Thermodynamic model for arsenic speciation in sulfidic waters: A novel use of ab initio computations

Recent discoveries demonstrate that the chemistry of arsenic in sulfidic waters is much more complex that previously believed. One implication is that all earlier thermodynamic data on stabilities of As thioanions require revision. Previously used experimental approaches for determining As thioanion stabilities may be inadequate to deal with the full range of complexity. Here we use computational as well as empirical information to construct a provisional model for equilibrium As thioanion distributions in sulfidic waters. Whereas previous authors have argued for either As(III) or As(V) thioanions, the new model predicts that both are important and can occur simultaneously under commonly encountered pH and ΣS^−II conditions. At the order of magnitude level, the model reasonably predicts the solubility of As₂S₃ in sulfidic solutions, provides tentative peak assignments for published Raman spectroscopic data and plausibly accounts for how sulfide modifies the bacterial toxicity of As. The model yields a thermodynamic justification for how sulfide, which is usually regarded as a reducing agent, can counter-intuitively drive oxidation of As(III) to As(V), as has been observed both in the laboratory and in the field. Despite its uncertain accuracy, the model serves as a useful source of new, testable hypotheses about As geochemistry and highlights crucial experimental data needs.     

The mobility of radium-226 and trace metals in pre-oxidized subaqueous uranium mill tailings

The exchange of ²²⁶Ra and trace metals across the tailings-water interface and the mechanisms governing their mobility were assessed via sub-centimetre resolution profiling of dissolved constituents across the tailings–water interface in Cell 14 of the Quirke Waste Management Area at Rio Algom's Quirke Mine, near Elliot Lake, Ontario, Canada. Shallow zones (<1.5 m water depth) are characterized by sparse filamentous vegetation, well-mixed water columns and fully oxygenated bottom waters. Profiles of dissolved O₂, Fe and Mn indicate that the tailings deposits in these areas are sub-oxic below tailings depths of ∼3 cm. These zones exhibit minor remobilization of Ra in the upper 5 cm of the tailings deposit; ²²⁶Ra fluxes at these sites are relatively small, and contribute negligibly to the water column activity of ²²⁶Ra. The shallow areas also exhibit minor remobilization of Ni, As, Mo and U. The release of these elements to the water cover is, however, limited by scavenging mechanisms in the interfacial oxic horizons. The presence of thick vegetation (Chara sp.) in the deeper areas (>2 m water depth) fosters stagnant bottom waters and permits the development of anoxia above the benthic boundary. These anoxic tailings are characterized by substantial remobilization of ²²⁶Ra, resulting in a relatively large flux of ²²⁶Ra from the tailings to the water column. The strong correlation between the porewater profiles of ²²⁶Ra and Ba (r²=0.99), as well as solubility calculations, indicate that the mobility of Ra is controlled by saturation with respect to a poorly ordered and/or impure barite phase [(Ra,Ba)SO₄]. In the anoxic zones, severe undersaturation with respect to barite is sustained by microbial SO₄ reduction. Flux calculations suggest that the increase in ²²⁶Ra activity in the water cover since 1995 (from <0.5 to 2.5 Bq l⁻¹) can be attributed to an increase in the spatial distribution of anoxic bottom waters caused by increased density of benthic flora. The anoxic, vegetated areas also exhibit minor remobilization with respect to dissolved As, Ni and Zn. The removal of trace metals in the anoxic bottom waters appears to be limited by the availability of free sulphide. Collectively, the data demonstrate that while the water cover over the U mill tailings minimizes sulphide oxidation and metal mobility, anoxic conditions which have developed in deeper areas have led to increased mobility of ²²⁶Ra.     

