Arsenic mobility in mildly alkaline drainage from an orogenic lode gold deposit,Bralorne mine,British Columbia

The historical (1932–1971) Bralorne mine produced over 87 million grams of Au from an archetypal orogenic lode gold deposit in southwest British Columbia. High concentrations of As in mine drainage, however, represent an on-going environmental concern prompting a detailed study of effluent chemistry. The discharge rate at the mine portal was monitored continuously over a fourteen-month period during which effluent samples were collected on a quasi-weekly basis. Water samples were also collected on synoptic surveys of the adit between the portal and the main source of flow in the flooded workings. Total concentrations of As in the mildly alkaline (pH = 8.7) portal drainage average 3034 μg/L whereas at the source they average 5898 μg/L. As emergent waters from the flooded workings flow toward the portal, their dissolved oxygen content and pH increase from 0 to 10 mg/L and from 7.7 to 9, respectively. Near the emergence point, dissolved Fe precipitates rapidly, sorbing both As(III) and As(V). With increasing distance from the emergence point, dissolved As(III) concentrations drop to detection limits through sorption on hydrous ferric oxide and through oxidation to As(V). Concentrations of dissolved As(V), on the other hand, increase and stabilize, reflecting lower sorption at higher pH and the lack of available sorbent. Nonetheless, based on synoptic surveys, approximately 35% of the source As load is sequestered in the adit resulting in As sediment concentrations averaging 8.5 wt%. The remaining average As load of 1.34 kg/d is discharged from the portal. Partitioning of As(V) between dissolved and particulate phases in portal effluent is characterized by a sorption density of 0.37 mol As (mol Fe)⁻¹ and by a distribution coefficient (K_d) of 130 L/g HFO. The relatively high sorption density may reflect co-precipitation of As with Fe oxyhydroxides rather than a purely adsorption-controlled process. Results of this study show that the As self-mitigating capacity of drainage from orogenic lode gold deposits may be poor in high-pH and Fe-limited settings.     

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.     

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.     

Sorption and precipitation of Co(II) in Hanford sediments and alkaline aluminate solutions

Sorption and precipitation of Co(II) in simplified model systems related to the Hanford site high-level nuclear waste tank leakage were investigated through solution studies, geochemical modeling, and X-ray absorption fine structure (XAFS) spectroscopy. Studies of Co(II) sorption to pristine Hanford sediments (ERDF and Sub), which consist predominantly of quartz, plagioclase, and alkali feldspar, show an adsorption edge centered at pH ≈ 8.0 for both sediments studied, with sorption >99% above pH ≈ 9.0. Aqueous SiO₂ resulting from dissolution of the sediments increased in concentration with increasing pH, though the systems remained undersaturated with respect to quartz. XAFS studies of Co(II) sorption to both sediment samples reveal the oxidation of Co(II) to Co(III), likely by dissolved O₂, although this oxidation was incomplete in the Sub sediment samples. The authors propose that Fe(II) species, either in aqueous solution or at mineral surfaces, partially inhibited Co(II) oxidation in the Sub sediment samples, as these sediments contain significantly higher quantities of Fe(II)-bearing minerals which likely partially dissolved under the high-pH solution conditions. In alkaline solutions, Al precipitated as bayerite, gibbsite, or a mixture of the two at pH > 7; an amorphous gel formed at pH values less than 7. Aqueous Co concentrations were well below the solubility of known Co-bearing phases at low pH, suggesting that Co was removed from solution through an adsorption mechanism. At higher pH values, Co concentrations closely matched the solubility of a Co-bearing hydrotalcite-like solid. XAFS spectra of Co(II) sorbed to Al-hydroxide precipitates are similar to previously reported spectra for such hydrotalcite-like phases. The precipitation processes observed in this study can significantly reduce the environmental hazard posed by ⁶⁰Co in the environment.     

