rank correlation coefcients were calculated for As with Ca, Cu, Fe, Mn, Pb, and Zn (Table 2). Arsenic was signicantly correlated with Cu, Pb, and Zn ( p < 0.01) and Ca ( p < 0.05). Upon examination of a plot of As vs. Ca, the correlation seems fortuitous and due simply to the fact that at high Ca concentrations, the As concentrations are constant (Fig. 2a). This is distinctly different from the graphs of As with Cu, Pb and Zn (Fig. 2b). There is no signicant correlation of As with Fe. The relationships of As with Cu, Zn, and Pb, as well the signicant correlation between these metals suggest that much of the arsenic in the soils is from primary minerals of the local ores and tailings, as was found in a neighboring Mexican mining area (Razo et al., 2004). The semi-arid climate likely minimized the weathering of these minerals. 3.3. Arsenic speciation in surcial samples n area is relatively immoMost As in the soils of the Zimapa bile, bound to iron and manganese oxyhydroxides, organic matter, and carbonates or found in the residual mineral fraction, i.e. in refractory minerals. In each sample, the soluble and exchangeable fractions have low to undetectable arsenic

concentrations (<1%). A difference in speciation was found between uncontaminated soils, slightly contaminated soils, and severely contaminated tailings (Table 3). Generally, Fe/ Mn oxyhydroxide-bound As was the largest fraction (64%) in uncontaminated soils. A signicant portion was in the organic (20%) and carbonate (10%) fractions and a smaller amount in the residual fraction (6%). In contrast, in the Group B samples the largest percentage of arsenic was found in the residual fraction (52%). The Group B samples also had 34% of arsenic associated with Fe and Mn oxyhydroxides and some with the organic matter (22%) and carbonate (2%) fractions. The most extreme was the tailings sample (in Group D) e 95% of the arsenic was in the residual fraction. The strong association of arsenic with Fe and Mn oxyhydroxides in both the Group A and B soils is in agreement with the ndings of the distribution of arsenic in soils of uncontaminated and contaminated regions (Ahumada et al., 2004; Filippi et al., 2004; Ghosh et al., 2004; Lombi et al., 2000; Matera et al., 2003; Van Herreweghe et al., 2003). This arsenic, which has been shown to bind by ligand exchange (Manning et al., 1998; Savage et al., 2000) is relatively immobile. Signicant release of this arsenic due to reductive dissolution of the Fe and n because of the semiMn oxyhydroxides is unlikely in Zimapa arid climate. The sample with the greatest organic sorbed fraction, an agricultural soil, had the highest organic matter content. This fraction should also be fairly stable, but the organic matter will decompose slowly over time. The extraction for this fraction also measures some suldes, and so the organic fraction may be overestimated. Although As has been shown to bind to organic matter in the laboratory (Thanabalasingam and Pickering, 1986), very few eld studies have found organically bound As in soils (Lombi et al., 2000). A small amount of As was bound to carbonates, another fraction that should be fairly n (Romero et al., 2004). stable in Zimapa The major presence of arsenic in the residual phases in the slightly contaminated soils and tailings suggests that much of the arsenic remains in primary and secondary arsenic-containing z and Armienta, minerals originating from ores or tailings (Mende 2003). The strong correlation of soil arsenic with Cu, Pb, and Zn n discussed above, as well as the ore composition in the Zimapa area supports this nding. This fraction of arsenic is very immobile, especially given the semi-arid climate and the carbonate a buffered soils and sediments (pH 6e8) of the region (Garc et al., 2001). However, in the presence of tailings leachate, ore process water, or municipal wastewater, these minerals may dissolve releasing the arsenic. In any case, the residual material represents a long-term source of arsenic to the environment of n as the minerals are slowly oxidized, especially in the exZimapa tremely contaminated tailings. 3.4. Arsenic in soil proles The soil proles included an uncontaminated Group A soil (San Juan), a slightly contaminated Group B soil (Barron) and two contaminated soils (Banamex and Via Real) (Figs. 1 and 3). San Juan, the site most removed from any arsenic source, had less than 40 mg kg1 arsenic throughout the prole. Barron,

L.K. Ongley et al. / Environmental Pollution 145 (2007) 793e799

797

(a)
100000 Fe 10000 Ca

(b)
100000 Cu 10000 Pb Zn

Arsenic (mg/kg)

Arsenic (mg/kg)

1000

1000

100

100

10

10

10

15

20

25

30

10

100

1000

10000

100000

Calcium or Iron (wt

Metal (mg/kg)

Fig. 2. (a) Arsenic plotted as a function of Fe and Ca concentrations for the soil samples. (b) Arsenic in soils plotted as a function of the metals: Cu, Pb and Zn.