Arsenic speciation in Mono Lake, California: Response to seasonal stratification and anoxia

Mono Lake is a closed-basin, alkaline, hypersaline lake located at the western edge of the Great Basin in eastern California. We studied the distribution of arsenic (As) species in the water column of Mono Lake between February and November, 2002. This period captured the seasonal progression from winter mixing, through summer thermal stratification, to autumn overturn. Arsenic speciation was determined by ion chromatography-inductively coupled-plasma-mass spectrometry of samples preserved in the field by flash-freezing in liquid nitrogen. We found that arsenic speciation was dominated (>90%) by arsenate when oxygen was detectable. Once levels fell below 6 μmol/L O₂, arsenic speciation shifted to dominance by reduced species. Arsenate and arsenite co-occurred in a transition zone immediately below the base of the oxycline and low but significant concentrations of arsenate were occasionally detected in sulfidic hypolimnion samples. Thio-arsenic species were the dominant form of As found in sulfidic waters. Maxima of thio-arsenic species with stoichiometries consistent with mono-, di- and trithio-arsenic occurred in succession as sulfide concentration increased. A compound with a stoichiometry consistent with trithio-arsenic was the dominant As species (∼50% of total As) in high sulfide (2 mmol/L) bottom water. Lower concentrations of total As in bottom water relative to surface water suggest precipitation of As/S mineral phases in response to sulfide accumulation during prolonged anoxia.     

Surface chemistry of disordered mackinawite (FeS)

Disordered mackinawite, FeS, is the first formed iron sulfide in ambient sulfidic environments and has a highly reactive surface. In this study, the solubility and surface chemistry of FeS is described. Its solubility in the neutral pH range can be described by K_s^app = {Fe²⁺} · {H₂S(aq)} · {H⁺}⁻² = 10^+4.87±0.27. Acid-base titrations show that the point of zero charge (PZC) of disordered mackinawite lies at pH ∼7.5. The hydrated disordered mackinawite surface can be best described by strongly acidic mono-coordinated and weakly acidic tricoordinated sulfurs. The mono-coordinated sulfur site determines the acid-base properties at pH < PZC and has a concentration of 1.2 × 10⁻³ mol/g FeS. At higher pH, the tricoordinated sulfur, which has a concentration of 1.2 × 10⁻³ mol/g FeS, determines surface charge changes. Total site density is 4 sites nm⁻². The acid-base titration data are used to develop a surface complexation model for the surface chemistry of FeS.     

The behavior of molybdenum and its isotopes across the chemocline and in the sediments of sulfidic Lake Cadagno, Switzerland

Molybdenum (Mo) isotope studies in black shales can provide information about the redox evolution of the Earth’s oceans, provided the isotopic consequences of Mo burial into its major sinks are well understood. Previous applications of the Mo isotope paleo-ocean redox proxy assumed quantitative scavenging of Mo when buried into sulfidic sediments. This paper contains the first complete suite of Mo isotope fractionation observations in a sulfidic water column and sediment system, the meromictic Lake Cadagno, Switzerland, a small alpine lake with a pronounced oxygen-sulfide transition reaching up to H₂S ∼ 200 μM in the bottom waters (or about 300 μM total sulfide: ΣS²⁻ = H₂S + HS⁻ + S²⁻). We find that Mo behaves conservatively in the oxic zone and non-conservatively in the sulfidic zone, where dissolved Mo concentrations decrease from 14 nM to 2-8 nM across this transition. Dissolved Mo in the upper oxic waters has a δ⁹⁸Mo_oxic = 0.9 ± 0.1‰, which matches that of the riverine input, δ⁹⁸Mo_river = 0.9 ± 0.1‰. In the deeper sulfidic waters, a subaquatic source delivers Mo at 1.55 ± 0.1‰, but the dissolved Mo is even heavier at δ⁹⁸Mo_sulfidic = 1.8‰. Sediment traps in the sulfidic zone of the lake collect particles increasingly enriched in Mo with depth, with δ⁹⁸Mo values significantly fractionated at −0.8‰ to −1.2‰ both near the chemocline and in the deepest trap. Suspended particulates in the sulfidic waters carry lighter Mo than the ambient dissolved Mo pool by ∼0.3-1.5‰. Sedimentary Mo concentrations correlate with total organic carbon and yield Mo levels which are two orders of magnitude higher than typical crustal values found in rocks from the catchment area. Solid-phase Mo in the sediment shows a slightly positive δ⁹⁸Mo trend with depth, from δ⁹⁸Mo = 1.2‰ to 1.4‰ while the pore waters show dramatic enrichments of Mo (>2000 nM) with a relatively light isotope signature of δ⁹⁸Mo = 0.9-1.0‰.These data are explained if Mo is converted to particle-reactive oxythiomolybdates in the sulfidic waters and is fractionated during removal from solution onto particles. Isotope fractionation is expressed in the water column, despite the high sulfide concentrations, because the rate of Mo removal is fast compared to the slow reaction kinetics of thiomolybdate formation. However, elemental and isotopic mass balances show that Mo is indeed quantitatively removed to the lake sediments and thus the isotopic composition of the sediments reflects sources to the sulfidic water. This efficient Mo drawdown is expected to occur in settings where H₂S is very much in excess over Mo or in a restricted setting where the water renewal rate is slow compared to the Mo burial rate. We present a model for the Mo isotope fractionation in sulfidic systems associated with the slow reaction kinetics and conclude that quantitative removal will occur in highly sulfidic and restricted marine systems.     