Seasonal variations of arsenic at the sediment–water interface of Poyang Lake,China

Arsenic species including arsenite, arsenate, and organic arsenic were measured in the porewaters collected from Poyang Lake, the largest freshwater lake of China. The vertical distributions of dissolved arsenic species and some diagenetic constituents [Fe(II), Mn(II), S(−II)] were also obtained in the same porewater samples in summer and winter. In sediments the concentration profiles of total As and As species bound to Fe–Mn oxyhydroxides and to organic matter were also determined along with the concentrations of Fe, Mn and S in different extractable fractions. Results indicate that, in the summer season, the concentrations of total dissolved As varying from 3.9 to 55.8 μg/L in sediments were higher than those (5.3–15.7 μg/L) measured in the winter season, while the concentrations of total As species in the solid phase varied between 10.97 and 25.32 mg/kg and between 7.84 and 30.52 mg/kg on a dry weight basis in summer and winter, respectively. Seasonal profiles of dissolved As suggest downward and upward diffusion, and the flux of dissolved As across the sediment–water interface (SWI) in summer and winter were estimated at 3.88 mg/m² a and 0.79 mg/m² a, respectively. Based on porewater profiles and sediment phase data, the main geochemical behavior of As was controlled by adsorption/desorption, precipitation and molecular diffusion. The solubility and migration of inorganic As are controlled by Fe–Mn oxyhydroxides in summer whereas they appear to be more likely controlled by both amorphous Fe–Mn oxyhydroxides and sulfides in winter. A better knowledge of the cycle of As in Poyang Lake is essential to a better management of its hydrology and for the environmental protection of biota in the lake.     

Influence of arsenic on iron sulfide transformations

The association of arsenate, As(V), and arsenite, As(III), with disordered mackinawite, FeS, was studied in sulfide-limited (Fe:S = 1:1) and excess-sulfide (Fe:S = 1:2) batch experiments. In the absence of arsenic, the sulfide-limited experiments produce disordered mackinawite while the excess-sulfide experiments yield pyrite with trace amounts of mackinawite. With increasing initially added As(V) concentrations the transformation of FeS to mackinawite and pyrite is retarded. At S:As = 1:1 and 2:1, elemental sulfur and green rust are the end products. As(V) oxidizes S(-II) in FeS and (or) in solution to S(0), and Fe(II) in the solid phase to Fe(III). Increasing initially added As(III) concentrations inhibit the transformation of FeS to mackinawite and pyrite and no oxidation products of FeS or sulfide, other than pyrite, were observed. At low arsenic concentrations, sorption onto the FeS surface may be the reaction controlling the uptake of arsenic into the solid phase. Inhibition of iron(II) sulfide transformations due to arsenic sorption suggests that the sorption sites are crucial not only as sorption sites, but also in iron(II) sulfide transformation mechanisms.     

Laboratory study of calcite–gypsum sludge–water interactions in a flooded tailings impoundment at the Kristineberg Zn–Cu mine,northern Sweden

Due to liming of acid mine drainage, a calcite–gypsum sludge with high concentrations of Zn (24,400 ± 6900 μg g⁻¹), Cu (2840 ± 680 μg g⁻¹) and Cd (59 ± 20 μg g⁻¹) has formed in a flooded tailings impoundment at the Kristineberg mine site. The potential metal release from the sludge during resuspension events and in a long-term perspective was investigated by performing a shake flask test and sequential extraction of the sludge. The sequentially extracted carbonate and oxide fractions together contained ⩾97% of the total amount of Cd, Co, Cu, Ni, Pb and Zn in the sludge. The association of these metals with carbonates and oxides appears to result from sorption and/or coprecipitation reactions at the surfaces of calcite and Fe, Al and Mn oxyhydroxides forming in the impoundment. If stream water is diverted into the flooded impoundment, dissolution of calcite, gypsum and presumably also Al oxyhydroxides can be expected during resuspension events. In the shake flask test (performed at a pH of 7–9), remobilisation of Zn, Cu, Cd and Co from the sludge resulted in dissolved concentrations of these metals that were significantly lower than those predicted to result from dissolution of the carbonate fraction of the sludge. This may suggest that cationic Zn, Cu, Cd and Co remobilised from dissolving calcite, gypsum and Al oxyhydroxides were readsorbed onto Fe oxyhydroxides remaining stable under oxic conditions. In a long-term perspective (≳10² a), ⩾97% of the Cd, Co, Cu, Ni, Pb and Zn content of the sludge potentially is available for release by dissolution of calcite and reductive dissolution of Fe oxyhydroxides if the sludge is subject to a soil environment with lower dissolved Ca concentrations, pH and redox than in the impoundment.     