west of town, had slightly elevated arsenic concentrations (59 mg kg1) at the surface. The Via Real prole, which had surface arsenic concentration of 640 mg kg1, was only 100 m from tailings. The Banamex prole, located in a construction site, also had elevated arsenic in the layer 20 cm from the surface (880 mg kg1). The nearest old smelter was less than 100 m away and so the contamination is likely due to smelter particulate deposition. The surface layer was not sampled for the prole, as the material appeared to be construction ll. In each prole, arsenic concentrations decrease with depth within the rst 50 cm, most dramatically for proles within arsenic-inuenced zones (Fig. 3). Below this depth, the soils were uncontaminated or only slightly contaminated. The prole with surface contamination of arsenic suggests that some movement of arsenic may have occurred down the proles due to leaching perhaps from garden irrigation. This urban recharge has high arsenic concentrations, up to at least 0.3 mg L1, as well as the capability to dissolve some soil arsenic and carry it slightly deeper (Ongley et al., 1999).
Table 3 Arsenic sequential extraction results Sample Surface Tenguedho San Pedro La Perla III Ojo de Agua El Muhi San Juan San Miquel Nuevo Proles Banemex Banemex Banemex Banemex 40 cm 60 cm 1m 1.2 m Water-soluble (%) (range) nd nd nd <1 (nde<1) nd <1 (nde<1) nd 1.2 (1.0e1.3) <1 (nde2.4) <1 (nde2.9) nd Exchangeable (%) (range) nd nd nd nd nd <1 (nde<1) <1 (nde<1) <1 (nde<1) 2.6 (<1e2.8) nd <1 (nde<1)

3.5. Arsenic speciation in soil proles In the contaminated Banamex soil prole, as with the contaminated surface soils, most of the As was associated with the residual fraction. The percentage of As associated with the residual fraction decreased with depth in the prole, while the As percentage in the Fe and Mn oxyhydroxide fraction increased. These two Fe-rich fractions may explain the lack of correlation of As with total Fe and with Mn. The high level of residual arsenic in the top layer most likely reects the original smelter dry deposition deposits, some of which has leached down the prole to adsorb to or co-precipitate with secondary Fe and Mn oxyhydroxides. In the oxidizing conditions of the soil, these oxyhydroxides are stable. In the event of anaerobic conditions, this As phase would likely be mobilized by reduction to As(III). Since the total As concentration at 120 cm in the soil is only slightly contaminated and is in mineral form or bound to minerals, it is unlikely to leach to the groundwater.

Carbonate (%) (range) nd 16 3.5 24 2.5 1.3 <1 1.1 9.2 6.3 8.2

Fe/Mn bound (%) (range) 102 40 100 62 41 28 2 17 34 28 47 (3.3e200) (34e60) (45e140) (17e92) (18e54) (<1e33) (1.2e2.1) (<1e22) (31e65) (<1e33) (20e49)

Organic (%) (range) nd 20 73 19 2.7 18 <1 4.8 5.4 <3 24

Residual (%) 2 24 76 6 54 51 95 75 48 62 20

Total As (mg/kg) 6 10 11 26 44 150 20 000 250 74 45 37

(nde31) (3.4e3.6) (nde32) (nde2.8) (nde2.4)

(20e24) (13e91) (17e21) (1.8e54) (12e65) (<1e1.7) (3.8e7.2) (5.4e14) (<3e4.4) (nde36)

(nde5.7) (6.1e18) (2.8e6.8) (4.2e35)

The percent of arsenic in each fraction is listed using the median of all measurements. After our samples had been destroyed, Keon et al. (2001) published a sequential extraction technique for arsenic that might have been more appropriate for the uncontaminated samples.

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Arsenic (mg/kg)
10 0 100 1000

Peter Beeson developed the Geographic Information System database. Samples and data were collected by more than n over the course of the 45 members of Team REU Zimapa program. References

20

40

60

80

Banamex Barron San Juan Via Real

100

120

Fig. 3. Arsenic concentration proles with depth from ve locations.

4. Conclusions n The spatial distribution of arsenic in the soils of the Zimapa Valley is highly inuenced by the mining and ore processing activities of the past four centuries. The most contaminated area is concentrated along the southern boundary of town near the tailings along the river. Soil contamination generally decreases with distance from a known arsenic source. In general, soil arsenic concentration decreases with depth in the prole. There was no signicant correlation between As and Fe in the soils. Arsenic is more abundant in residual fractions in areas of anthropogenic inuence, while in areas not likely contaminated by smelter fumes or tailings material, a greater arsenic fraction was found to occupy non-residual fractions, such as the Fe/Mn bound fraction. In the arid environment of the n Valley, arsenic in both of these fractions is stable, Zimapa and so in the short term, this As is not very mobile. However, the soils may represent a long-term source of arsenic to the environment with weathering.