Sequestration mechanisms and anthropogenic inputs of rhenium in sediments from Eastern Canada lakes

The concentrations of Re, as well as those of several other geochemical variables, were measured in dated sediment cores and in porewater samples from four lacustrine basins in Eastern Canada: one, perennially oxic, located 40 km from Québec City and three, seasonally anoxic, located within 25 km of non-ferrous metal smelters. The drainage basins of these lakes are uninhabited and have not been affected by human activity or wildfires. All of the depth profiles of dissolved Re indicate: higher Re concentrations in the water overlying the sediment than in the porewater; diffusion of Re across the sediment-water interface; a progressive decrease in porewater Re concentrations to reach minimum values of ∼0.5 pM within a 10-cm sediment depth interval. Modeling of these Re porewater profiles with a one-dimensional transport-reaction equation indicates that Re is removed from porewater within this depth interval. Based on thermodynamic predictions of Re speciation and of saturation states and on comparison of these predictions with sulfide porewater profiles, we infer that Re is removed from porewater by precipitation of rheniite (ReS_2(s)). The rate constant for the formation of ReS_2(s) in sediments is estimated from the modeling exercise to be 0.51 ± 0.64 × 10⁻²¹ mol cm⁻³ s⁻¹. Accumulation of sedimentary Re shows a strong authigenic component, as in anoxic marine sediments. Sharp increases in solid-phase Re during the last century are attributed to atmospheric deposition of anthropogenic Re deriving from coal burning and nearby smelter emissions.     

Monitoring and Modeling of Metal Concentration Distributions in Anoxic Basins: Aitoliko Lagoon, Greece

The balance between physicochemical processes, influencing vertical and temporal distributions of metal compounds in one relatively isolated anoxic environment, constitutes the objective of the present work. Ion activity product (IAP) was calculated for manganese and iron sulfides, in order to define the metal sulfide forms that control Fe and Mn solubility in the bottom waters of anoxic lagoons. Iron solubility depended on amorphous FeS formation, while manganese sulfides were a minor component in a solid solution lowering its solid-phase activity. A theoretical physicochemical model was developed for the iron speciation, based on experimental pH and redox potential data. A very good match was achieved for the measured and the theoretical total dissolved iron, at all depths. The dominance of oxidant iron species Fe(OH) ₃ ^? in the surface waters and their sequence by FeSH⁺ and FeS_aq in the deeper layers brings out the influence of physicochemical parameters (dissolved oxygen, sulfide, pH and E_h) in vertical distribution of dissolved metal species, in anoxic/hypoxic basins. Based on these findings, we can conclude that the distribution of manganese and iron is of special interest, not only because these are the indicators of redox conditions but also for the role of their oxidized/reduced forms in the formation of the biogeochemical structure of redox zone.     

The post-depositional reactivity of iron and managanese in the sediments of a macrotidal estuarine system

