Trace elements in organic- and iron-rich surficial fluids of the boreal zone: Assessing colloidal forms via dialysis and ultrafiltration

On-site size fractionation of about 40 major and trace elements (TE) was performed on waters from boreal small rivers and their estuaries in the Karelia region of North-West Russia around the “Vetreny Belt” mountain range and in Paanajärvi National Park (Northern Karelia). Samples were filtered in the field using a progressively decreasing pore size (5 μm, 2.5 (3) μm, 0.22 (0.45) μm, 100 kDa, 10 and 1 kDa) by means of frontal filtration and ultrafiltration (UF) techniques and employing in-situ dialysis with 10 and 1 kDa membranes followed by ICP-MS analysis. For most samples, dialysis yields a systematically higher (factor of 2-3) proportion of colloidal forms compared to UF. Nevertheless, dialysis is able to provide a fast and artefact-free in-situ separation of colloidal and dissolved components.Similar to previous studies in European subarctic zones, poor correlation of iron concentration with that of organic carbon (OC) in (ultra)filtrates and dialysates reflect the presence of two pools of colloids composed of organic-rich and Fe-rich particles. All major anions and silica are present as dissolved species (or solutes) passing through the 1-kDa membrane. Size-separation ultrafiltration experiments show the existence of larger or smaller pools of colloidal particles different for each of the considered elements.The effect of rock lithology (acidic versus basic) on the colloidal speciation of TE is seen solely in the increase of Fe and some accompanying TE concentrations in catchment areas dominated by basic rocks compared to granitic catchments. Neither the ultrafiltration pattern nor the relative proportions of colloidal versus truly dissolved TE are affected by the lithology of the underlying rocks: within ±10% uncertainty, the two colloidal (10 kDa-0.22 μm and 1-10 kDa) and the truly dissolved (<1 kDa) pools show no difference in percentage of TE distribution between two types of bedrock lithology. The same conclusion is held for organic- and Fe-rich waters. In contrast, landscape context analysis demonstrated slight dominance, for most TE affected by UF, of large-size colloids (10 kDa-0.22 μm) in rivers and streams and small-size colloids and truly dissolved fractions in swamp stagnant surface waters. This supports the existence of two pathways of colloids formation: during the plant litter degradation in wetland zones and at the redox front in river riparian zone.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

Trace element fractionation and transport in boreal rivers and soil porewaters of permafrost-dominated basaltic terrain in Central Siberia

The chemical status of ∼40 major and trace elements (TE) and organic carbon (OC) in pristine boreal rivers draining the basaltic plateau of Central Siberia (Putorana) and interstitial solutions of permafrost soils was investigated. Water samples were filtered in the field through progressively decreasing pore size (5 μm → 0.22 μm → 0.025 μm → 10 kDa → 1 kDa) using cascade frontal filtration technique. Most rivers and soil porewaters exhibit 2-5 times higher than the world average concentration of dissolved (i.e., <0.22 μm) iron (0.03-0.4 mg/L), aluminum (0.03-0.4 mg/L), OC (10-20 mg/L) and various trace elements that are usually considered as immobile in weathering processes (Ti, Zr, Ga, Y, REEs). Ultrafiltration revealed strong relationships between concentration of TE and that of colloidal Fe and Al. According to their partition during filtration and association with colloids, two groups of elements can be distinguished: (i) those weakly dependent on ultrafiltration and that are likely to be present as truly dissolved inorganic species (Li, Na, K, Si, Mn, Mo, Rb, Cs, As, Sb) or, partially (20-30%) associated with small size Fe- and Al-colloids (Ca, Mg, Sr, Ba) and to small (<1-10 kDa) organic complexes (Co, Ni, Cu, Zn), and (ii) elements strongly associated with colloidal iron and aluminum in all ultrafiltrates largely present in 1-100 kDa fraction (Ga, Y, REEs, Pb, V, Cr, Ti, Ge, Zr, Th, U). TE concentrations and partition coefficients did not show any detectable variations between different colloidal fractions for soil porewaters, suprapermafrost flow and surface streams. TE concentration measurements in river suspended particles demonstrated significant contribution (i.e., ?30%) of conventionally dissolved (<0.22 μm) forms for usually “immobile” elements such as divalent transition metals, Cd, Pb, V, Sn, Y, REEs, Zr, Hf, Th. The Al-normalized accumulation coefficients of TE in vegetation litter compared to basalts achieve 10-100 for B, Mn, Zn, As, Sr, Sn, Sb, and the larch litter degradation is able to provide the major contribution to the annual dissolved flux of most trace elements. It is hypothesized that the decomposition of plant litter in the topsoil horizon leads to Fe(III)-, Al-organic colloids formation and serves as an important source of elements in downward percolating fluids.     

Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Speciation and colloid transport of arsenic from mine tailings

In addition to affecting biogeochemical transformations, the speciation of As also influences its transport from tailings at inoperative mines. The speciation of As in tailings from the Sulfur Bank Mercury Mine site in Clear Lake, California (USA) (a hot-spring Hg deposit) and particles mobilized from these tailings have been examined during laboratory-column experiments. Solutions containing two common, plant-derived organic acids (oxalic and citric acid) were pumped at 13 pore volumes d⁻¹ through 25 by 500 mm columns of calcined Hg ore, analogous to the pedogenesis of tailings. Chemical analysis of column effluent indicated that all of the As mobilized was particulate (1.5 mg, or 6% of the total As in the column through 255 pore volumes of leaching). Arsenic speciation was evaluated using X-ray absorption spectroscopy (XAS), indicating the dominance of arsenate [As(V)] sorbed to poorly crystalline Fe(III)-(hydr)oxides and coprecipitated with jarosite [KFe₃(SO₄, AsO₄)₂(OH)₆] with no detectable primary or secondary minerals in the tailings and mobilized particles. Sequential chemical extractions (SCE) of <45 μm mine tailings fractions also suggest that As occurs adsorbed to Fe (hydr)oxides (35%) and coprecipitated within poorly crystalline phases (45%). In addition, SCEs suggest that As is associated with 1 N acid-soluble phases such as carbonate minerals (20%) and within crystalline Fe-(hydr)oxides (10%). The finding that As is transported from these mine tailings dominantly as As(V) adsorbed to Fe (hydr)oxides or coprecipitated within hydroxysulfates such as jarosite suggests that As release from soils and sediments contaminated with tailings will be controlled by either organic acid-promoted dissolution or reductive dissolution of host phases.     

Biogeochemical redox cycling of arsenic in mine-impacted lake sediments and co-existing pore waters near Giant Mine,Yellowknife Bay,Canada

Lacustrine sediments, submerged tailings, and their pore waters have been collected at several sites in Yellowknife Bay, Great Slave Lake, Canada, in order to investigate the biogeochemical controls on the remobilization of As from mining-impacted materials under different depositional conditions. Radiometric dating confirms that a mid-core enrichment of Pb, Zn, Cu and Sb corresponds to the opening of a large Au mine 60 a ago. This was evident even in a relatively remote site. Arsenic was enriched at mid-core, coincident with mining activity, but clearly exhibited post-depositional mobility, migrating upwards towards the sediment water interface (SWI) as well as down-core. Deep-water (15 m) Yellowknife Bay sediments that contain buried mine waste are suboxic, relatively organic-rich and abundant in microbes with As in pore waters and sediments reaching 585 μg/L and 1310 mg/kg, respectively. Late summer pore waters show equal proportions of As(III) and As(V) (16–415 μg/L) whereas late winter pore waters are dominated by As(III) (284–947 μg/L). This can be explained by As(III) desorption mechanisms associated with the conversion of FeS to FeS₂ and the reduction of As(V) to As(III) through the oxidation of dissolved sulfide, both microbially-mediated processes. Processes affecting As cycling involve the attenuating efficiency of the oxic zone at the SWI, sediment redox heterogeneity and the reductive dissolution of Fe(hydr)oxides by labile organic matter, temporarily and spatially variable.     