Acknowledgements This material is based on work supported by the National Science Foundation under Grant Nos. 9619810 and 9424249. Any opinions, ndings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reect the views of the National Science Foundation, Bates College, or the Univerisdad Nacional Autonoma de Mexico.

Ahumada, I., Escudero, P., Ascar, L., Mendoza, J., Richeter, P., 2004. Extractability of arsenic, copper, and lead in soils of a mining and agricultural zone in Central Chile. Commun. Soil Sci. Plant Anal. 35, 1615e1634. or, G., Armienta, M.A., Rodriguez, R., Aguayo, A., Ceniceros, N., Villasen n, Cruz, O., 1997a. Arsenic contamination of groundwater at Zimapa Mexico. Hydrogeol. J. 5, 39e46. Armienta, M.A., Rodriguez, R., Cruz, O., 1997b. Arsenic content in hair of n, Me xpeople exposed to natural arsenic polluted groundwater at Zimapa ico. Bull. Environ. Contam. Toxicol. 59, 583e589. guez, R., Ongley, L.K., Mango, H., or, G., Rodr Armienta, M.A., Villasen 2001. The role of arsenic-bearing rocks in groundwater pollution at n Valley, Me xico. Environ. Geol. 40, 571e581. Zimapa Boersma, P., 2005. Rank correlation coefcients. <www.fon.hum.uva.nl/Service/Statistics/RankCorrelation_coefcient.html> (accessed 11.08.05.). Cheng, L., Fenter, P., Sturchio, N., Zhong, Z., Bedzyk, M., 1999. X-ray standing wave study of arsenite incorporation at the calcite surface. Geochim. Cosmochim. Acta 63, 3153e3157. Davis, A., Ruby, M., Bloom, M., Schoof, R., Freeman, F., Bergstrom, P., 1996. Mineralogic constraints on the bioavailability of arsenic in smelterimpacted soils. Environ. Sci. Technol. 30, 392e399. az, L., 1995. A simultaneous view of history, the creation of a hypermedia D database. LEONARDO 28, 257e264. Dixit, S., Hering, J., 2003. Effects of arsenate reduction and iron oxide transformation on arsenic mobility. Environ. Sci. Technol. 37, 4182e4189. Dudka, S., Miller, W.P., 1999. Permissible concentrations of arsenic and lead in soils based on risk assessment. Water Air Soil Pollut. 113, 127e132. Fendorf, S., La Force, M., Li, G., 2004. Temporal changes in soil partitioning and bioaccessibility of arsenic, chromium, and lead. J. Environ. Qual. 33, 2049e2055. Filippi, M., Golia, V., Pertold, Z., 2004. Arsenic in contaminated soils and anthropogenic deposits at the Mokrsko, Roundy, and Kasperske Hory gold deposits, Bohemiam Massif (CZ). Environ. Geol. 45, 716e730. a, A., Armienta, M.A., Cruz, O., 2001. Sources, distribution and fate of Garc n, Me xico. In: Acreman, M.C. arsenic along the Toliman river, Zimapa (Ed.), Hydro-ecology: Linking Hydrology and Aquatic Ecology. IAHS Publication 266, pp. 57e64. Ghosh, A.K., Sarkar, D., Nayak, D., Bhattacharyya, P., 2004. Assessment of a sequential extraction procedure for fractionation of soil arsenic in contaminated soils. Arch. Agron. Soil Sci. 50, 583e591. Goldberg, S., 2002. Competitive adsorption of arsenate and arsenite on oxides and clay minerals. Soil Sci. Soc. Am. J. 66, 413e421. Goldberg, S., Glaubig, R., 1988. Anion sorption on a calcareous, montmorillonitic soil e arsenic. Soil Sci. Soc. Am. J. 52, 1297e1300. Hansen, H., Larssen, T., Seip, H.M., Vogt, R.D., 2001. Trace metals in forest soils at four sites in southern China. Water Air Soil Pollut. 130, 1721e1726. stica Geograph ca e Informa tica, digINEGI, 2005. Instituto Nacional de Estat ital Data and maps of Mexico. <www.inegi.gob.mx/inegi/default.asp> (accessed 05.08.05.). Keon, N., Swartz, C., Brabander, D., Harvery, C., Hemond, H., 2001. Validation of an arsenic sequential extraction method for evaluating mobility in sediments. Environ. Sci. Technol. 35, 2778e2784. La Force, M., Hansel, C., Fendorf, S., 2000. Arsenic speciation, seasonal transformations, and co-distribution with iron in a mine waste-inuences Palustrine emergent wetland. Environ. Sci. Technol. 34, 3937e3943. Lalor, G., Rattray, R., Simpson, P., Vutchkov, M.K., 1999. Geochemistry of an arsenic anomaly in St. Elizabeth, Jamaica. Environ. Geochem. Health 21, 3e11.