Four cores of anoxic sediments were collected from the Seine estuary to assess the early diagenesis pathways leading to the formation of previously reactive phase. Pore waters were analyzed for dissolved iron (Fe) and manganese (Mn) and different ligands (e.g., sulfate, chloride, total inorganic carbon). The anoxic zone is present up to the first centimeter depth, in these conditions the reduction of Mn and Fe oxides and SO₄ ²⁻ was verified. The sulfate reduction was well established with a subsequent carbon mineralization in the NORMAI94 core. The chemical speciation of Mn and Fe in the dissolved and solid phases was determined. For the dissolved phase, thermodynamic calculations were used to characterize and illustrate the importance of carbonate and phosphate phases as sinks for Fe and Mn. The ion activity product (IAP) of Fe and Mn species was compared to the solubility products (Ks) of these species. In the solid phase, the presence of higher concentration of calcium carbonate in the Seine sediments is an important factor controlling Mn cycle. The carbonate-bound Mn can reach more than 75% of the total concentration. This result is confirmed by the use of electron spin resonance (ESR) spectroscopy. The reduction of Fe is closely coupled to the sulfate reduction by the formation of new solid phases such as FeS and FeS₂, which can be regarded as temporal sinks for sulfides. These forms were quantified in all cores as acid volatile sulfide (AVS: FeS+ free sulfide) and chromium reducible sulfide (CRS: FeS₂+elemental sulfur S⁰).     

Catalysis by mineral surfaces: Implications for Mo geochemistry in anoxic environments

Fixation of Mo in sulfidic environments is believed to be preceded by conversion of geochemically passive MoO₄²⁻ to particle-reactive thiomolybdates (MoO_xS_4−x²⁻). In aqueous solution, these transformations are general-acid catalyzed, implying that proton donors can accelerate both the forward and reverse reactions. Here, we explore whether mineral surfaces also catalyze thiomolybdate interconversions. The rate of MoS₄²⁻ hydrolysis is investigated in the presence and absence of natural kaolinite (KGa-1b) and synthetic Al₂O₃ and SiO₂ phases. Comparison of rates achieved with these phases suggests that the Al oxyhydroxide component in kaolinite furnishes the catalytic activity. An anhydrous Al₂O₃ phase is catalytically inactive until hydrated (and therefore protonated). Surface kinetics with kaolinite at mildly alkaline pH are consistent with rate limitation by formation or decomposition of monomeric surface complexes; oligomeric surface intermediates may become important at MoS₄²⁻ > 20 μmol/L, higher than is likely to be found in nature. The pH dependence of the kaolinite-catalyzed reaction suggests that weak-acid surface sites promote hydrolysis. Intermediate thiomolybdates or molybdate appears to compete for active sites, inhibiting MoS₄²⁻ hydrolysis. Catalysis of MoOS₃²⁻ hydrolysis is also observed but has not been studied systematically. Thiomolybdate hydrolysis is inhibited slightly by sulfate and more strongly by phosphate. Low NaCl concentrations (<10⁻² mol/L) promote hydrolysis, but higher NaCl concentrations retard the reaction to a small extent. A mechanism is postulated involving expansion of the coordination number around Mo from 4 to 6 under the influence of the surface. The effective concentration of surface sites available to Mo in sediment pore waters is likely to be large enough to greatly accelerate thiomolybdate hydrolysis and sulfidation. Possibly this explains why Mo capture in seasonally or intermittently anoxic environments often occurs through processes operating within sediments but not in overlying waters.     

Distribution, characterization, and geochemical controls of elements of concern in uranium mine tailings, Key Lake, Saskatchewan, Canada

The distribution of As, Mo, Ni and Se in the aqueous and solid phases of U mine tailings in the Deilmann Tailings Management Facility (DTMF), located at the Key Lake mine in northern Saskatchewan, Canada, was defined using as-discharged tailings samples collected monthly starting in 1996 and core samples collected from the DTMF from 3 locations on 3 occasions between 2004 and 2009. These data indicated that the DTMF can be divided into two geochemical zones; tailings generated from the Deilmann ore body between 1996 and 2000 and tailings from the McArthur River ore body, mined after July 2000. The Deilmann tailings solids are generally characterized by greater elemental concentrations than those in the McArthur River tailings, particularly for As, Co and Ni. These elevated concentrations are attributed to the abundance of Ni–Co–As–S minerals in this ore. The mean aqueous concentrations of As, Mo, Ni, and Se are 3.7, 23.2, 0.14, and 0.02 mg L⁻¹, respectively, in the Deilmann porewaters and 0.20, 4.16, 0.06, and 0.03 mg L⁻¹, respectively, in the McArthur River porewaters. Similarly, the mean As, Mo, Ni, and Se solid phase concentrations are 5.89 × 10³, 69.9, 3.20 × 10³, and 17.4 μg g⁻¹, respectively, for the Deilmann tailings and 440, 13.6, 551, and 3.03 μg g⁻¹ in the McArthur River tailings. Statistically, pH remained unchanged from the time of discharge while Eh values have remained oxic with no significant change between the two tailings types over 15 a of residence time. Results from sequential extractions, thermodynamic modeling, and results of complimentary research indicated that ferrihydrite solubility is the dominant control on aqueous As concentrations and also plays a role in controlling dissolved Mo, Ni and Se.     