Evidence of microbially mediated arsenic mobilization from sediments of the Aquia aquifer, Maryland, USA

Sediments from the Aquia aquifer in coastal Maryland were collected as part of a larger study of As in the Aquia groundwater flow system where As concentration are reported to reach levels as high as 1072 nmol kg⁻¹, (i.e., ∼80 μg/L). To test whether As release is microbially mediated by reductive dissolution of Fe(III) oxides/oxyhydroxides within the aquifer sediments, the Aquia aquifer sediment samples were employed in a series of microcosm experiments. The microcosm experiments consisted of sterilized serum bottles prepared with aquifer sediments and sterilized (i.e., autoclaved), artificial groundwater using four experimental conditions and one control condition. The four experimental conditions included the following scenarios: (1) aerobic; (2) anaerobic; (3) anaerobic + acetate; and (4) anaerobic + acetate + AQDS (anthraquinone-2,6-disulfonic acid). AQDS acts as an electron shuttle. The control condition contained sterilized aquifer sediments kept under anaerobic conditions with an addition of AQDS. Over the course of the 27 day microcosm experiments, dissolved As in the unamended (aerobic and anaerobic) microcosms remained constant at around ∼28 nmol kg⁻¹ (2 μg/L). With the addition of acetate, the amount of As released to the solution approximately doubled reaching ∼51 nmol kg⁻¹ (3.8 μg/L). For microcosm experiments amended with acetate and AQDS, the dissolved As concentrations exceeded 75 nmol kg⁻¹ (5.6 μg/L). The As concentrations in the acetate and acetate + AQDS amended microcosms are of similar orders of magnitude to As concentrations in groundwaters from the aquifer sediment sampling site (127-170 nmol kg⁻¹). Arsenic concentrations in the sterilized control experiments were generally less than 15 nmol kg⁻¹ (1.1 μg/L), which is interpreted to be the amount of As released from Aquia aquifer sediments owing to abiotic, surface exchange processes. Iron concentrations released to solution in each of the microcosm experiments were higher and more variable than the As concentrations, but generally exhibited similar trends to the As concentrations. Specifically, the acetate and acetate + AQDS amended microcosm typically exhibited the highest Fe concentrations (up to 1725 and 6566 nmol kg⁻¹, respectively). The increase in both As and Fe in the artificial groundwater solutions in these amended microcosm experiments strongly suggests that microbes within the Aquia aquifer sediments mobilize As from the sediment substrate to the groundwaters via Fe(III) reduction.     

Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

Removal of arsenic from aqueous solution by natural siderite and hematite

Batch and column experiments were conducted to examine the capability of naturally formed hematite and siderite to remove As from drinking water. Results show that both minerals were able to remove As from aqueous solutions, but with different efficiencies. In general, each material removed arsenate much more efficiently than As–DMA (dimethylarsinic acid), with the lowest adsorption efficiency for arsenite. The best removal efficiency for As species was obtained using a hematite, with a grain size range between 0.25 and 0.50 mm. The adsorption capacity for inorganic As(V) reached 202 μg/g. The pH generally had a great impact on the arsenate removal by the Fe minerals studied, while arsenite removal was slightly dependent on the initial pH of between 3 and 10. The presence of phosphate always had a negative effect on arsenate adsorption, due to competitive adsorption between them. A column packed with hematite in the upper half and siderite in the lower half with a grain size range of 0.25–0.5 mm proved to be an efficient reactive filter for the removal of all As species, causing a decrease in As concentration from 500 μg/L (including 200 μg/L As(V) as arsenate, 200 μg/L As(III) as arsenite and 100 μg/L As(V) as DMA) to less than 10 μg/L after 1055 pore volumes of water were filtered at a flow rate of 0.51 mL/min. After 2340 pore volumes passed through the column filter, the total inorganic As in the effluent was less than 5 μg/L. The total As load in the column filter was estimated to be 0.164 mg/g. Results of μ-synchrotron X-ray fluorescence analysis (μ-XRFA) suggest that coatings of fresh Fe(III) oxides, formed on the surface of the siderite grains after two weeks of operation, greatly increased the adsorption capacity of the filling material towards As.     