Depth (cm)

L.K. Ongley et al. / Environmental Pollution 145 (2007) 793e799 Lin, Z., Puls, R., 2000. Adsorption, desorption and oxidation of arsenic affected by clay minerals and aging process. Environ. Geol. 39, 753e759. Lombi, E., Slettern, R.S., Wenzel, W., 2000. Sequentially extracted arsenic from different size fractions of contaminated soils. Water Air Soil Pollut. 124, 319e332. Magalh~ aes, V.F., Carvalho, C.E.V., Pfeiffer, W.C., 2001. Arsenic contamination and dispersion in the Engenho Inlet, Sepetiba Bay, SE, Brazil. Water Air Soil Pollut. 129, 83e90. Manning, B.A., Fendorf, S.E., Goldberg, S., 1998. Surface structures and stability of arsenic(III) on goethite: spectroscopic evidence for inner-sphere complexes. Environ. Sci. Technol. 32, 2383e2388. Matera, V., Le Hecho, I., Laboudigue, A., Thomas, P., Tellier, S., Astruc, M., 2003. A methodological approach for the identication of arsenic bearing phases in polluted soils. Environ. Pollut. 126, 51e64. ndez, M., Armienta, M.A., 2003. Arsenic phase distribution in Zimapa n Me mine tailings, Mexico. Geo. Int. 42, 131e140. Moore, J., Ficklin, W., Johns, C., 1988. Partitioning of arsenic and metals in reducing suldic sediments. Environ. Sci. Technol. 22, 432e437. NAS, 1977. Arsenic. National Academy of Sciences, Washington, DC. Nelson, D., Sommers, L., 1996. Total carbon, inorganic carbon and organic matter. In: Sparks, D.L. (Ed.), Methods of Soil Analysis, Part 3. Chemical Methods. SSSA Book Series No. 5. SSSA, Madison, WI, pp. 961e1010. Nriagu, J.O. (Ed.), 1994. Arsenic in the Environment. Part 1: Cycling and Characterization. John Wiley & Sons, New York. Ongley, L.K., Beeson, P., Rodriguez, R., Armienta, M.A., 1999. Groundwater n, Mexico. Ground Water Supow simulation of the urban area of Zimapa ply Issues in the Next Century. In: Proceedings of the Annual Meeting of the National Ground Water Association AGWESE, Nashville, TN, December 1999.

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Ongley, L.K., Armienta, M.A., Heggeman, K., Lathrop, A.S., Mango, H., Miller, W., Pickelner, S., 2001. Arsenic removal from contaminated water n Mining District, Mexico e a potential by the Soyatal Formation, Zimapa low-cost low-tech remediation system. Geochem. Explor. Environ. Anal. 1, 23e31. Razo, I., Carrizales, L., Castro, J., Diaz-Barriga, F., Monroy, M., 2004. Arsenic and heavy metal pollution of soil, water and sediments in a semi-arid climate mining area in Mexico. Water Air Soil Pollut. 152, 129e152. Reynolds, J., Naylor, D., Fendorf, S., 1999. Arsenic sorption in phosphateamended soils during ooding and subsequent aeration. Soil Sci. Soc. Am. J. 63, 1149e1156. vez, A., 2004. Arsenic sorption by Romero, F.M., Armienta, M.A., Carrillo-Cha n, carbonate-rich aquifer material, a control on arsenic mobility at Zimapa xico. Arch. Environ. Contam. Toxicol. 47, 1e13. Me Savage, K., Tingle, T., ODay, P., Waychunas, A., Bird, D., 2000. Arsenic speciation in pyrite and secondary weathering phases, Mother Lode Gold District, Tuolumne County, California. Appl. Geochem. 15, 1219e1244. Stu ben, D., Berner, Z., Kappes, B., Puchelt, H., 2001. Environmental monitoring of heavy metals and arsenic from AgePbeZn mining. A case study over two millennia. Environ. Monit. Assess. 70, 181e200. Tessier, A., Campbell, P.G.C., Bisson, M., 1979. Sequential extraction procedure for the speciation of particulate trace metals. Anal. Chem. 51, 844e850. Thanabalasingam, P., Pickering, W., 1986. Arsenic sorption by humic acids. Environ. Pollut. 12, 233e246. Van Herreweghe, S., Swennen, R., Vandescasteele, C., Cappuyns, V., 2003. Solid phase speciation of arsenic by sequential extraction in standard reference materials and industrially contaminated soil samples. Environ. Pollut. 122, 323e342.