Methylmercury in tailings ponds of Amazonian gold mines (French Guiana): Field observations and an experimental flocculation method for in situ remediation

Sites of monomethylmercury (MMHg) production in Amazonian regions have been identified in hydraulic reservoirs, lake sediments and wetlands, but tailings ponds have not yet received sufficient attention for this purpose. This work evidenced high MMHg production within the water column and the interstitial water of two tailings ponds of French Guiana Au mines located; (i) in a small scale exploitation (Combat) where Hg was used for Au amalgamation, and (ii) in an industrial on-going Au mine (Yaoni) processing without Hg. The (MMHg)_D maximum (2.5 ng L⁻¹) occurred in the oxic water column above the sediment-water interface (SWI) of the most recent tailings pond (Combat), where the substrate was fresh, the redox transition was sharp and the pool of total Hg was large. In the Yaoni pond, the (MMHg)_D maximum concentration (1.4 ng L⁻¹) was located at the SWI where suboxic conditions prevailed. Using the (MMHg)_D concentration as a proxy for Hg methylation rates, the present results show that Hg methylation may occur in various redox conditions in tailings ponds, and are favored in areas where the organic matter regeneration is more active.A 3-month long laboratory experiment was performed in oxic and anoxic boxes filled with high turbidity waters from the Combat Au mine to simulate tailings ponds. Slaked lime was added in an experimental set (2 mg L⁻¹) and appeared to be very efficient for the reduction of suspended particulate matter (SPM) to environmentally acceptable concentrations. However, at the end of the experiment, large (MMHg)_D concentrations were monitored under treated anoxic conditions with the (MMHg)_D maximum located at the SWI above the Fe-reducing zones. No (MMHg)_D was detected in oxic experiments. The use of slaked lime for SPM decantation appears to be an efficient and non-onerous process for Au miners to avoid Hg methylation in tailings ponds when it is combined with rapid drainage of the mine waters. A subsequent human intervention is however necessary for the recovery of soil structure through the cover of dried ponds with organic rich materials and reforestation to avoid the stagnation of rain waters and the occurrence of anoxia.     

Thermodynamics and organic matter: constraints on neutralization processes in sediments of highly acidic waters

The controls on the internal neutralization of low productivity, highly acidified waters by sulfide accumulation in sediments are yet poorly understood. It is demonstrated that the neutralization process is constrained by organic matter quality and thermodynamic effects which control the relative rates of SO₄ and Fe reduction, and the fate of the reduced Fe and S in the sediments. The investigated sediments were rich in dissolved Fe(II) (0.005–12 mmol l⁻¹) and SO₄ (1.3–22 mmol l⁻¹). The pH ranged from 3.0 to 6.8. Contents of reduced inorganic S (0.1–9.5%), molar C/N ratios of the organic matter (12–80) and metabolic turnover rates (1–110 μeq cm⁻³ a⁻¹) varied strongly. Substantial amounts of Fe sulfides were only found at a simultaneous partial thermodynamic and solubility equilibrium of the involved biogeochemical processes. Sulfide oxidation was apparently inhibited, and SO₄ and Fe reduction coexisted. In this type of sediment increases in C availability cause enhanced neutralization rates. In the absence of a partial equilibrium, the sediments were in a sulfide oxidizing and Fe reducing state, and did not accumulate Fe sulfides. The latter type of sediment will increase neutralization rates in response to decreasing deposition of reactive Fe oxides but not necessarily in response to increases in lake productivity by e.g. fertilization measures.     

Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (∼15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ∼15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H₂S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ∼90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ∼15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS⁻ production.     

