Arsenic enrichment in groundwater of West Bengal,India: geochemical evidence for mobilization of As under reducing conditions

The mechanism of As release and source(s) of As has been investigated in a small part of a watershed in the Murshidabad district of West Bengal. Analyses include major ion and trace element concentrations, as well as O, H and S isotope ratios of groundwater, surface water and a thermal spring. The results indicate that all water samples belong to the Ca–HCO₃ type, except for the thermal spring which is of the Na–HCO₃ type. Shallow and deeper groundwaters have distinct hydrochemical features. High As contents were registered only in the deeper groundwater horizon. Factor analysis and the distribution pattern of major and trace elements indicate that As is present in the aquifer as a scavenged phase by Fe(III) and to a lesser extent by Mn(IV) phases. The release of As into the groundwater occurs gradually in successive stages, corresponding to the actual redox state in the aquifer. The main stage of As release is related to the bacterial reduction of Fe(III) to Fe(II) (i.e. to the simultaneous dissolution of Fe oxyhydroxides). Low redox conditions in highly polluted areas are indicated by low SO₄ concentration and high δ³⁴S values. During bacterial SO₄ reduction, residual SO₄ in groundwater is depleted in the lighter S isotope (³²S). However, the cause of the gradual decrease of the redox state in the groundwater is still not well understood.     

Interplay of S and As in Mekong Delta sediments during redox oscillations

The cumulative effects of periodic redox cycling on the mobility of As,Fe,and S from alluvial sediment to groundwater were investigated in bioreactor experiments.Two particular sediments from the alluvial floodplain of the Mekong Delta River were investigated:Matrix A(14 m deep)had a higher pyrite concentration than matrix B(7 m deep)sediments.Gypsum was present in matrix B but absent in matrix A.In the reactors,the sediment suspensions were supplemented with As(Ⅲ)and SO_4~(2-),and were subjected to three full-redox cycles entailing phases of nitrogen/CO_2,compressed air sparging,and cellobiose addition.Major differences in As concentration and speciation were observed upon redox cycling.Evidences support the fact that initial sediment composition is the main factor controlling arsenic release and its speciation during the redox cycles.Indeed,a high pyrite content associated with a low SO_4~(2-)content resulted in an increase in dissolved As concentrations,mainly in the form of As(Ⅲ),after anoxic half-cycles;whereas a decrease in As concentrations mainly in the form of As(Ⅴ),was instead observed after oxic half-cycles.In addition,oxic conditions were found to be responsible for pyrite and arsenian pyrite oxidation,increasing the As pool available for mobilization.The same processes seem to occur in sediment with the presence of gypsum,but,in this case,dissolved As were sequestered by biotic or abiotic redox reactions occurring in the Fe—S system,and by specific physico-chemical condition(e.g.pH).The contrasting results obtained for two sediments sampled from the same core show that many complexes and entangled factors are at work,and further refinement is needed to explain the spatial and temporal variability of As release to groundwater of the Mekong River Delta(Vietnam).     

Simultaneous oxidation of arsenic and antimony at low and circumneutral pH,with and without microbial catalysis

Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H₂SO₄ solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl⁻ concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.     

Hydrochemical evolution and arsenic release in shallow aquifer in the Titas Upazila,Eastern Bangladesh