Characterisation of organic matter and microbial communities in contrasting arsenic-rich Holocene and arsenic-poor Pleistocene aquifers,Red River Delta,Vietnam

High concentrations of geogenic As in the groundwaters of south and SE Asia, which are used as drinking waters, are causing severe health impacts to the exposed human populations. It is widely accepted that As mobilisation from sediments into these shallow reducing groundwaters requires active metal-reducing microbes and electron donors such as organic matter (OM). Although OM in such Holocene aquifers has been characterised, there is a dearth of data on Pleistocene aquifers from the same areas. Reported here are preliminary studies of OM and microbial communities present in two aquifers, one of Pleistocene and one of Holocene age, with contrasting concentrations of As (viz. Pleistocene: low As <10 μg/L; Holocene: high As up to 600 μg/L) from Van Phuc village in the Red River Delta, Vietnam. Results revealed OM inputs from multiple sources, including potential contributions from naturally occurring petroleum seeping into the shallow aquifer sediments from deeper thermally mature source rocks. Although concentrations vary, no noticeable systematic differences in biomarker distribution patterns within the OM were observed between the two sites. Microbial analyses did not show a presence of microbial communities previously associated with As mobilisation. All clone libraries were dominated by α-, β-, and γ-Proteobacteria not known to be able to reduce Fe(III) or sorbed As(V). Furthermore, representatives of the Fe(III)-reducing genus Geobacter could only be detected at very low abundance by PCR, using highly selective 16S rRNA gene primers, supporting the hypothesis that metal reduction is not a dominant in situ process in these sediments. No correlation between As concentration in groundwater and OM composition nor microbial community in the host sediments was found. This suggests that either (i) As is not being significantly mobilised in situ in these sediments, instead As appears to be mobilised elsewhere and transported by groundwater flow to the sites or (ii) sorption/desorption processes, as implicated by geochemical data from the cores, play a critical role in controlling As concentrations at these sites.     

Comparison of arsenic concentrations in simultaneously-collected groundwater and aquifer particles from Bangladesh,India, Vietnam,and Nepal

One of the reasons the processes resulting in As release to groundwater in southern Asia remain poorly understood is the high degree of spatial variability of physical and chemical properties in shallow aquifers. In an attempt to overcome this difficulty, a simple device that collects groundwater and sediment as a slurry from precisely the same interval was developed in Bangladesh. Recently published results from Bangladesh and India relying on the needle-sampler are augmented here with new data from 37 intervals of grey aquifer material of likely Holocene age in Vietnam and Nepal. A total of 145 samples of filtered groundwater ranging in depth from 3 to 36 m that were analyzed for As (1–1000 μg/L), Fe (0.01–40 mg/L), Mn (0.2–4 mg/L) and S (0.04–14 mg/L) are compared. The P-extractable (0.01–36 mg/kg) and HCl-extractable As (0.04–36 mg/kg) content of the particulate phase was determined in the same suite of samples, in addition to Fe(II)/Fe ratios (0.2–1.0) in the acid-leachable fraction of the particulate phase. Needle-sampler data from Bangladesh indicated a relationship between dissolved As in groundwater and P-extractable As in the particulate phase that was interpreted as an indication of adsorptive equilibrium, under sufficiently reducing conditions, across 3 orders of magnitude in concentrations according to a distribution coefficient of 4 mL/g. The more recent observations from India, Vietnam and Nepal show groundwater As concentrations that are often an order of magnitude lower at a given level of P-extractable As compared to Bangladesh, even if only the subset of particularly reducing intervals characterized by leachable Fe(II)/Fe >0.5 and dissolved Fe >0.2 mg/L are considered. Without attempting to explain why As appears to be particularly mobile in reducing aquifers of Bangladesh compared to the other regions, the consequences of increasing the distribution coefficient for As between the particulate and dissolved phase to 40 mL/g for the flushing of shallow aquifers of their initial As content are explored.     