Organic complexation of rare earth elements in natural waters: Evaluating model calculations from ultrafiltration data

The Stockholm Humic Model (SHM) and Humic Ion-Binding Models V and VI were compared for their ability to predict the role of dissolved organic matter (DOM) in the speciation of rare earth elements (REE) in natural waters. Unlike Models V and VI, SHM is part of a speciation code that also allows us to consider dissolution/precipitation, sorption/desorption and oxidation/reduction reactions. In this context, it is particularly interesting to test the performance of SHM. The REE specific equilibrium constants required by the speciation models were estimated using linear free-energy relationships (LFER) between the first hydrolysis constants and the stability constants for REE complexation with lactic and acetic acid. Three datasets were used for the purpose of comparison: (i) World Average River Water (Dissolved Organic Carbon (DOC) = 5 mg L⁻¹), previously investigated using Model V, was reinvestigated using SHM and Model VI; (ii) two natural organic-rich waters (DOC = 18-24 mg L⁻¹), whose REE speciation has already been determined with both Model V and ultrafiltration studies, were also reinvestigated using SHM and Model VI; finally, (iii) new ultrafiltration experiments were carried out on samples of circumneutral-pH (pH 6.2-7.1), organic-rich (DOC = 7-20 mg L⁻¹) groundwaters from the Kervidy-Naizin and Petit-Hermitage catchments, western France. The results were then compared with speciation predictions provided by Model VI and SHM, successively. When applied to World Average River Water, both Model VI and SHM yield comparable results, confirming the earlier finding that a large fraction of the dissolved REE in rivers occurs as organic complexes This implies that the two models are equally valid for calculating REE speciation in low-DOC waters at circumneutral-pH. The two models also successfully reproduced ultrafiltration results obtained for DOC-rich acidic groundwaters and river waters. By contrast, the two models yielded different results when compared to newly obtained ultrafiltration results for DOC-rich (DOC > 7 mg L⁻¹) groundwaters at circumneutral-pH, with Model VI predictions being closer to the ultrafiltration data than SHM. Sensitivity analysis indicates that the “active DOM parameter” (i.e., the proportion of DOC that can effectively complex with REE) is a key parameter for both Model VI and SHM. However, a survey of ultrafiltration results allows the “active DOM parameter” to be precisely determined for the newly ultrafiltered waters studied here. Thus, the observed discrepancy between SHM predictions and ultrafiltration results cannot be explained by the use of inappropriate “active DOM parameter” values in this model. Save this unexplained discrepancy, the results presented in this study demonstrate that both Model VI and SHM can provide reliable estimates of REE speciation in organic-rich waters. However, it is essential to know the proportion of DOM that can actively complex REE before running these two speciation models.     

Geological analogue for circumneutral pH mine tailings: implications for long-term storage,Macraes Mine,Otago, New Zealand

Tailings from the Macraes Au mine cyanidation process are stored in an impoundment about 0.6 km² and 80 m deep whose pH is maintained near 8 by the neutralizing capacity of the gangue minerals. The tailings are sandy (>50 μm particles), have a hydraulic conductivity of about 10⁻² m/day, and contain 0.1–1.0 wt.% S and 0.1–1.5 wt.% graphitic C from the primary deposit. Concentrations of As in the pore water of the mixed tailings, which are a combination of various tailings types, range from 0.1 to 20 ppm, HCO₃^- is 100 to 200 ppm, and dissolved SO₄ is 100–1700 ppm. The mixed tailings will be stored in this impoundment in perpetuity after mining ceases. Confidence in the long-term pH stability of these tailings can be gained from examination of mineralogically and chemically similar geological analogues in the immediate vicinity. A sequence, typically about 5 m thick, of sands and gravels derived from the Macraes mineralized zone 12–28 ka ago contains rounded detrital sulfide mineral grains which are unoxidized despite their close proximity to the surface and the occasional incursion of oxygenated waters. These sediments have a hydraulic conductivity of about 10⁻⁴ m/day. Saturating water pH is currently 7–8. Sands with 0.2–0.8 wt.% organic C host SO₄-reducing bacteria (SRB), and local cementation by authigenic framboidal pyrite has occurred. SRB were found in water-saturated sediments with decreased hydraulic conductivity and alkaline and anoxic conditions. These bacteria are involved in the formation of authigenic framboidal pyrite, reducing the cycling of dissolved Fe in the sediments. Carbon is not a limiting factor in this process as organic matter is present in the sandstone and ground water contains up to 180 ppm HCO₃^-. Comparison of the 28 ka old sediments with the modern tailings suggests that the chemical behaviour of the two will be similar, possibly with the crystallization of authigenic pyrite in the tailings over the long term. As long as the present slightly anoxic and circumneutral pH environmental conditions are maintained in the mixed tailings impoundment, sulfide decomposition and acidification are unlikely.     