Copper and iron isotope fractionation in mine tailings at the Laver and Kristineberg mines,northern Sweden

Previous research has shown that Cu and Fe isotopes are fractionated by dissolution and precipitation reactions driven by changing redox conditions. In this study, Cu isotope composition (⁶⁵Cu/⁶³Cu ratios) was studied in profiles through sulphide-bearing tailings at the former Cu mine at Laver and in a pilot-scale test cell at the Kristineberg mine, both in northern Sweden. The profile at Kristineberg was also analysed for Fe isotope composition (⁵⁶Fe/⁵⁴Fe ratios). At both sites sulphide oxidation resulted in an enrichment of the lighter Cu isotope in the oxidised zone of the tailings compared to the original isotope ratio, probably due to preferential losses of the heavier Cu isotope into the liquid phase during oxidation of sulphides. In a zone with secondary enrichment of Cu, located just below the oxidation front at Laver, δ⁶⁵Cu (compared to ERM-AE633) was as low as −4.35 ± 0.02‰, which can be compared to the original value of 1.31 ± 0.03‰ in the unoxidised tailings. Precipitation of covellite in the secondary Cu enrichment zone explains this fractionation. The Fe isotopic composition in the Kristineberg profile is similar in the oxidised zone and in the unoxidised zone, with average δ⁵⁶Fe values (relative to the IRMM-014) of −0.58 ± 0.06‰ and −0.49 ± 0.05‰, respectively. At the well-defined oxidation front, δ⁵⁶Fe was less negative, −0.24 ± 0.01‰. Processes such as Fe(II)–Fe(III) equilibrium and precipitation of Fe-(oxy)hydroxides at the oxidation front are assumed to cause this Fe isotope fractionation. This field study provides additional support for the importance of redox processes for the isotopic composition of Cu and Fe in natural systems.     

Composition and characteristics of the ferromanganese crusts from the western Arctic Ocean

Layered ferromanganese crusts collected by dredge from a water depth range of 2770 to 2200 m on Mendeleev Ridge, Arctic Ocean, were analyzed for mineralogical and chemical compositions and dated using the excess ²³⁰Th technique. Comparison with crusts from other oceans reveals that Fe-Mn deposits of Mendeleev Ridge have the highest Fe/Mn ratios, are depleted in Mn, Co, and Ni, and enriched in Si and Al as well as some minor elements, Li, Th, Sc, As and V. However, the upper layer of the crusts shows Mn, Co, and Ni contents comparable to crusts from the Atlantic and Indian Oceans. Growth rates vary from 3.03 to 3.97 mm/Myr measured on the uppermost 2 mm. Mn and Fe oxyhydroxides (vernadite, ferroxyhyte, birnessite, todorokite and goethite) and nonmetalliferous detrital minerals characterize the Arctic crusts. Temporal changes in crust composition reflect changes in the depositional environment. Crust formation was dominated by three main processes: precipitation of Fe-Mn oxyhydroxides from ambient ocean water, sorption of metals by those Fe and Mn phases, and fluctuating but large inputs of terrigenous debris.     

Elemental sulfur in drain sediments associated with acid sulfate soils

This paper reports the abundance of elemental S in drain sediments associated with acid sulfate soils. The sediments exhibited near-neutral pH (5.97–7.27), high concentrations of pore-water Fe²⁺ (1.37–15.9 mM) and abundant oxalate-extractable Fe (up to 4300 μmol g⁻¹). Maximum acid-volatile sulfide (AVS) concentrations in each sediment profile were high (118–1019 μmol g⁻¹), with AVS often exceeding pyrite-S. Elemental S occurred at concentrations of 13–396 μmol g⁻¹, with the higher concentrations exceeding previous concentrations reported for other sedimentary systems. Up to 62% of reduced inorganic S near the sediment/water interface was present as elemental S, due to reaction between AVS and oxidants such as O₂ and Fe(III). Significant correlation (r = 0.74; P < 0.05) between elemental S and oxalate-extractable Fe(III) is indicative of elemental S formation by in situ oxidation of AVS. The results indicate that AVS oxidation in near-surface sediments is dynamic in acidified coastal floodplain drains, causing elemental S to be a quantitatively important intermediate S fraction. Transformations of elemental S may therefore strongly influence water quality in ASS landscapes.     

Pyrite oxidation by Acidithiobacillus ferrooxidans at various concentrations of dissolved oxygen

Pyrite oxidation rates were examined at various concentrations of dissolved oxygen (DO) in the presence of the sulfur and iron oxidizer Acidithiobacillus ferrooxidans. Five different batch experiments were performed at room temperature for 75 days under various DO levels (273, 129, 64.8, 13.2, and ≤ 0.006 μM), containing pyrite grains (particle size 63–250 μm) and a modified 9K nutrient medium at pH 3. The reactors were inoculated with A. ferrooxidans. In all experiments, pH decreased with time and sulfur and iron were released to the solution, indicating pyrite oxidation at all DO levels. Pyrite oxidation rates (ca. 5 × 10^− 10 mol m^− 2 s^− 1 at 273 μM DO) from all experiments showed positive correlation with DO, Fe(III), and bacterial concentration. These rates were significantly slower than rates presented in other published studies, but this is probably due to the significantly greater Fe(III) concentration at lower pH in these previous studies. The results obtained in this study suggest that ferric iron reduction at the pyrite surface is the primarily mechanism for microbial pyrite oxidation in the presence of DO. The results from our study support the indirect mechanism of sulfide oxidation, where A. ferrooxidans oxidizes ferrous iron in the presence of DO, which then oxidizes pyrite.     

Geochemical patterns of arsenic-enriched ground water in fractured,crystalline bedrock,Northport, Maine,USA

High mean As concentrations of up to 26.6 μmol/L (1990 μg/L) occur in ground water collected from a fractured-bedrock system composed of sulfidic schist with granitic to dioritic intrusions. Sulfides in the bedrock are the primary source of the As in the ground water, but the presence of arsenopyrite in rock core retrieved from a borehole with As concentrations in the ground water barely above the detection limit of 2.0 μmol/L, shows that there are complicating factors. Chemical analyses of water from 35 bedrock wells throughout a small watershed reveal spatial clustering of wells with high As concentrations. Stiff diagrams and box plots distinguish three distinct types; calcium-bicarbonate-dominated water with low As concentrations (CaHCO₃ type), sodium-bicarbonate-dominated water with moderately high As concentrations (NaHCO₃ type), and calcium-bicarbonate-dominated water with very high As concentrations (High-As type). It is proposed that differences in recharge area and ground-water evolution, and possible bedrock composition difference are responsible for the chemical distinctions within the watershed. Lack of correlation of As concentrations with pH indicates that desorption of As is an insignificant control on As concentration. Correlations of As concentrations with Fe and redox parameters indicates that reductive dissolution of Fe(III) oxyhydroxides may play a role in the occurrence of high As concentrations in the NaHCO₃ and High-As type water. The oxidation of sulfide minerals occurs within the ground-water system and is ultimately responsible for the existence of As in the ground water, but there is no correlation between As and SO₄ concentrations, probably due to precipitation of Fe(III) oxyhydroxides and adsorption of As under oxidizing conditions.     

Adsorption and heterogeneous oxidation of arsenite on modified granular natural siderite: Characterization and behaviors

Although natural siderite has been investigated to remove both As(III) and As(V), it has relatively low adsorption rate and capacity. It is crucial to enhance its adsorption characteristics for As removal prior to being used in practical application. Modified granular natural siderite (MGNS) was fabricated through addition of organic binder, extrusion granulation and calcination, and evaluated for adsorption characteristics by means of batch and column tests. Results showed that MGNS had higher adsorption rate and capacity for As(III) in comparison with natural siderite. Arsenic(III) adsorption achieved equilibrium at 24 h, with adsorption capacity of 9.43 mg/g estimated from Langmuir isotherm at 25 °C. Column tests showed that there was less difference in total As loads in MGNS-packed filters for As(III)-spiked deionized water, As(III)-spiked tap water, and real-world high-As groundwater. The coexistence of anions had no significant effect on As adsorption in both batch and column experiments. Results of XRD, SEM and BET analysis indicated that MGNS, as an Fe(II)/(III) hybrid system, had a much larger specific surface area relative to the pristine natural siderite due to massive spherical aggregates attaching to the siderite matrix. XANES spectra showed that As(V) was the major species in the adsorbent after As(III) adsorption. Its proportion in total As slightly increased with the increase in contact time. Adsorption and heterogeneous oxidation of As(III) were believed to be the main mechanisms of As(III) removal by MGNS. This study suggested that MGNS is a potential adsorbent for effectively removing As from As-contaminated groundwater in filter application.     

Arsenic,iron and organic matter in sediments and groundwater in the Pannonian Basin,Hungary

In the central part of the Pannonian Basin, factors controlling the distribution of As in sediments and groundwater of the upper 500 m were studied. In core samples, the amounts of As, Fe and Mn extractable with hydroxylamine hydrochloride (NH₂OH · HCl) in 25% acetic acid, the proportion of the <0.063 mm size fraction, and the sediment organic C (C_org) contents were measured. In the groundwaters concentrations of As, humic substances, and selected major chemical components were determined. In most core samples extractable Fe, as FeOOH, and C_org are correlated, but some samples have excess Fe, or organic matter. In cases where either excess Fe or excess organic matter is found, the amount of As is also elevated. The spatial distribution of As in the groundwater and the lack of a consistent correlation of As with a single component indicate that there is no single factor controlling the concentration of dissolved As over the entire study area. The only consistent feature is enrichment of As relative to Fe in the groundwater, compared to the sediments. This suggests that the dissolution of Fe minerals, which primarily adsorb As, is not congruent. In reducing conditions Fe(III) oxyhydroxides together with adsorbed As dissolve, and siderite with little or no As precipitates. When sub-regions are separated and studied individually, it can be shown that hydrogeological features of the sediments, the proportions of Fe minerals and sedimentary organic matter, and the concentration of dissolved humic materials, all influence the accumulation and mobilization of As. The significance of the different mobilizing processes, however, and the mean concentration of As, is different in the recharge, through-flow and discharge areas.     

Fe(III) mobilisation by carbonate in low temperature environments: Study of the solubility of ferrihydrite in carbonate media and the formation of Fe(III) carbonate complexes

The linkage between the iron and the carbon cycles is of paramount importance to understand and quantify the effect of increased CO₂ concentrations in natural waters on the mobility of iron and associated trace elements. In this context, we have quantified the thermodynamic stability of mixed Fe(III) hydroxo-carbonate complexes and their effect on the solubility of Fe(III) oxihydroxides. We present the results of carefully performed solubility measurements of 2-line ferrihydrite in the slightly acidic to neutral–alkaline pH ranges (3.8–8.7) under constant pCO₂ varying between (0.982–98.154 kPa) at 25 °C.The outcome of the work indicates the predominance of two Fe(III) hydroxo carbonate complexes FeOHCO₃ and Fe(CO₃)₃³⁻, with formation constants log^*β°_1,1,1 = 10.76 ± 0.38 and log β°_1,0,3 = 24.24 ± 0.42, respectively.The solubility constant for the ferrihydrite used in this study was determined in acid conditions (pH: 1.8–3.2) in the absence of CO₂ and at T = (25 ± 1) °C, as log^*K_s,0 = 1.19 ± 0.41.The relative stability of the Fe(III)-carbonate complexes in alkaline pH conditions has implications for the solubility of Fe(III) in CO₂-rich environments and the subsequent mobilisation of associated trace metals that will be explored in subsequent papers.     

Arsenic associations in sediments from the loess aquifer of La Pampa,Argentina

Groundwater from the Quaternary loess aquifer of La Pampa, central Argentina, has significant problems with high concentrations of As (up to 5300 μg L⁻¹) as well as other potentially toxic trace elements such as F, B, Mo, U, Se and V. Total As concentrations in 45 loess samples collected from the aquifer have a range of 3–18 mg kg⁻¹ with a mean of 8 mg kg⁻¹. These values are comparable to world-average sediment As concentrations. Five samples of rhyolitic ash from the area have As concentrations of 7–12 mg kg⁻¹. Chemical analysis included loess sediments and extracted porewaters from two specially cored boreholes. Results reveal a large range of porewater As concentrations, being generally higher in the horizons with highest sediment As concentrations. The displaced porewaters have As concentrations ranging up to 7500 μg L⁻¹ as well as exceptionally high concentrations of some other oxyanion species, including V up to 12 mg L⁻¹. The highest concentrations are found in a borehole located in a topographic depression, which is a zone of likely groundwater discharge and enhanced residence time. Comparison of sediment and porewater data does not reveal unequivocally the sources of the As, but selective extract data (acid-ammonium oxalate and hydroxylamine hydrochloride) suggest that much of the As (and V) is associated with Fe oxides. Primary oxides such as magnetite and ilmenite may be partial sources but given the weathered nature of many of the sediments, secondary oxide minerals are probably more important. Extract compositions also suggest that Mn oxide may be an As source. The groundwaters of the region are oxidising, with dissolved O₂, NO₃ and SO₄ normally present and As(V) usually the dominant dissolved As species. Under such conditions, the solubility of Fe and Mn oxides is low and As mobilisation is strongly controlled by sorption–desorption reactions. Desorption may be facilitated by the relatively high-pH conditions of the groundwaters in the region (7.0–8.8) and high concentrations of potential competitors (e.g. V, P, HCO₃). PHREEQC modelling suggests that the presence of V at the concentrations observed in the Pampean porewaters can suppress the sorption of As to hydrous Fe(III) oxide (HFO) by up to an order of magnitude. Bicarbonate had a comparatively small competitive effect. Oxalate extract concentrations have been used to provide an upper estimate of the amount of labile As in the sediments. A near-linear correlation between oxalate-extractable and porewater As in one of the cored boreholes investigated has been used to estimate an approximate K_d value for the sediments of 0.94 L kg⁻¹. This low value indicates that the sediments have an unusually low affinity for As.     

Mobilization of arsenic from acid deposition – The Elbe River catchment,Czech Republic

Temporal changes of As concentration in surface waters were observed in some areas of the Czech Republic. Mobilized As originates from past atmospheric deposition. To understand the factors influencing As aqueous concentration and mobility the chemistry and runoff generation of a number of brooks, springs and rivers in the central part of the Elbe River catchment, Czech Republic, were monitored. Seasonal variations of As (from 0.5 to 10.5 μg L⁻¹), Fe (from 0.05 to 3.9 mg L⁻¹) and DOC (dissolved organic C – from 1.2 to 17.5 mg L⁻¹) were observed in monitored stream waters with maximum values of As and Fe in the summer months at pH values 7.6–7.8. The concentration of As in particles with a diameter < 60 μm correlates with the Fe concentration. There is no correlation between Fe and As in filtered samples (<0.45 μm). The As concentration in stream water colloids depends on an increase in DOC concentration and a decrease in ionic strength. The DOC stabilizes As in solution and reduces its re-adsorption on Fe colloids and consequently As concentration in the stream increases.     

Tracing source and evolution of suspended particles in the Rio Negro Basin (Brazil) using chemical species of iron

Suspended solids found in porewaters obtained in waterlogged soil sequences that included representative laterite–podzol transitions, associated brooks and major rivers of the Rio Negro watershed (Brazil) were studied using electron paramagnetic resonance (EPR) and Fourier-transform infrared spectroscopies. The main goal was to ascertain sources and track the evolution of suspended matter using a ubiquitous chemical species, FeIII complexed to organic matter (FeOM). Three size fractions were separated by tangential-flow (ultra)filtration: particulate (> 0.2 μm), dense (P) and light (Ps), and colloidal (5 kD < Col. < 0.2 μm) fractions. Quantitative results were acquired for Col. and Ps fractions which are predominantly organic in nature.FeOM concentration (in ‰ dry weight) was determined to be relatively low in suspended solids found in black waters from podzol porewaters and brooks whereas in the main rivers it was several times higher. FeOM concentrations were also correlated with Fe(II)/Fe(III) ratios in solution; these ratios were high in podzol porewaters and low in the rivers. Considering that organic complexation of Fe(II) is minor when compared to that of Fe(III), two interpretations were proposed to account for the above observation. First, [FeOM] was assumed to be distributed along a mixing line, with the clear waters from laterites and the black waters from podzols being its end-members. Consequently, [FeOM] can be used to trace the source of suspended material. Second, dissolved Fe(II) from podzol areas was considered to be progressively oxidized as pore waters move towards the mainstream. According to this mechanism, iron is complexed by organic matter or precipitated as oxides, thus producing an evolution of colloidal matter. As a result of these mechanisms' action, both the high production of Fe(II) and organic matter at the waterlogged podzol–laterite transition areas are major factors affecting iron export in the Rio Negro watershed.     

Net alkalinity and net acidity 2: Practical considerations

The pH, alkalinity, and acidity of mine drainage and associated waters can be misinterpreted because of the chemical instability of samples and possible misunderstandings of standard analytical method results. Synthetic and field samples of mine drainage having various initial pH values and concentrations of dissolved metals and alkalinity were titrated by several methods, and the results were compared to alkalinity and acidity calculated based on dissolved solutes. The pH, alkalinity, and acidity were compared between fresh, unoxidized and aged, oxidized samples.Data for Pennsylvania coal mine drainage indicates that the pH of fresh samples was predominantly acidic (pH 2.5–4) or near neutral (pH 6–7); ≈ 25% of the samples had pH values between 5 and 6. Following oxidation, no samples had pH values between 5 and 6.The Standard Method Alkalinity titration is constrained to yield values >0. Most calculated and measured alkalinities for samples with positive alkalinities were in close agreement. However, for low-pH samples, the calculated alkalinity can be negative due to negative contributions by dissolved metals that may oxidize and hydrolyze.The Standard Method hot peroxide treatment titration for acidity determination (Hot Acidity) accurately indicates the potential for pH to decrease to acidic values after complete degassing of CO₂ and oxidation of Fe and Mn, and it indicates either the excess alkalinity or that required for neutralization of the sample. The Hot Acidity directly measures net acidity (= −net alkalinity). Samples that had near-neutral pH after oxidation had negative Hot Acidity; samples that had pH < 6.3 after oxidation had positive Hot Acidity. Samples with similar pH values before oxidation had dissimilar Hot Acidities due to variations in their alkalinities and dissolved Fe, Mn, and Al concentrations. Hot Acidity was approximately equal to net acidity calculated based on initial pH and dissolved concentrations of Fe, Mn, and Al minus the initial alkalinity. Acidity calculated from the pH and dissolved metals concentrations, assuming equivalents of 2 per mole of Fe and Mn and 3 per mole of Al, was equivalent to that calculated based on complete aqueous speciation of Fe^II/Fe^III. Despite changes in the pH, alkalinity, and metals concentrations, the Hot Acidities were comparable for fresh and most aged samples.A meaningful “net” acidity can be determined from a measured Hot Acidity or by calculation from the pH, alkalinity, and dissolved metals concentrations. The use of net alkalinity = (Alkalinity_measured − Hot Acidity_measured) to design mine drainage treatment can lead to systems with insufficient Alkalinity to neutralize metal and H⁺ acidity and is not recommended. The use of net alkalinity = −Hot Acidity titration is recommended for the planning of mine drainage treatment. The use of net alkalinity = (Alkalinity_measured − Acidity_calculated) is recommended with some cautions.     

The transition to microbial photosynthesis in hot spring ecosystems

Even casual observations of continental hot springs reveal that photosynthesis has its limits. In an effort to explore the transition to photosynthesis, field measurements of temperature and pH were made at 996 hot spring locations at Yellowstone National Park ranging from 14° to 94 °C and pH from 0.8 to 9.7. In addition, sulfide measurements were made in 426 of these locations showing concentrations up to 8820 μg L^? 1 total sulfide. These data indicate that the previously established upper temperature (73–75 °C) for the transition to photosynthesis is reached in many basic hot springs, but that the transition occurs at lower temperature with decreasing pH below ~ 6.5. As an example, no strong evidence for photosynthesis was found above 45 °C at pH ~ 2. In several locations, photosynthesis appears to be suppressed despite temperatures and pH values that permit photosynthesis elsewhere. Sulfide concentrations may be responsible for the suppression of photosynthesis at these sites. Total sulfide concentrations were observed to decrease downstream in hot spring outflow channels. Abiotic processes (degassing, oxidation, mineral precipitation, etc.) are too slow to account for these decreases, suggesting an explanation from microbial sulfide oxidation that is supported by field experiments. Microbial sulfide oxidation may determine the ultimate suitability of some hot springs for microbial photosynthesis.