Groundwater arsenic (As) concentrations above 10 μg/L (World Health Organization; WHO standard) are frequently found in the Titas Upazila in Bangladesh. This paper evaluates the groundwater chemistry and the mechanisms of As release acting in an underground aquifer in the middle-northeast part of the Titas Upazila in Bangladesh. Previous measurements and analyses of 43 groundwater samples from the region of interest (ROI) are used. Investigation is based on major ions and important trace elements, including total As and Fe in groundwater samples from shallow (8–36 m below ground level: mbgl) and deep (85–295 mbgl) tube wells in the aforementioned ROI. Principal hydrochemical facies are Ca–HCO₃, with circumneutral pH. The different redox-sensitive constituents (e.g., As, Fe, Mn, NH₄, and SO₄) indicate overlapping redox zones, leading to differences regarding the redox equilibrium. Multivariate statistical analysis (factor analysis) was applied to reduce 20 chemical variables to four factors but still explain 81% of the total variance. The component loadings give hints as to the natural processes in the shallow aquifers, in which organic matter is a key reactant. The observed chemistry of As, Fe, and Mn can be explained by simultaneous equilibrium between Fe-oxide and SO₄ reduction and an equilibrium of rhodochrosite precipitation/dissolution. A correlation test indicates the likeliness of As release by the reductive dissolution of Fe-oxides driven by the degradation of sediments organic matter. Other mechanisms could play a role in As release, albeit to a lesser extent. Reactive transport modeling using PHREEQC reproduced the observed chemistry evolution using simultaneous equilibrium between Fe-oxide and SO₄ reduction and the equilibrium of rhodochrosite dissolution/precipitation alongside organic matter oxidation.     

Lepidocrocite-catalyzed Mn(II) oxygenation by air and its effect on the oxidation and mobilization of As(III)

Manganese (oxy)hydroxides (MnO_X) play important roles in the oxidation and mobilization of toxic As(III) in natural environments. Abiotic oxidation of Mn(II) to MnO_X in the presence of Fe minerals has been proved to be an important pathway in the formation of Mn(III, IV) (oxy)hydroxides. However, interactions between Mn(II) and As(III) in the presence of Fe minerals are still poorly understood. In this study, abiotic oxidation of Mn(II) on lepidocrocite, and its effect on the oxidation and mobilization of As(III) were investigated. The results show that MnO_X species are detected on lepidocrocite and their contents increase with increasing pH values ranging from 7.5 to 8.4. After 10 days, an MnOx component, groutite (α-MnOOH) was found on lepidocrocite. During the simultaneous oxidation of Mn(II) and As(III), and the As(III) pre-adsorbed processes, the presence and oxidation of Mn(II) significantly promotes the removal of soluble As(III). In addition, MnOx formed on lepidocrocite also contributes to the oxidation of soluble and adsorbed As(III) to As(V), the latter being subsequently released into solution. In the process where Mn(II) is pre-adsorbed on lepidocrocite, less As(III) is removed, given that the active sites occupied by MnOx inhibit the adsorption of As(III). In all experiments, the removal percentages of As(III) and the release of As(V) are correlated positively with pH values and initial concentrations of Mn(II), although they are not apparent in the Mn(II) pre-adsorbed system.     

Arsenic in shallow groundwater of Bangladesh: investigations from three different physiographic settings

Occurrences of arsenic (As) in the Bengal Basin of Bangladesh show close relationships with depositional environments and sediment textures. Hydrochemical data from three sites with varying physiography and sedimentation history show marked variations in redox status and dissolved As concentrations. Arsenic concentration in groundwater of the Ganges Flood Plain (GFP) is characteristically low, where high Mn concentrations indicate redox buffering by reduction of Mn(IV)-oxyhydroxides. Low DOC, \( {\text{HCO}}^{ - }_{3} \), \( {\text{NH}}^{ + }_{4} \) and high \( {\text{NO}}^{ - }_{3} \) and \( {\text{SO}}^{{2 - }}_{4} \) concentrations reflect an elevated redox status in GFP aquifers. In contrast, As concentration in the Ganges Delta Plain (GDP) is very high along with high Fe and low Mn. In the Meghna Flood Plain (MFP), moderate to high As and Fe concentrations and low Mn are detected. Degradation of organic matter probably drives redox reactions in the aquifers, particularly in MFP and GDP, thereby mobilising dissolved As. Speciation calculations indicate supersaturation with respect to siderite and vivianite in the groundwater samples at MFP and GDP, but groundwater in the GFP wells is generally supersaturated with respect to rhodochrosite. Values of log P_CO2 at MFP and GDP sites are generally higher than at the GFP site. This is consistent with Mn(IV)-redox buffering suggested at the GFP site compared to Fe(III)-redox buffering at MFP and GDP sites.     

Geochemical and mineralogical aspects of sulfide mine tailings

Tailings generated during processing of sulfide ores represent a substantial risk to water resources. The oxidation of sulfide minerals within tailings deposits can generate low-quality water containing elevated concentrations of SO₄, Fe, and associated metal(loid)s. Acid generated during the oxidation of pyrite [FeS₂], pyrrhotite [Fe_(1−x)S] and other sulfide minerals is neutralized to varying degrees by the dissolution of carbonate, (oxy)hydroxide, and silicate minerals. The extent of acid neutralization and, therefore, pore-water pH is a principal control on the mobility of sulfide-oxidation products within tailings deposits. Metals including Fe(III), Cu, Zn, and Ni often occur at high concentrations and exhibit greater mobility at low pH characteristic of acid mine drainage (AMD). In contrast, (hydr)oxyanion-forming elements including As, Sb, Se, and Mo commonly exhibit greater mobility at circumneutral pH associated with neutral mine drainage (NMD). These differences in mobility largely result from the pH-dependence of mineral precipitation–dissolution and sorption–desorption reactions. Cemented layers of secondary (oxy)hydroxide and (hydroxy)sulfate minerals, referred to as hardpans, may promote attenuation of sulfide-mineral oxidation products within and below the oxidation zone. Hardpans may also limit oxygen ingress and pore-water migration within sulfide tailings deposits. Reduction–oxidation (redox) processes are another important control on metal(loid) mobility within sulfide tailings deposits. Reductive dissolution or transformation of secondary (oxy)hydroxide phases can enhance Fe, Mn, and As mobility within sulfide tailings. Production of H₂S via microbial sulfate reduction may promote attenuation of sulfide-oxidation products, including Fe, Zn, Ni, and Tl, via metal-sulfide precipitation. Understanding the dynamics of these interrelated geochemical and mineralogical processes is critical for anticipating and managing water quality associated with sulfide mine tailings.     

Mechanisms controlling acid neutralization and metal mobility within a Ni-rich tailings impoundment

Low-quality pore waters containing high concentrations of dissolved H⁺, SO₄, and metals have been generated in the East Tailings Management Area at Lynn Lake, Manitoba, as a result of sulfide-mineral oxidation. To assess the abundance, distribution, and solid-phase associations of S, Fe, and trace metals, the tailings pore water was analyzed, and investigations of the geochemical and mineralogical characteristics of the tailings solids were completed. The results were used to delineate the mechanisms that control acid neutralization, metal release, and metal attenuation. Migration of the low-pH conditions through the vadose zone is limited by acid-neutralization reactions, resulting in the development of distinct pore-water pH zones at depth; the neutralization reactions involve carbonate (pH ⩾ 5.7), Al-hydroxide (pH ⩾ 4.0), and aluminosilicate solids. As the zone of low-pH pore water expands, the pH will then be primarily controlled by less soluble solids, such as Fe(III) oxyhydroxides (pH < 3.5) and the relatively more recalcitrant aluminosilicates (pH ⩾ 1.3). Precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxides and hydroxysulfates control the concentrations of dissolved Fe(III). Concentrations of dissolved SO₄ are principally controlled by the formation of gypsum and jarosite. Geochemical extractions indicate that the solid-phase concentrations of Ni, Co, and Zn are associated predominantly with reducible and acid-soluble fractions. The concentrations of dissolved trace metals are therefore primarily controlled by adsorption/complexation and (or) co-precipitation/dissolution reactions involving secondary Fe(III) oxyhydroxide and hydroxysulfate minerals. Concentrations of dissolved metals with relatively low mobility, such as Cu, are also controlled by the precipitation of discrete minerals. Because the major proportion of metals is sequestered through adsorption and (or) co-precipitation, the metals are susceptible to remobilization if low-pH or reducing conditions develop within the tailings.     

Heavy metal pollution in the surrounding ore deposits and mining activity: a case study from Koyulhisar (Sivas-Turkey)

The oxidation of sulfide minerals generates acidic waters containing high levels of SO₄ and Fe. The study area has active Pb?CZn?CCu mining. It is thought that the surface/subsurface/underground sulfide minerals in the region generally contribute to the acidification of groundwater. Low pH values are also responsible for dissolved metals (Al, Fe, Mn, SO₄, Pb, Zn) in the groundwater and river. Furthermore, current mining wastes have affected concentrations of trace elements in the water. High Fe and Mn concentrations are generally found in the spring which has acidic and low Eh values, while Al, Fe and Mn concentrations in the acidic waters show notable increases with the maximum values reaching 8,829, 19,084 and 1,708?ppb, respectively. These values exceed the Turkish drinking water standard of 200, 200 and 50?ppb, respectively.     

Chemical evolution of groundwater in the Wilcox aquifer of the northern Gulf Coastal Plain,USA

The Wilcox aquifer is a major groundwater resource in the northern Gulf Coastal Plain (lower Mississippi Valley) of the USA, yet the processes controlling water chemistry in this clastic aquifer have received relatively little attention. The current study combines analyses of solutes and stable isotopes in groundwater, petrography of core samples, and geochemical modeling to identify plausible reactions along a regional flow path ～300 km long. The hydrochemical facies evolves from Ca-HCO₃ upgradient to Na-HCO₃ downgradient, with a sequential zonation of terminal electron-accepting processes from Fe(III) reduction through SO₄ ^2? reduction to methanogenesis. In particular, decreasing SO₄ ^2? and increasing δ³⁴S of SO₄ ^2? along the flow path, as well as observations of authigenic pyrite in core samples, provide evidence of SO₄ ^2? reduction. Values of δ¹³C in groundwater suggest that dissolved inorganic carbon is contributed both by oxidation of sedimentary organic matter and calcite dissolution. Inverse modeling identified multiple plausible sets of reactions between sampled wells, which typically involved cation exchange, pyrite precipitation, CH₂O oxidation, and dissolution of amorphous Fe(OH)₃, calcite, or siderite. These reactions are consistent with processes identified in previous studies of Atlantic Coastal Plain aquifers. Contrasts in groundwater chemistry between the Wilcox and the underlying McNairy and overlying Claiborne aquifers indicate that confining units are relatively effective in limiting cross-formational flow, but localized cross-formational mixing could occur via fault zones. Consequently, increased pumping in the vicinity of fault zones could facilitate upward movement of saline water into the Wilcox.     

Arsenic behaviour in gold-ore mill tailings,Massif Central,France: hydrogeochemical study and investigation of in situ redox signatures

Historical Au-ore exploitation at the Chéni mine in the Massif Central, France, generated 525,000 tonnes of finely ground mill tailings deposited in a heap that has spread with time into three settling basins. The tailings, which are rich in quartz (80%), mica and clay minerals (10% of illite, smectite, kaolinite and chlorite), feldspars (5%) but poor in carbonates (<1%), also contain sulphides (around 5%, mainly pyrite and arsenopyrite). Arsenic content of the tailings is around 6 g kg. This paper describes the geochemistry of drainage waters, with special attention paid to in situ values of the three major redox couples, namely Fe(II)/Fe(III), As(III)/As(V) and S(IV)/S(VI). The water samples range from acidic and oxidized (pH 2.9, E_h +700 mV) to moderate pH and weakly reducing (pH 7.6, E_h 15 mV). The waters are rich in SO₄ and Ca and have variable As (0.05–95 mg L⁻¹) and Fe concentrations (0.07–141 mg L⁻¹). Reduced As(III) species predominate over As(V) species (As(III)/As(V) up to 21), whereas oxidized forms of Fe and S are favoured (Fe(II)/Fe(III) up to 0.5, and S(IV)/S(VI) up to 1).Thermodynamic calculations were performed with the PHREEQC and EQ3NR codes based on a revised As database to evaluate saturation indices (SI) of the waters in relation to the main minerals and define which redox couples control the redox state of the system. The important role of carbonates, though only present in small amounts, explains the acid buffering generated by the oxidation of sulphides for waters in the pH 7–7.5 range. Measured E_h appears to fall between the calculated E_h of the Fe(II)/Fe(III) couple and that of the As(III)/As(V) couple, illustrating redox disequilibrium.     

Factor and cluster analysis of water quality data of the groundwater wells of Kushtia, Bangladesh: Implication for arsenic enrichment and mobilization

The study area is located in the southwestern part of Bangladesh. Twenty-six groundwater samples were collected from both shallow and deep tube wells ranging in depth from 20 to 60 m. Multivariate statistical analyses including factor analysis, cluster analysis and multidimensional scaling were applied to the hydrogeochemical data. The results show that a few factors adequately represent the traits that define water chemistry. The first factor of Fe and HCO₃ is strongly influenced by bacterial Fe (III) reduction which would raise both Fe and HCO₃ concentrations in water. Na, Cl, Ca, Mg and PO₄ are grouped under the second factor representing the salinity sources of waters. The third factor, represented by As, Mn, SO₄ and K is related to As mobilization processes. Cluster analysis has been applied for the interpretation of the groundwater quality data. Initially Piper methods have been employed to obtain a first idea on the water types in the study area. Hierarchical cluster analysis was carried out for further classification of water types in the study area. Twelve components, namely, pH, Fe, Mn, As, Ca, Mg, Na, K, HCO₃, Cl, SO₄ and NO₃ have been used for this purpose. With hierarchical clustering analysis the water samples have been classified into 3 clusters. They are very high, high and moderately As-enriched groundwater as well as groundwater with elevated SO₄.     

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.     

Oxidation of As(III) by MnO2 in the absence and presence of Fe(II) under acidic conditions

Oxidation of As(III) by natural manganese (hydr)oxides is an important geochemical reaction mediating the transformation of highly concentrated As(III) in the acidic environment such as acid mine drainage (AMD) and industrial As-contaminated wastewater, however, little is known regarding the presence of dissolved Fe(II) on the oxidation process. In this study, oxidation of As(III) in the absence and presence of Fe(II) by MnO₂ under acidic conditions was investigated. Kinetic results showed that the presence of Fe(II) significantly inhibited the removal of As(III) (including oxidation and sorption) by MnO₂ in As(III)-Fe(II) simultaneous oxidation system even at the molar ratio of Fe(II):As(III) = 1/64:1, and the inhibitory effects increased with the increasing ratios of Fe(II):As(III). Such an inhibition could be attributed to the formation of Fe(III) compounds covering the surface of MnO₂ and thus preventing the oxidizing sites available to As(III). On the other hand, the produced Fe(III) compounds adsorbed more As(III) and the oxidized As(V) on the MnO₂ surface with an increasing ratio of Fe(II):As(III) as demonstrated in kinetic and XPS results. TEM and EDX results confirmed the formation of Fe compounds around MnO₂ particles or separated in solution in Fe(II) individual oxidation system, Fe(II) pre-treated and simultaneous oxidation processes, and schwertmannite was detected in Fe(II) individual and Fe pre-treated oxidation processes, while a new kind of mineral, probably amorphous FeOHAs or FeAsO₄ particles were detected in Fe(II)-As(III) simultaneous oxidation process. This suggests that the mechanisms are different in Fe pre-treated and simultaneous oxidation processes. In the Fe pre-treated and MnO₂-mediated oxidation pathway, As(III) diffused through a schwertmannite coating formed around MnO₂ particles to be oxidized. The newly formed As(V) was adsorbed onto the schwertmannite coating until its sorption capacity was exceeded. Arsenic(V) then diffused out of the coating and was released into the bulk solution. The diffusion into the schwertmannite coating and the oxidation of As(III) and sorption of both As(V) and As(III) onto the coating contributed to the removal of total As from the solution phase. In the simultaneous oxidation pathway, the competitive oxidation of Fe(II) and As(III) on MnO₂ occurred first, followed by the formation of FeOHAs or FeAsO₄ around MnO₂ particles, and these poorly crystalline particles of FeOHAs and FeAsO₄ remained suspended in the bulk solution to adsorb As(III) and As(V). The present study reveals that the formation of Fe(III) compounds on mineral surfaces play an important role in the sorption and oxidation of As(III) by MnO₂ under acidic conditions in natural environments, and the mechanisms involved in the oxidation of As(III) depend upon how Fe(II) is introduced into the As(III)-MnO₂ system.     

The oxidation of pyrite at pH 7 in the presence of reducing and nonreducing Fe(III)-chelators

The oxidation rate of pyrite at pH 7, 25°C and at constant partial pressure of oxygen (0.21 and 0.177 atm) was measured in the presence of the Fe(III)-chelators NTA, oxalate, leucine, EDTA, citrate, IDA and the Fe(III)-reductant ascorbic acid. With the exception of leucine and EDTA, non-reducing Fe(III)-chelators increased the oxidation rate relative to the reference state of formation of the Fe(OH)₂⁺ complex at pH 7. The rate increase was proportional to the logarithm of the conditional stability constant of the ligands for the complexation of Fe³⁺. No effect on the oxidation rate was observed in the presence of EDTA, which shifted the redox potential of the redox couple Fe²⁺/Fe³⁺ to a value below that in the absence of any ligand at pH 7. Ascorbic acid decreased the pyrite oxidation rate by a factor of 5 at ascorbic acid concentrations between 10⁻⁴ and 10⁻² mol L⁻¹. Comparison of the rate constants for the oxidation of ascorbic acid by surface bound Fe(III) in the absence and presence of pyrite shows that the pyrite surface accelerates this reaction by a factor of 10. The oxidation of both pyrite and ascorbic acid is of fractional order with respect to ascorbic acid (HAsc): r_py=0.55 c(HAsc)^−0.35 r_HAsc=3.6 c(HAsc)^0.59. Both the results from experiments with Fe(III)-chelating ligands and the Fe(III)-reductant, suggest a very efficient interference in the electron cycling between Fe(II) and Fe(III) at the pyrite surface. The interference seems to be mainly related to the reductive side of the iron cycling. It is therefore concluded that the electron transfer between ferric iron and pyritic sulfur limits the pyrite oxidation rate at pH 7.     

Behavior of arsenic and geochemical modeling of arsenic enrichment in aqueous environments

Arsenic is present in aqueous environments in +III and +V oxidation states. In oxidizing environments, the principle attenuation mechanism of As migration is its adsorption on Fe(III) oxide and hydroxides. The adsorption affinity is higher for As(V) under lower pH conditions and for As(III) under higher pH conditions. Ferric oxide and hydroxides can dissolve under low Eh and pH conditions releasing adsorbed As. Oxidation-reduction processes often involve high organic matter content in sediments and also contamination by organics such as BTEX. Arsenic may desorb under high pH conditions. Changes of pH can be related to some redox reactions, cation exchange reactions driving dissolution of carbonates, and dissolution of silicates. In very reducing environments, where SO₄ reduction takes place, secondary sulfide minerals like As-bearing pyrite and orpiment, As₂S₃, can incorporate As. Geochemical modeling can be divided into two principal categories: (a) forward modeling and (b) inverse modeling. Forward modeling is used to predict water chemistry after completion of predetermined reactions. Inverse modeling is used to suggest which processes take place along a flowpath. Complex coupled transport and geochemistry programs, which allow for simulation of As adsorption, are becoming available. A common modeling approach is based on forward modeling with surface complexation modeling (SCM) of As adsorption, which can incorporate the effect of different adsorbent/As ratios, adsorption sites density, area available for adsorption, pH changes and competition of As for adsorption sites with other dissolved species such as phosphate. The adsorption modeling can be performed in both batch and transport modes in codes such as PHREEQC. Inverse modeling is generally used to verify hypotheses on the origin of As. Basic prerequisites of inverse modeling are the knowledge of flow pattern (sampling points used in model have to be hydraulically connected) and information about mineralogy including As mineral phases. Case studies of geochemical modeling including modeling of As adsorption are presented.     

Effect of phosphate, silicate, and Ca on Fe(III)-precipitates formed in aerated Fe(II)- and As(III)-containing water studied by X-ray absorption spectroscopy

We studied the local coordination and structure of Fe(III)-precipitates formed in aerated Fe(II)- and As(III)-containing water (buffered to pH 7 by 8 mM bicarbonate) using synchrotron-based X-ray absorption spectroscopy (XAS) at the K-edges of Fe, P, Ca, and As. Dissolved phosphate, silicate, and Ca at different ratios relative to each other and to Fe affect the forming Fe(III)-phases in a complex manner. The high affinity of phosphate for Fe(III) results in the predominant precipitation of Fe(III)-phosphate as long as dissolved phosphate is present, with Fe(III) polymerization limited to small oligomers. In Ca-containing solution, Ca uptake by Fe(III)-Ca-phosphate involves the linkage and coagulation of negatively charged Fe(III)-phosphate oligomers via Ca-O-P bonds. In the absence of phosphate, dissolved silicate at Si/Fe ratios above ∼0.5 results in the formation of hydrous ferric oxide (HFO) with mainly edge-sharing Fe-Fe linkage. At lower Si/Fe ratios of ∼0.5-0.1, mainly 2-line ferrihydrite (2L-Fh) with both edge- and corner-sharing Fe-Fe linkage forms. Only in the absence of phosphate at low Si/Fe ratio, lepidocrocite (Lp) forms. In solutions containing sufficient Fe(II), aeration results in the sequential precipitation of Fe(III)-(Ca-)phosphate, HFO or 2L-Fh (depending on solution Si/Fe), and finally Lp. The amount and oxidation state of As co-precipitated with Fe(III) are controlled by the co-oxidation of As(III) with Fe(II), which increases with initial Fe/As ratio, and the competitive uptake of phosphate, As(V) and less strongly sorbing silicate and As(III). This study demonstrates that the diversity and sequence of short-range-ordered Fe(III)-precipitates forming by Fe(II) oxidation in near-neutral natural waters depend on water chemistry. Because differences in the colloidal stability and biogeochemical reactivity of these phases will affect the fate of associated major and trace elements, the different Fe(III)-precipitates and their specific biogeochemical properties must be taken into account when addressing nutrient and contaminant dynamics at redox boundaries in natural and engineered systems.     

Redox processes in the Oderbruch polder groundwater flow system in Germany

Large scale redox processes were investigated in a river recharged aquifer in the Oderbruch polder alongside the river Oder in north-eastern Germany. Major hydraulic and hydrochemical processes were identified qualitatively. As a result of intensive drainage activities in the past 250 a, the groundwater level within the polder is situated below the river water level and a levee prevents flooding of the lowland. As a consequence, river water permanently infiltrates into the shallow confined aquifer. A sequence of redox reactions, driven by organic matter degradation, can be observed during infiltration of oxic river water into the groundwater. Up to 3 km from the river, reduction processes from O₂ respiration to SO²⁻₄ reduction dominate the groundwater chemistry. While reduction of Fe- and Mn(hydr)oxides is the source of the high amounts of dissolved Fe²⁺ and Mn²⁺, carbonate dissolution/precipitation reactions control the actual groundwater concentration of Mn²⁺. The first order rate constant for SO²⁻₄ reduction was found to be −0.0169 a⁻¹. Fe²⁺ is released into the groundwater at a rate of 0.0033 mmol l⁻¹ a⁻¹. The groundwater chemistry is strongly linked to the hydraulic conditions. Near the river, the groundwater is confined and recharged by bank-filtration only. In contrast, in the central polder the groundwater is unconfined and percolation of rainwater through the dried loam is possible because of texture changes such as shrinkage fissures. Geogenic pyrite present within the alluvial loam is oxidised and large amounts of SO²⁻₄ are released into the groundwater.     

A kinetic study of the oxidation of arsenopyrite in acidic solutions: implications for the environment

Arsenopyrite is an important component of many ore deposits and dissolves in the O₂-rich, acidic surface waters that are commonly found in the vicinity of active mines, releasing As, Fe and S to the environment. However, despite the potentially serious effect of this pollution on the human and animal population, the rate at which such oxidation occurs is poorly known. Kinetic experiments were therefore conducted in a mixed flow reactor to investigate the oxidation of arsenopyrite in Fe₂(SO₄)₃ solutions (pH=l.8) having a concentration of l×l0⁻² to 1 ×l0⁻⁵ mol kg⁻¹ at temperatures of 45, 35, 25 and 15 °C. The results of these experiments show that the rate of oxidation of arsenopyrite increases with increasing concentration of dissolved Fe₂(SO₄)₃ and temperature. They also show that As released during the oxidation of arsenopyrite has the form As(III), and that the rate of conversion of As(III) to As(V) is relatively low, although it tends to increase with increasing concentration of dissolved Fe₂(SO₄)₃ and temperature. In the presence of Cl⁻, oxidation of arsenopyrite is accelerated, as is the conversion of As(III) to As(V). These findings indicate that exploitation of arsenopyrite-bearing ores will cause contamination of groundwaters by As at levels sufficient to have a major negative effect on the health of humans and animals.     

Arsenic redox transformation by humic substances and Fe minerals

The toxicity and mobility of the redox-active metalloid As strongly depends on its oxidation state, with As(III) (arsenite) being more toxic and mobile than As(V) (arsenate). It is, therefore, necessary to know the biogeochemical processes potentially influencing As redox state to understand and predict its environmental behavior. The first part of this presentation will discuss the quantification of As redox changes by pH-neutral mineral suspensions of goethite [α-Fe^IIIOOH] amended with Fe(II) using wet-chemical and synchrotron X-ray absorption (XANES) analysis (Amstaetter et al., 2010). First, it was found that goethite itself did not oxidize As(III). Second, in contrast to thermodynamic predictions, Fe(II)–goethite systems did not reduce As(V). However, surprisingly, rapid oxidation of As(III) to As(V) was observed in Fe(II)–goethite systems. Iron speciation and mineral analysis by Mössbauer spectroscopy showed rapid formation of ⁵⁷Fe–goethite after ⁵⁷Fe(II) addition and the formation of a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mössbauer spectroscopy, EXAFS, scanning electron microscopy, X-ray diffraction or high-resolution transmission electron microscopy. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite.The second part of the presentation will show that semiquinone radicals produced during microbial or chemical reduction of a humic substance model quinone (AQDS, 9,10-anthraquinone-2,6-disulfonic acid) can react with As and change its redox state (Jiang et al., 2009). The results of these experiments showed that these semiquinone radicals are strong oxidants and oxidize arsenite to arsenate, thus decreasing As toxicity and mobility. The oxidation of As(III) depended strongly on pH. More arsenite (up to 67.3%) was oxidized at pH 11 compared to pH 7 (12.6% oxidation) and pH 3 (0.5% oxidation). In addition to As(III) oxidation by semiquinone radicals, hydroquinones that were also produced during quinone reduction, reduced As(V) to As(III) at neutral and acidic pH values (less than 12%) but not at alkaline pH. In an attempt to understand the observed redox reactions between As and reduced/oxidized quinones present in humic substances, the radical content in reduced AQDS solutions was quantified and Eh-pH diagrams were constructed. Both the radical quantification and the Eh-pH diagram allowed explaining the observed redox reactions between the reduced AQDS solutions and the As.In summary these studies indicate that in the simultaneous presence of Fe(III) oxyhydroxides, Fe(II), and humic substances as commonly observed in environments inhabited by Fe-reducing microorganisms, As(III) oxidation can occur. This potentially explains the presence of As(V) in reduced groundwater aquifers.