Transport of particulate organic carbon by the Mississippi River and its fate in the Gulf of Mexico

This study was designed to determine the amount of particulate organic carbon (POC) introduced to the Gulf of Mexico by the Mississippi River and assess the influence of POC inputs on the development of hypoxia and burial of organic carbon on the Louisiana continental shelf. Samples of suspended sediment and supporting hydrographic data were collected from the river and >50 sites on the adjacent shelf. Suspended particles collected in the river averaged 1.8±0.3% organic carbon. Because of this uniformity, POC values (in μmol l^?1) correlated well with concentrations of total suspended matter. Net transport of total organic carbon by the Mississippi-Atchafalaya River system averaged 0.48×10¹² moles y^?1 with 66% of the total organic carbon carried as POC. Concentrations of POC decreased from as high as 600 μmol l^?1 in the river to <0.8 μmol l^?1 in offshore waters. In contrast, the organic carbon fraction of the suspended matter increased from <2% of the total mass in the river to >35% along the shelf at ≥10 km from the river mouth. River flow was a dominant factor in controlling particle and POC distributions; however, time-series data showed that tides and weather fronts can influence particle movement and POC concentrations. Values for apparent oxygen utilization (AOU) increased from ～60 μmol l^?1 to >200 μmol l^?1 along the shelf on approach to the region of chronic hypoxia. Short-term increases in AOU were related to transport of more particle-rich waters. Sediments buried on the shelf contained less organic carbon than incoming river particles. Orgamic carbon and δ¹³C values for shelf sediments indicated 3 that large amounts of both terrigenous and marine organic carbon are being decomposed in shelf waters and sediments to fuel observed hypoxia.     

Particulate sulfur species in the water column of the Cariaco Basin

The biogeochemistry of iron sulfide minerals in the water column of the Cariaco Basin was investigated in November 2007 (non-upwelling season) and May 2008 (upwelling season) as part of the on-going CARIACO (CArbon Retention In A Colored Ocean) time series project. The concentrations of particulate sulfur species, specifically acid volatile sulfur (AVS), greigite, pyrite, and particulate elemental sulfur, were determined at high resolution near the O₂/H₂S interface. In November 2007, AVS was low throughout the water column, with the highest concentration at the depth where sulfide was first detected (260 m) and with a second peak at 500 m. Greigite, pyrite, and particulate elemental sulfur showed distinct concentration maxima near the interface. In May 2008, AVS was not detected in the water column. Maxima for greigite, pyrite, and particulate elemental sulfur were again observed near the interface. We also studied the iron sulfide flux using sediment trap materials collected at the Cariaco station. Pyrite comprised 0.2-0.4% of the total particulate flux in the anoxic water column, with a flux of 0.5-1.6 mg S m⁻² d⁻¹.Consistent with the water column concentration profiles for iron sulfide minerals, the sulfur isotope composition of particulate sulfur found in deep anoxic traps was similar to that of dissolved sulfide near the O₂/H₂S interface. We conclude that pyrite is formed mainly within the redoxcline where sulfur cycling imparts a distinct isotopic signature compared to dissolved sulfide in the deep anoxic water. This conclusion is consistent with our previous study of sulfur species and chemoautotrophic production, which suggests that reaction of sulfide with reactive iron is an important pathway for sulfide oxidation and sulfur intermediate formation near the interface. Pyrite and elemental sulfur distributions favor a pathway of pyrite formation via the reaction of FeS with polysulfides or particulate elemental sulfur near the interface. A comparison of thermodynamic predictions with actual concentration profiles for iron sulfides leads us to argue that microbes may mediate this precipitation.     