New operational method of testing colloid complexation with metals in natural waters

A dialysis procedure was used to assess the distribution coefficients of ∼50 major and trace elements (TEs) between colloidal (1 kDa–0.22 μm) and truly dissolved (<1 kDa) phases in Fe- and organic-rich boreal surface waters. These measurements allowed quantification of both TE partitioning coefficients and the proportion of colloidal forms as a function of solution pH (from 3 to 8). Two groups of elements can be distinguished according to their behaviour during dialysis: (i) elements which are strongly associated with colloids and exhibit significant increases of relative proportion of colloidal forms with pH increase (Al, Ba, Cd, Co, Cr, Cu, Fe, Ga, Hf, Mn, Ni, Pb, rare earth elements (REEs), Sr, Th, U, Y, Zn, Zr and dissolved organic C) and (ii) elements that are weakly associated with colloids and whose distribution coefficients between colloidal and truly dissolved phases are not significantly affected by solution pH (As, B, Ca, Cs, Ge, K, Li, Mg, Mo, Na, Nb, Rb, Sb, Si, Sn, Ti, V). Element speciation was assessed using the Visual MINTEQ computer code with an implemented NICA-Donnan humic ion binding model and database. The model reproduces quantitatively the pH-dependence of colloidal form proportion for alkaline-earth (Ba, Ca, Mg, Sr) and most divalent metals (Co, Cd, Mn, Ni, Pb, Zn) implying that the complexation of these metals with low molecular weight organic matter (<1 kDa fraction) is negligible. In contrast, model prediction of colloidal proportion (fraction of 1 kDa–0.22 μm) of Cu²⁺ and all trivalent and tetravalent metals is much higher than that measured in the experiment. This difference may be explained by (i) the presence of strong metal-binding organic ligands in the <1 kDa fraction whose stability constants are several orders of magnitude higher than those of colloidal humic and fulvic acids and/or (ii) coprecipitation of TE with Fe(Al) oxy(hydr)oxides in the colloidal fraction, whose dissolution and aggregation controls the pH-dependent pattern of TE partitioning. Quantitative modeling of metal – organic ligand complexation and empirical distribution coefficients corroborate the existence of two colloidal pools, formerly reported in boreal surface waters: “classic” fulvic or humic acids binding divalent transition metals and alkaline-earth elements and large-size organo-ferric colloids transporting insoluble trivalent and tetravalent elements.     

Spatial variation in arsenic and fluoride concentrations of shallow groundwater from the town of Shahai in the Hetao basin,Inner Mongolia

Twenty-nine wells were selected for groundwater sampling in the town of Shahai, in the Hetao basin, Inner Mongolia. Four multilevel samplers were installed for monitoring groundwater chemistry at depths of 2.5–20 m. Results show that groundwater As exhibits a large spatial variation, ranging between 0.96 and 720 μg/L, with 71% of samples exceeding the WHO drinking water guideline value (10 μg/L). Fluoride concentrations range between 0.30 and 2.57 mg/L. There is no significant correlation between As and F⁻ concentrations. Greater As concentrations were found with increasing well depth. However, F⁻ concentrations do not show a consistent trend with depth. Groundwater with relatively low Eh has high As concentrations, indicating that the reducing environment is the major factor controlling As mobilization. Low As concentrations (<10 μg/L) are found in groundwater at depths less than 10 m. High groundwater As concentration is associated with aquifers that have thick overlying clay layers. The clay layers, mainly occurring at depths <10 m, have low permeability and high organic C content. These strata restrict diffusion of atmospheric O₂ into the aquifers, and lead to reducing conditions that favor As release. Sediment composition is an additional factor in determining dissolved As concentrations. In aquifers composed of yellowish-brown fine sands at depths around 10 m, groundwater generally has low As concentrations which is attributed to the high As adsorption capacity of the yellow–brown Fe oxyhydroxide coatings. Fluoride concentration is positively correlated with pH and negatively correlated with Ca²⁺ concentration. All groundwater samples are over-saturated with respect to calcite and under-saturated with respect to fluorite. Dissolution and precipitation of Ca minerals (such as fluorite and calcite), and F⁻ adsorption–desorption are likely controlling the concentration of F⁻ in groundwater.     

The occurrence and geochemistry of arsenic in groundwaters of the Newark basin of Pennsylvania

Elevated As concentrations in groundwater in the eastern United States have been recognized predominantly in the accretionary geologic terranes of northern New England. A retrospective examination of more than 18,000 existing groundwater samples from the Pennsylvania Department of Environmental Protection (PA DEP) Drinking Water and Sampling Information System database indicates that elevated groundwater As concentrations occur throughout the northern half of the Piedmont Province of Pennsylvania. Chemical analyses of 53 samples collected in 2005 from drinking water wells in this area all had detectable As, and 23% of these samples contained elevated (>133 nmol/L or >10 μg/L) concentrations of As. Elevated concentrations of As in the groundwater samples were most common in the Mesozoic sedimentary strata composed of sandstone and red mudstone with interbedded gray shale, and gray to black siltstone and shale. Arsenic was typically not elevated in groundwater of diabase intrusions of the Newark Basin or in crystalline and calcareous aquifers to the north of the Newark Basin. Geochemical parameters such as pH and oxidation–reduction potential can indicate mobility mechanisms of As in some regions. In this area, measured groundwater conditions were predominantly oxidizing (Eh > +50 mV), and more than 85% of samples contained arsenate as the dominant As species. Variations in pH were strongly correlated to the As concentration, with highest As concentrations observed at pH values greater than 6.4. The original source of As is most likely the black and gray shales that contain some arsenian pyrite with groundwater concentrations likely to be controlled by adsorption/desorption reactions with Fe oxides in the red mudstone aquifer materials.     

Effects of desferrioxamine-B on the release of arsenic from volcanic rocks

Microorganisms play an important role in As mobilization into groundwater by directly influencing As speciation or indirectly inducing solubilisation from As-bearing phases, such as Fe, Mn and Al oxides. Iron oxide dissolution could also be induced by siderophores, small-molecule compounds produced by microorganisms to favour Fe uptake. Well waters exceeding the potable water limit of 10 μg As L⁻¹ (0.133 μM) have been widely reported in geothermal areas. Mechanisms responsible for these high As concentrations have not yet been thoroughly elucidated and the complexity of As mobilization in volcanic aquifers is still open to multiple interpretations. The present study was based on batch release experiments aimed at verifying and quantifying the effect of siderophores on As mobilization from volcanic rocks (lava, tuff, peperino and fallout deposit) at different pH and ligand concentration. In the experiments the siderophore trihydroxamate desferroxamine B (Dfob) was used and its effect on As release from volcanic rocks was manifest after the first days. The most favourable pH for As release was pH 6 while concentrations above 250 μM Dfob considerably enhanced As and Fe concentrations in solution. The As release from rocks was between 2.0–10% at pH 6 and 2.4–8.8% at pH 8. The As/Fe ratio in solution changed with time suggesting different release mechanisms and higher mobility of As compared to Fe during the first phase of the experiment. The presence of siderophore increased Fe dissolution rates up to 10 orders of magnitude. The As release correlated with Al, Mn, Fe, Si, V, Ga and Sb and the release of all these elements increased with increasing Dfob concentration. In alkaline environments also Cu, Zn and Pb were mobilized. The presence of siderophores represents a possible trigger for As mobilization from iron binding minerals to the water phase, with interesting implications for groundwater quality, plant uptake and bacterial communities.     

Arsenic and Antimony in Groundwater Flow Systems: A Comparative Study

Arsenic (As) and antimony (Sb) concentrations and speciation were determined along flow paths in three groundwater flow systems, the Carrizo Sand aquifer in southeastern Texas, the Upper Floridan aquifer in south-central Florida, and the Aquia aquifer of coastal Maryland, and subsequently compared and contrasted. Previously reported hydrogeochemical parameters for all three aquifer were used to demonstrate how changes in oxidation–reduction conditions and solution chemistry along the flow paths in each of the aquifers affected the concentrations of As and Sb. Total Sb concentrations (Sb_T) of groundwaters from the Carrizo Sand aquifer range from 16 to 198 pmol kg⁻¹; in the Upper Floridan aquifer, Sb_T concentrations range from 8.1 to 1,462 pmol kg⁻¹; and for the Aquia aquifer, Sb_T concentrations range between 23 and 512 pmol kg⁻¹. In each aquifer, As and Sb (except for the Carrizo Sand aquifer) concentrations are highest in the regions where Fe(III) reduction predominates and lower where SO₄ reduction buffers redox conditions. Groundwater data and sequential analysis of the aquifer sediments indicate that reductive dissolution of Fe(III) oxides/oxyhydroxides and subsequent release of sorbed As and Sb are the principal mechanism by which these metalloids are mobilized. Increases in pH along the flow path in the Carrizo Sand and Aquia aquifer also likely promote desorption of As and Sb from mineral surfaces, whereas pyrite oxidation mobilizes As and Sb within oxic groundwaters from the recharge zone of the Upper Floridan aquifer. Both metalloids are subsequently removed from solution by readsorption and/or coprecipitation onto Fe(III) oxides/oxyhydroxides and mixed Fe(II)/Fe(III) oxides, clay minerals, and pyrite. Speciation modeling using measured and computed Eh values predicts that Sb(III) predominate in Carrizo Sand and Upper Floridan aquifer groundwaters, occurring as the Sb(OH)₃⁰ species in solution. In oxic groundwaters from the recharge zones of these aquifers, the speciation model suggests that Sb(V) occurs as the negatively charged Sb(OH)₆⁻ species, whereas in sufidic groundwaters from both aquifers, the thioantimonite species, HSb₂S₄ ⁻ and Sb₂S₄ ²⁻, are predicted to be important dissolved forms of Sb. The measured As and Sb speciation in the Aquia aquifer indicates that As(III) and Sb(III) predominate. Comparison of the speciation model results based on measured Eh values, and those computed with the Fe(II)/Fe(III), S(-II)/SO₄, As(III)/As(V), and Sb(III)/Sb(V) couples, to the analytically determined As and Sb speciation suggests that the Fe(II)/Fe(III), S(-II)/SO₄ couples exert more control on the in situ redox condition of these groundwaters than either metalloid redox couple.     

Role of Fe(II) and phosphate in arsenic uptake by coprecipitation

Natural attenuation of arsenic by simple adsorption on oxyhydroxides may be limited due to competing oxyanions, but uptake by coprecipitation may locally sequester arsenic. We have systematically investigated the mechanism and mode (adsorption versus coprecipitation) of arsenic uptake in the presence of carbonate and phosphate, from solutions of inorganic composition similar to many groundwaters. Efficient arsenic removal, >95% As(V) and ∼55% in initial As(III) systems, occurred over 24 h at pHs 5.5-6.5 when Fe(II) and hydroxylapatite (Ca₅(PO₄)₃OH, HAP) “seed” crystals were added to solutions that had been previously reacted with HAP, atmospheric CO_2(g) and O_2(g). Arsenic adsorption was insignificant (<10%) on HAP without Fe(II). Greater uptake in the As(III) system in the presence of Fe(II) was interpreted as due to faster As(III) to As(V) oxidation by molecular oxygen in a putative pathway involving Fe(IV) and As(IV) intermediate species. HAP acts as a pH buffer that allows faster Fe(II) oxidation. Solution analyses coupled with high-resolution transmission electron microscopy (HRTEM), X-ray Energy-Dispersive Spectroscopy (EDS), and X-Ray Absorption Spectroscopy (XAS) indicated the precipitation of sub-spherical particles of an amorphous, chemically-mixed, nanophase, Fe^III[(OH)₃(PO₄)(As^VO₄)]·nH₂O or Fe^III[(OH)₃( PO₄)(As^VO₄)(As^IIIO₃)_minor]·nH₂O, where As^IIIO₃ is a minor component.The mode of As uptake was further investigated in binary coprecipitation (Fe(II) + As(III) or P), and ternary coprecipitation and adsorption experiments (Fe(II) + As(III) + P) at variable As/Fe, P/Fe and As/P/Fe ratios. Foil-like, poorly crystalline, nanoparticles of Fe^III(OH)₃ and sub-spherical, amorphous, chemically-mixed, metastable nanoparticles of Fe^III[(OH)₃, PO₄]·nH₂O coexisted at lower P/Fe ratios than predicted by bulk solubilities of strengite (FePO₄·2H₂O) and goethite (FeOOH). Uptake of As and P in these systems decreased as binary coprecipitation > ternary coprecipitation > ternary adsorption.Significantly, the chemically-mixed, ferric oxyhydroxide-phosphate-arsenate nanophases found here are very similar to those found in the natural environment at slightly acidic to circum-neutral pHs in sub-oxic to oxic systems, such phases may naturally attenuate As mobility in the environment, but it is important to recognize that our system and the natural environment are kinetically evolving, and the ultimate environmental fate of As will depend on the long-term stability and potential phase transformations of these mixed nanophases. Our results also underscore the importance of using sufficiently complex, yet systematically designed, model systems to accurately represent the natural environment.     

Occurrence and geochemistry of arsenic in the groundwater of Eastern Croatia

In order to examine the extent of the As enrichment and the factors influencing this enrichment in the groundwater of Eastern Croatia, groundwater samples were collected from 56 production wells in two counties, Osijek-Baranja and Vukovar-Srijem, suspected to be more affected. Hydrochemical analyses were performed at all locations including in situ As speciation at 32 locations. Arsenic was detected in 46 out of 56 groundwater samples with total As concentrations up to 491 μg/L. Thirty-six of the studied wells yielded groundwater with total As concentrations that exceeded the WHO Maximum Contaminant Level for arsenic in drinking water of 10 μg/L. Only inorganic As species were detected with arsenite As(III) as the predominant form. The spatial distribution of As in the groundwater was significantly linked with geological, geomorphological and hydrogeological development of the alluvial basin of the Drava and Sava rivers. The most probable groundwater As sources are deeper sediments from the Middle and Upper Pleistocene. The results obtained suggest that biogeochemical processes controlling As concentration in the groundwater are complex and location-specific. Reductive dissolution of Fe oxides, desorption of As from Fe oxides and/or clay minerals as well as competition for the sorption sites with organic matter and phosphate could be the principal mechanisms that control As mobilization. The extent of those processes vary in the different parts of the Drava and Sava depressions and could be linked to different site related parameters, such as lithology, mineralogy, local hydrology and hydrogeology; thus different processes of As mobilization have been proposed for the different types of water in relation to groundwater evolution.     

Mobility of arsenic in West Bengal aquifers conducting low and high groundwater arsenic. Part I: Comparative hydrochemical and hydrogeological characteristics

The present study demonstrates the importance of hydrogeochemical characteristics (groundwater flow and recharge) of an aquifer in the release of As to groundwater. The study area (∼20 km²) is located in Chakdaha block, Nadia district, West Bengal, which hosts groundwaters of variable As content. The spatial distribution pattern of As is patchy with areas containing groundwater that is high in As (>200 μg L⁻¹) found in close vicinity to low As (<50 μg L⁻¹) groundwaters (within 100 m). The concentration of groundwater As is found to decrease with depth. In addition, the data shows that there is no conspicuous relationship between high groundwater As concentration and high groundwater abstraction, although the central cone of depression has enlarged over 2 a and is extending towards the SE of the study area. The river Hooghly, which forms the NW boundary of the study site, shows dual behaviour (effluent and influent during pre- and post-monsoon periods, respectively), complicating the site hydrogeology. The observed groundwater flow lines tend to be deflected away from the high As portion of the aquifer, indicating that groundwater movement is very sluggish in the As-rich area. This leads to a high residence time for this groundwater package, prolonging sediment–water interaction, and hence facilitating groundwater As release.