Role of molecular oxygen in the dissolution of siderite and rhodochrosite

The dissolution of siderite (FeCO₃) and rhodochrosite (MnCO₃) under oxic and anoxic conditions is investigated at 298 K. The anoxic dissolution rate of siderite is 10^−8.65 mol m⁻² s⁻¹ for 5.5 < pH < 12 and increases as [H⁺]^0.75 for pH < 5.5. The pH dependence is consistent with parallel proton-promoted and water hydrolysis dissolution pathways. Atomic force microscopy (AFM) reveals a change in pit morphology from rhombohedral pits for pH > 4 to pits elongated at one vertex for pH < 4. Under oxic conditions the dissolution rate decreases to below the detection limit of 10⁻¹⁰ mol m⁻² s⁻¹ for 6.0 < pH < 10.3, and hillock precipitation preferential to steps is observed in concurrent AFM micrographs. X-ray photoelectron spectroscopy (XPS) and thermodynamic analysis identify the precipitate as ferrihydrite. At pH > 10.3, the oxic dissolution rate is as high as 10^−7.5 mol m⁻² s⁻¹, which is greater than under the corresponding anoxic conditions. A fast electron transfer reaction between solution O₂ or [Fe³⁺(OH)₄]⁻ species and surficial >Fe^II hydroxyl groups is hypothesized to explain the dissolution kinetics. AFM micrographs do not show precipitation under these conditions. Anoxic dissolution of rhodochrosite is physically observed as rhombohedral pit expansion for 3.7 < pH < 10.3 and is chemically explained by parallel proton- and water-promoted pathways. The dissolution rate law is 10^−4.93[H⁺] + 10^−8.45 mol m⁻² s⁻¹. For 5.8 < pH < 7.7 under oxic conditions, the AFM micrographs show a tabular precipitate growing by preferential expansion along the a-axis, though the macroscopic dissolution rate is apparently unaffected. For pH > 7.7 under oxic conditions, the dissolution rate decreases from 10^−8.45 to 10^−9.0 mol m⁻² s⁻¹. Flattened hillock precipitates grow across the entire surface without apparent morphological influence by the underlying rhodochrosite surface. XPS spectra and thermodynamic calculations implicate the precipitate as bixbyite for 5.8 < pH < 7.7 and MnOOH (possibly feitnkechtite) for pH >7.7.     

Methane and sulfide fluxes in permanent anoxia: In situ studies at the Dvurechenskii mud volcano (Sorokin Trough, Black Sea)

The Dvurechenskii mud volcano (DMV) is located in permanently anoxic waters at 2060 m depth (Sorokin Trough, Black Sea). The DMV was studied during the RV Meteor expedition M72/2 as an example of an active mud volcano system, to investigate the significance of submarine mud volcanism for the methane and sulfide budget of the anoxic Black Sea hydrosphere. Our studies included benthic fluxes of methane and sulfide, as well as the factors controlling transport, consumption and production of both compounds within the sediment. The pie-shaped mud volcano showed temperature anomalies as well as solute and gas fluxes indicating high fluid flow at its summit north of the geographical center. The anaerobic oxidation of methane (AOM) coupled to sulfate reduction (SR) was repressed in this zone due to the upward flow of sulfate-depleted fluids through recently deposited subsurface muds, apparently limiting microbial methanotrophic activity. Consequently, the emission of dissolved methane into the water column was high, with an estimated rate of 0.46 mol m⁻² d⁻¹. On the wide plateau and edge of the mud volcano surrounding the summit, fluid flow and total methane flux were lower, allowing higher SR and AOM rates correlated with an increase in sulfate penetration into the sediment. Here, between 50% and 70% of the methane flux (0.07-0.1 mol m⁻² d⁻¹) was consumed within the upper 10 cm of the sediment. The overall amount of dissolved methane released from the entire mud volcano structure into the water column was significant with a discharge of 1.3 × 10⁷ mol yr⁻¹. The DMV maintains also high areal rates of methane-fueled sulfide production and emission of on average 0.05 mol m⁻² d⁻¹. This is a difference to mud volcanoes in oxic waters, which emit similar amounts of methane, but not sulfide. However, based on a comparison of this and other mud volcanoes of the Black Sea, we conclude that sulfide and methane emission into the hydrosphere from deep-water mud volcanoes does not significantly contribute to the sulfide and methane inventory of the Black Sea.     

Arsenic mobility in the ambient sulfidic environment: Sorption of arsenic(V) and arsenic(III) onto disordered mackinawite

Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The K_d (L g⁻¹) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility.