Aeration to degas CO2, increase pH,and increase iron oxidation rates for efficient treatment of net alkaline mine drainage

Passive treatment systems for mine drainage use no energy other than gravity, but they require greater area than active treatment systems. Researchers are considering “hybrid” systems that have passive and active components for increased efficiency, especially where space limitations render passive-only technology ineffective. Flow-through reactor field experiments were conducted at two large net-alkaline anthracite mine discharges in central Pennsylvania. Assuming an Fe removal rate of 20 g m⁻² day⁻¹ and Fe loading from field data, 3.6 × 10³ and 3.0 × 10⁴ m² oxidation ponds would be required for the passive treatment of Site 21 and Packer 5 discharges, respectively. However, only a small area is available at each site. This paper demonstrates aeration to drive off CO₂, increase pH, and increase Fe(II) oxidation rates, enabling treatment within a small area compared to passive treatment methods, and introduces a geochemical model to accurately predict these rates as well as semi-passive treatment system sizing parameters. Both net-alkaline discharges were suboxic with a pH of ≈5.7, Fe(II) concentration of ≈16 mg L⁻¹, and low Mn and Al concentrations. Flow rates were ≈4000 L min⁻¹ at Site 21 and 15,000 L min⁻¹ at Packer 5. Three-h aeration experiments with flow rates scaled to a 14-L reactor resulted in pH increases from 5.7 to greater than 7, temperature increases from 12 to 22 °C, dissolved O₂ increases to saturation with respect to the atmosphere, and Fe(II) concentration decreases from 16 to <0.05 mg L⁻¹. A 17,000-L pilot-scale reactor at Site 21 produced similar results although aeration was not as complete as in the smaller reactor. Two non-aerated experiments at Site 21 with 13 and 25-h run times resulted in pH changes of ?0.2 and Fe(II) concentration decreases of less than 3 mg L⁻¹.     

Sulfur speciation in natural hydrothermal waters, Iceland

The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pH_T was between 2.20 and 9.30 at the discharge temperature and the SO₄ and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg⁻¹, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻) and polythionates (S_xO₆²⁻) and titration and/or colorimetry for total dissolved sulfide (S²⁻). Sulfite (SO₃²⁻) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S²⁻ were detected in all samples with concentrations of 0.02-52.7 mmol kg⁻¹ and <1-4100 μmol kg⁻¹, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg⁻¹ (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg⁻¹. Thiosulfate and SO₃²⁻ were not detected in <100 °C well waters and S₂O₃²⁻ was observed only at low concentrations (<1-8 μmol kg⁻¹) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S₂O₃²⁻ was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (S_TOT). In steam-heated acid-sulfate waters, S₂O₃²⁻ was not a significant sulfur species. The results demonstrate that S₂O₃²⁻ and SO₃²⁻ do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O₂, S²⁻ is degassed and oxidized to SO₃²⁻ and S₂O₃²⁻ and eventually to SO₄²⁻ at pH >8. In near-neutral hydrothermal waters the oxidation of S²⁻ and the interaction of S²⁻ and S⁰ resulting in the formation of S_x²⁻ are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO₄²⁻ and the sulfur chemistry of acid-sulfate pools was dominated by SO₄²⁻, which corresponded to >99% of S_TOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations.     

Geochemical characteristics of waters in mineralised area of Peloritani Mountains (Sicily,Italy)

This paper presents the results of a study on the geochemistry of waters circulating in the mineralised area of the south-eastern sector of Mt. Peloritani (north-eastern Sicily, Italy), aimed at basic understanding of the geochemical processes influencing their chemical composition. Chemico-physical parameters and data on 26 major and minor chemical elements are reported for 103 water samples. Water chemistry is mainly dominated by dissolution of carbonates and hydrolysis of aluminosilicate minerals. Total dissolved salts (TDS) range from 80 to 1398 mg/L. All the waters exhibit E_H characteristic of an oxygenated environment. Excluding two samples, which show very high H⁺ activity (pH = 3.0 and 2.7), all the waters have pH values in the range 6.2–8.6. Cluster analysis based on major ion contents defined three main chemical water types, reflecting different hydrochemical processes. The first, group I, has low salinity (average TDS = 118 ± 30 mg/L) and abundance orders (meq/L) Na > Ca ≈ Mg > K and Cl ≈ HCO₃ > SO₄. With increased water–rock interaction, waters in groups II and III become more saline, changing composition towards SO₄–Cl-alkaline earth and HCO₃-alkaline earth types. Weathering of carbonate minerals causes waters to become saturated with respect to calcite and dolomite, whereas the incongruent dissolution of aluminosilicate minerals causes the solution to reach equilibrium with kaolinite and to form smectites. Trace element geochemistry in the analysed waters reflects interactions between waters and existing mineralisation, with elemental concentrations showing highly variable values, and higher concentrations of As, Pb, Sb and Zn near known mineralisation. Lead–Zn and As–Sb statistical associations, probably distinguishing interactions with different mineralogical phase paragenesis, were revealed by factor analysis. The main aqueous chemical forms of trace elements predicted by chemical speciation calculations are also reported. As most of the analysed spring waters provide the main source of freshwater for domestic purposes, attention should be given to As and Sb, whose concentrations exceed the recommended limits.     

Dissolution kinetics of diopside as a function of solution saturation state: Macroscopic measurements and implications for modeling of geological storage of CO2

Measurements of the dissolution rate of diopside (r) were carried out as a function of the Gibbs free energy of the dissolution reaction (ΔG_r) in a continuously stirred flow-through reactor at 90 °C and pH_90 °C = 5.05. The overall relation between r and ΔG_r was determined over a free energy range of −130.9 < ΔG_r < −47.0 kJ mo1⁻¹. The data define a highly non-linear, sigmoidal relation between r and ΔG_r. At far-from-equilibrium conditions (ΔG_r ? −76.2 kJ mo1⁻¹), a rate plateau is observed. In this free energy range, the rates of dissolution are constant, independent of [Ca], [Mg] and [Si] concentrations, and independent of ΔG_r. A sharp decrease of the dissolution rate (∼1 order of magnitude) occurs in the transition ΔG_r region defined by −76.2 < ΔG_r ? −61.5 kJ mo1⁻¹. Dissolution closer to equilibrium (ΔG_r > −61.5 kJ mo1⁻¹) is characterised by a much weaker inverse dependence of the rates on ΔG_r. Modeling the experimental r-ΔG_r data with a simple classical transition state theory (TST) law as implemented in most available geochemical codes is found inappropriate. An evaluation of the consequences of the use of geochemical codes where the r-ΔG_r relation is based on basic TST was carried out and applied to carbonation reactions of diopside, which, among other reactions with Ca- and Mg-bearing minerals, are considered as a promising process for the solid state sequestration of CO₂ over long time spans. In order to take into account the actual experimental r-ΔG_r relation in the geochemical code that we used, a new module has been developed. It reveals a dramatic overestimation of the carbonation rate when using a TST-based geochemical code. This points out that simulations of water-rock-CO₂ interactions performed with classical geochemical codes should be evaluated with great caution.     

Mineralogical,geochemical, and microbial investigation of a sulfide-rich tailings deposit characterized by neutral drainage

Mineralogical, geochemical and microbial characterization of tailings solids from the Greens Creek Mine, Juneau, Alaska, was performed to evaluate mechanisms controlling aqueous geochemistry of near-neutral pH pore water and drainage. Core samples of the tailings were collected from five boreholes ranging from 7 to 26 m in depth. The majority of the 51 samples (77%) were collected from the vadose zone, which can extend >18 m below the tailings surface. Mineralogical investigation indicates that the occurrence of sulfide minerals follows the general order: pyrite [FeS₂] >> sphalerite [(Zn,Fe)S] > galena [PbS], tetrahedrite [(Fe,Zn,Cu,Ag)₁₂Sb₄S₁₃] > arsenopyrite [FeAsS] and chalcopyrite [CuFeS₂]. Pyrite constitutes <20 to >35 wt.% of the tailings mineral assemblage, whereas dolomite [CaMg(CO₃)₂] and calcite [CaCO₃] are present at ?30 and 3 wt.%, respectively. The solid-phase geochemistry generally reflects the mineral assemblage. The presence of additional trace elements, including Cd, Cr, Co, Mo, Ni, Se and Tl, is attributed to substitution into sulfide phases. Results of acid–base accounting (ABA) underestimated both acid-generating potential (AP) and neutralization potential (NP). Recalculation of AP and NP based on solid-phase geochemistry and quantitative mineralogy yielded more representative results. Neutrophilic S-oxidizing bacteria (nSOB) and SO₄-reducing bacteria (SRB) are present with populations up to 10⁷ and 10⁵ cells g⁻¹, respectively. Acidophilic S-oxidizing bacteria (aSOB) and iron-reducing bacteria (IRB) were generally less abundant. Primary influences on aqueous geochemistry are sulfide oxidation and carbonate dissolution at the tailings surface, gypsum precipitation–dissolution reactions, as well as Fe reduction below the zone of sulfide oxidation. Pore-water pH values generally ranged from 6.5 to 7.5 near the tailings surface, and from approximately 7–8 below the oxidation zone. Elevated concentrations of dissolved SO₄, S₂O₃, Fe, Zn, As, Sb and Tl persisted under these conditions.     

Stream geochemistry, chemical weathering and CO2 consumption potential of andesitic terrains, Dominica, Lesser Antilles

Recent studies of chemical weathering of andesitic-dacitic material on high-standing islands (HSIs) have shown these terrains have some of the highest observed rates of chemical weathering and associated CO₂ consumption yet reported. However, the paucity of stream gauge data in many of these terrains has limited determination of chemical weathering product fluxes. In July 2006 and March 2008, stream water samples were collected and manual stream gauging was performed in watersheds throughout the volcanic island of Dominica in the Lesser Antilles. Distinct wet and dry season solute concentrations reveal the importance of seasonal variations on the weathering signal. A cluster analysis of the stream geochemical data shows the importance of parent material age on the overall delivery of solutes. Observed Ca:Na, HCO₃:Na and Mg:Na ratios suggest crystallinity of the parent material may also play an important role in determining weathering fluxes. From total dissolved solids concentrations and mean annual discharge calculations we calculate chemical weathering yields of (6-106 t km⁻² a⁻¹), which are similar to those previously determined for basalt terrains. Silicate fluxes (3.1-55.4 t km⁻² a⁻¹) and associated CO₂ consumption (190-1575 × 10³ mol km⁻² a⁻¹) determined from our study are among the highest determined to date. The calculated chemical fluxes from our study confirm the weathering potential of andesitic-dacitic terrains and that additional studies of these terrains are warranted.     

H2S fluxes from Mt. Etna, Stromboli, and Vulcano (Italy) and implications for the sulfur budget at volcanoes

We present here new measurements of sulfur dioxide and hydrogen sulfide emissions from Vulcano, Etna, and Stromboli (Italy), made by direct sampling at vents and by filter pack and ultraviolet spectroscopy in downwind plumes. Measurements at the F0 and FA fumaroles on Vulcano yielded SO₂/H₂S molar ratios of ≈0.38 and ≈1.4, respectively, from which we estimate an H₂S flux of 6 to 9 t · d⁻¹ for the summit crater. For Mt. Etna and Stromboli, we found SO₂/H₂S molar ratios of ≈20 and ≈15, respectively, which combined with SO₂ flux measurements, suggest H₂S emission rates of 50 to 113 t · d⁻¹ and 4 to 8 t · d⁻¹, respectively. We observe that “source” and plume SO₂/H₂S ratios at Vulcano are similar, suggesting that hydrogen sulfide is essentially inert on timescales of seconds to minutes. This finding has important implications for estimates of volcanic total sulfur budget at volcanoes since most existing measurements do not account for H₂S emission.     

Pathways and regulation of carbon, sulfur and energy transfer in marine sediments overlying methane gas hydrates on the Opouawe Bank (New Zealand)

This study combines sediment geochemical analysis, in situ benthic lander deployments and numerical modeling to quantify the biogeochemical cycles of carbon and sulfur and the associated rates of Gibbs energy production at a novel methane seep. The benthic ecosystem is dominated by a dense population of tube-building ampharetid polychaetes and conspicuous microbial mats were unusually absent. A 1D numerical reaction-transport model, which allows for the explicit growth of sulfide and methane oxidizing microorganisms, was tuned to the geochemical data using a fluid advection velocity of 14 cm yr⁻¹. The fluids provide a deep source of dissolved hydrogen sulfide and methane to the sediment with fluxes equal to 4.1 and 18.2 mmol m⁻² d⁻¹, respectively. Chemosynthetic biomass production in the subsurface sediment is estimated to be 2.8 mmol m⁻² d⁻¹ of C biomass. However, carbon and oxygen budgets indicate that chemosynthetic organisms living directly above or on the surface sediment have the potential to produce 12.3 mmol m⁻² d⁻¹ of C biomass. This autochthonous carbon source meets the ampharetid respiratory carbon demand of 23.2 mmol m⁻² d⁻¹ to within a factor of 2. By contrast, the contribution of photosynthetically-fixed carbon sources to ampharetid nutrition is minor (3.3 mmol m⁻² d⁻¹ of C). The data strongly suggest that mixing of labile autochthonous microbial detritus below the oxic layer sustains high measured rates of sulfate reduction in the uppermost 2 cm of the sulfidic sediment (100-200 nmol cm⁻³ d⁻¹). Similar rates have been reported in the literature for other seeps, from which we conclude that autochthonous organic matter is an important substrate for sulfate reducing bacteria in these sediment layers. A system-scale energy budget based on the chemosynthetic reaction pathways reveals that up to 8.3 kJ m⁻² d⁻¹ or 96 mW m⁻² of catabolic (Gibbs) energy is dissipated at the seep through oxidation reactions. The microorganisms mediating sulfide oxidation and anaerobic oxidation of methane (AOM) produce 95% and 2% of this energy flux, respectively. The low power output by AOM is due to strong bioenergetic constraints imposed on the reaction rate by the composition of the chemical environment. These constraints provide a high potential for dissolved methane efflux from the sediment (12.0 mmol m⁻² d⁻¹) and indicates a much lower efficiency of (dissolved) methane sequestration by AOM at seeps than considered previously. Nonetheless, AOM is able to consume a third of the ascending methane flux (5.9 mmol m⁻² d⁻¹ of CH₄) with a high efficiency of energy expenditure (35 mmol CH₄ kJ⁻¹). It is further proposed that bioenergetic limitation of AOM provides an explanation for the non-zero sulfate concentrations below the AOM zone observed here and in other active and passive margin sediments.     

Solubility products of amorphous ferric arsenate and crystalline scorodite (FeAsO4 · 2H2O) and their application to arsenic behavior in buried mine tailings

Published solubility data for amorphous ferric arsenate and scorodite have been reevaluated using the geochemical code PHREEQC with a modified thermodynamic database for the arsenic species. Solubility product calculations have emphasized measurements obtained under conditions of congruent dissolution of ferric arsenate (pH < 3), and have taken into account ion activity coefficients, and ferric hydroxide, ferric sulfate, and ferric arsenate complexes which have association constants of 10^4.04 (FeH₂AsO₄²⁺), 10^9.86 (FeHAsO₄⁺), and 10^18.9 (FeAsO₄). Derived solubility products of amorphous ferric arsenate and crystalline scorodite (as log K_sp) are −23.0 ± 0.3 and −25.83 ± 0.07, respectively, at 25 °C and 1 bar pressure. In an application of the solubility results, acid raffinate solutions (molar Fe/As = 3.6) from the JEB uranium mill at McClean Lake in northern Saskatchewan were neutralized with lime to pH 2-8. Poorly crystalline scorodite precipitated below pH 3, removing perhaps 98% of the As(V) from solution, with ferric oxyhydroxide (FO) phases precipitated starting between pH 2 and 3. Between pH 2.18 and 7.37, the apparent log K_sp of ferric arsenate decreased from −22.80 to −24.67, while that of FO (as Fe(OH)₃) increased from −39.49 to −33.5. Adsorption of As(V) by FO can also explain the decrease in the small amounts of As(V)(aq) that remain in solution above pH 2-3. The same general As(V) behavior is observed in the pore waters of neutralized tailings buried for 5 yr at depths of up to 32 m in the JEB tailings management facility (TMF), where arsenic in the pore water decreases to 1-2 mg/L with increasing age and depth. In the TMF, average apparent log K_sp values for ferric arsenate and ferric hydroxide are −25.74 ± 0.88 and −37.03 ± 0.58, respectively. In the laboratory tests and in the TMF, the increasing crystallinity of scorodite and the amorphous character of the coexisting FO phase increases the stability field of scorodite relative to that of the FO to near-neutral pH values. The kinetic inability of amorphous FO to crystallize probably results from the presence of high concentrations of sulfate and arsenate.     

Silicon control of strontium and cesium partitioning in hydroxide-weathered sediments

Cation partitioning and speciation in an aqueous soil suspension may depend on the coupling of reaction time, sorbate amount and mineral weathering reactions. These factors were varied in sediment suspension experiments to identify geochemical processes that affect migration of Sr²⁺ and Cs⁺ introduced to the subsurface by caustic high level radioactive waste (HLRW). Three glacio-fluvial and lacustrine sediments from the Hanford Site (WA, USA) were subjected to hyperalkaline (pH > 13), Na-Al-NO₃-OH solution conditions within a gradient field of (i) sorptive concentration (10⁻⁵-10⁻³ m) and (ii) reaction time (0-365 d). Strontium uptake (q_Sr) exceeded that of cesium at nearly all reaction times. Sorbent affinity for both Cs⁺ and Sr²⁺ increased with clay plus silt content at early times, but a prolonged slow uptake process was observed over the course of sediment weathering that erased the texture effect for Sr²⁺; all sediments showed similar mass normalized uptake after several months of reaction time. Strontium became progressively recalcitrant to desorption after 92 d, with accumulation and aging of neoformed aluminosilicates. Formation of Cs⁺ and Sr²⁺-containing cancrinite and sodalite was observed after 183 d by SEM and synchrotron μ-XRF and μ-XRD. EXAFS data for q_Sr ≈ 40 mmol kg⁻¹ showed incorporation of Sr²⁺ into both feldspathoid and SrCO₃(s) coordination environments after one year. Adsorption was predominant at early times and low sorbate amount, whereas precipitation, controlled largely by sediment Si release, became increasingly important at longer times and higher sorbate amount. Kinetics of contaminant desorption at pH 8 from one year-weathered sediments showed significant dependence on background cation (Ca²⁺ versus K⁺) composition. Results of this study indicate that co-precipitation and ion exchange in neoformed aluminosilicates may be an important mechanism controlling Sr²⁺ and Cs⁺ mobility in siliceous sediments impacted by hyperalkaline HLRW.     

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ²⁶Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ²⁶Mg values of loess-derived soil above the cave (−1.0 ± 0.5‰), soil water (−1.2 ± 0.5‰), the carbonate hostrock (−3.8 ± 0.5‰), dripwater in the cave (−1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; −4.3 ± 0.6‰), cave loam (−0.6 ± 0.1‰) and runoff water (−1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000lnα_Mg-cc-Mg(aq) = −2.4‰. A similar Mg-isotope fractionation (1000lnα_Mg-cc-Mg(aq) ≈ −2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, ²⁶Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg²⁺ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.     

Geochemical assessment of groundwater contamination with special emphasis on fluoride concentration, North Jordan

The concentrations of fluorine in groundwater of North Jordan range from 0.009 to 0.055 mg/l. Other chemical parameters, e.g. pH, EC, TDS, Cl, TH, HCO₃, PO₄, SO₄, NO₃, NH₄, K, Ca, Mg, and NO₃ have been studied and showed higher concentrations in HCO₃⁻ and NO₃⁻ of 307 and 51 mg/l, respectively. Thermodynamic considerations show that almost all the analyzed samples are undersaturated with respect to calcite and fluorite. This undersaturation is probably due to their low availability in the locations. Fluoride concentration shows a positive relation to pH and HCO₃, whereas Cl, Mg, Ca, and Na initially increase and then decrease with increasing fluoride in the water. Saturation indexes of fluorite and calcite are estimated. The chemistry of the groundwater is controlled by the fluorite and calcite solubility. The topography of the area has exerted control on the aerial extent of fluoride concentration.     

An attenuated total reflectance IR study of silicic acid adsorbed onto a ferric oxyhydroxide surface

Silicic acid (H₄SiO₄) can have significant effects on the properties of iron oxide surfaces in both natural and engineered aquatic systems. Understanding the reactions of H₄SiO₄ on these surfaces is therefore necessary to describe the aquatic chemistry of iron oxides and the elements that associate with them. This investigation uses attenuated total reflectance infrared spectroscopy (ATR-IR) to study silicic acid in aqueous solution and the products formed when silicic acid adsorbs onto the surface of a ferrihydrite film in 0.01 M NaCl at pH 4. A spectrum of 1.66 mM H₄SiO₄ at pH 4 (0.01 M NaCl) has an asymmetric Si-O stretch at 939 cm⁻¹ and a weak Si-O-H deformation at 1090 cm⁻¹. ATR-IR spectra were measured over time (for up to 7 days) for a ferrihydrite film (≈1 mg) approaching equilibrium with H₄SiO₄ at concentrations between 0.044 and 0.91 mM. Adsorbed H₄SiO₄ had a broad spectral feature between 750 and 1200 cm⁻¹ but the shape of the spectra changed as the amount of H₄SiO₄ adsorbed on the ferrihydrite increased. When the solid phase Si/Fe mole ratio was less than ≈0.01 the ATR-IR spectra had a maximum intensity at 943 cm⁻¹ and the spectral shape suggests that a monomeric silicate species was formed via a bidentate linkage. As the solid phase Si/Fe mole ratio increased to higher values a discrete oligomeric silicate species was formed which had maximum intensity in the ATR-IR spectra at 1001 cm⁻¹. The spectrum of this species suggests that it is larger than a dimer and it was tentatively identified as a cyclic tetramer. A small amount of a polymeric silica phase with a broad spectral feature centered at ≈1110 cm⁻¹ was also observed at high surface coverage. The surface composition was estimated from the relative contribution of each species to the area of the ATR-IR spectra using multivariate curve resolution with alternating least squares. For a ferrihydrite film approaching equilibrium with 0.044, 0.14, 0.40 and 0.91 mM H₄SiO₄ the area of the spectra accounted for by monomeric species were 92%, 49%, 23% and 6%, respectively. The remainder was oligomer apart from a small amount (<5%) of polymerized silica at the two higher H₄SiO₄ concentrations. The solid phase Si/Fe mole ratios for these samples were 0.020, 0.037, 0.071 and 0.138, respectively.     

Benthic nitrogen cycling traversing the Peruvian oxygen minimum zone

Benthic nitrogen (N) cycling was investigated at six stations along a transect traversing the Peruvian oxygen minimum zone (OMZ) at 11°S. An extensive dataset including porewater concentration profiles and in situ benthic fluxes of nitrate (NO₃⁻), nitrite (NO₂⁻) and ammonium (NH₄⁺) was used to constrain a 1-D reaction-transport model designed to simulate and interpret the measured data at each station. Simulated rates of nitrification, denitrification, anammox and dissimilatory nitrate reduction to ammonium (DNRA) by filamentous large sulfur bacteria (e.g. Beggiatoa and Thioploca) were highly variable throughout the OMZ yet clear trends were discernible. On the shelf and upper slope (80-260 m water depth) where extensive areas of bacterial mats were present, DNRA dominated total N turnover (?2.9 mmol N m⁻² d⁻¹) and accounted for ?65% of NO₃⁻ + NO₂⁻ uptake by the sediments from the bottom water. Nonetheless, these sediments did not represent a major sink for dissolved inorganic nitrogen (DIN = NO₃⁻ + NO₂⁻ + NH₄⁺) since DNRA reduces NO₃⁻ and, potentially NO₂⁻, to NH₄⁺. Consequently, the shelf and upper slope sediments were recycling sites for DIN due to relatively low rates of denitrification and high rates of ammonium release from DNRA and ammonification of organic matter. This finding contrasts with the current opinion that sediments underlying OMZs are a strong sink for DIN. Only at greater water depths (300-1000 m) did the sediments become a net sink for DIN. Here, denitrification was the major process (?2 mmol N m⁻² d⁻¹) and removed 55-73% of NO₃⁻ and NO₂⁻ taken up by the sediments, with DNRA and anammox accounting for the remaining fraction. Anammox was of minor importance on the shelf and upper slope yet contributed up to 62% to total N₂ production at the 1000 m station. The results indicate that the partitioning of oxidized N (NO₃⁻, NO₂⁻) into DNRA or denitrification is a key factor determining the role of marine sediments as DIN sinks or recycling sites. Consequently, high measured benthic uptake rates of oxidized N within OMZs do not necessarily indicate a loss of fixed N from the marine environment.     

Speciation and thermodynamic properties for cobalt chloride complexes in hydrothermal fluids at 35-440 °C and 600 bar: An in-situ XAS study

Aqueous Co(II) chloride complexes play a crucial role in cobalt transport and deposition in ore-forming hydrothermal systems, ore processing plants, and in the corrosion of special Co-bearing alloys. Reactive transport modelling of cobalt in hydrothermal fluids relies on the availability of thermodynamic properties for Co complexes over a wide range of temperature, pressure and salinity. Synchrotron X-ray absorption spectroscopy was used to determine the speciation of cobalt(II) in 0-6 m chloride solutions at temperatures between 35 and 440 °C at a constant pressure of 600 bar. Qualitative analysis of XANES spectra shows that octahedral species predominate in solution at 35 °C, while tetrahedral species become increasingly important with increasing temperature. Ab initio XANES calculations and EXAFS analyses suggest that in high temperature solutions the main species at high salinity (Cl:Co >> 2) is CoCl₄²⁻, while a lower order tetrahedral complex, most likely CoCl₂(H₂O)_2(aq), predominates at low salinity (Cl:Co ratios ∼2). EXAFS analyses further revealed the bonding distances for the octahedral Co(H₂O)₆²⁺ (^octCo-O = 2.075(19) Å), tetrahedral CoCl₄²⁻ (^tetCo-Cl = 2.252(19) Å) and tetrahedral CoCl₂(H₂O)_2(aq) (^tetCo-O = 2.038(54) Å and ^tetCo-Cl = 2.210(56) Å). An analysis of the Co(II) speciation in sodium bromide solutions shows a similar trend, with tetrahedral bromide complexes becoming predominant at higher temperature/salinity than in the chloride system. EXAFS analysis confirms that the limiting complex at high bromide concentration at high temperature is CoBr₄²⁻. Finally, XANES spectra were used to derive the thermodynamic properties for the CoCl₄²⁻ and CoCl₂(H₂O)_2(aq) complexes, enabling thermodynamic modelling of cobalt transport in hydrothermal fluids. Solubility calculations show that tetrahedral CoCl₄²⁻ is responsible for transport of cobalt in hydrothermal solutions with moderate chloride concentration (∼2 m NaCl) at temperatures of 250 °C and higher, and both cooling and dilution processes can cause deposition of cobalt from hydrothermal fluids.     

The dissolution rates of gibbsite in the presence of chloride, nitrate, silica, sulfate, and citrate in open and closed systems at 20°C

The dissolution of well crystallized gibbsite far at from equilibrium was studied in batch and mixed flow through reactors. The dissolution experiments were carried out between pH 2 and 6 in the presence of 10 mmol L⁻¹ citrate, at pH 2 and 3 in the presence of 10 mmol L⁻¹ chloride, nitrate, and sulfate, and at pH 2 and 3 in the presence of 1.5 mmol L⁻¹ silica at 20°C. The dissolution rate of gibbsite, R_Al (mol m⁻² s⁻¹), increases in the order of chloride ≈ nitrate < silica < sulfate ≈ citrate. In presence of silica, sulphate, and citrate dissolution is catalysed by the formation of aluminium complexes at the gibbsite surface (pH 2 and 3). From pH 2 to 3 no effect of R_Al on hydrogen activity is predicted as singly coordinated surface sites at the edges of the platy gibbsite crystals, [≡AlOH₂^+0.5] ≈ [≡AlOH], are almost saturated with protons. However at pH >3 dissolution is slowed by a decrease of [≡AlOH₂^+0.5].Gibbsite dissolution rates measured in closed and open systems were identical within the experimental and analytical uncertainty. This observation indicates that gibbsite dissolution is a surface controlled process. If dissolution of gibbsite occurs close to equilibrium R_Al values may be predicted by an approximately linear function of ΔG_r.     

Estimating specific surface area of fine stream bed sediments from geochemistry

Specific surface area (SSA) of headwater stream bed sediments is a fundamental property which determines the nature of sediment surface reactions and influences ecosystem-level, biological processes. Measurements of SSA – commonly undertaken by BET nitrogen adsorption – are relatively costly in terms of instrumentation and operator time. A novel approach is presented for estimating fine (<150 μm) stream bed sediment SSA from their geochemistry – after removal of organic matter – for agricultural headwater catchments across 15,400 km² of central England, UK. From a regional set of 1972 stream bed sediment sites with common characteristics for which geochemical data were available, 60 samples were selected – based on maximising their variation in Al concentrations – and their BET SSA measured by N₂ adsorption. After careful selection of potential regression predictors following a principal component analysis and removal of a subset of samples with the largest Mo concentrations (>2.5 mg kg⁻¹), four elements were identified as significant predictors of SSA (ordered by decreasing predictive power): V > Ca > Al > Rb. The optimum model from these four elements accounted for 73% of the variation in bed sediment SSA (range 6–46 m² g⁻¹) with a root mean squared error of prediction – based on leave-one-out cross-validation – of 6.3 m² g⁻¹. It is believed that V is the most significant predictor because its concentration is strongly correlated both with the quantity of Fe-oxides and clay minerals in the stream bed sediments, which dominate sediment SSA. Sample heterogeneity in SSA – based on triplicate measurements of sub-samples – was a substantial source of variation (standard error = 2.2 m² g⁻¹) which cannot be accounted for in the regression model.     

Geochemistry of natural chromium occurrence in a sandstone aquifer in Bauru Basin, São Paulo State, Brazil

Anomalous concentrations of Cr(VI) occur in groundwaters of the Adamantina Aquifer, in a large region in the western state of São Paulo, sometimes exceeding the potability limit (0.05 mg L⁻¹). To identify the possible geochemical reactions responsible for the occurrence of Cr in groundwater in Urânia, borehole rock samples were collected in order to carry out mineralogical and chemical analyses. In addition, multilevel monitoring wells were installed and groundwater samples were analyzed. Analyses of the borehole rock samples show the occurrence of a geochemical anomaly of Cr in the quartzose sandstones (average concentrations of 221 ppm). Chrome-diopside is one of the main minerals contributing to this anomaly, having an average Cr content of 1505 ppm. Sequential extraction experiments indicated weakly adsorbed Cr in the order of 0.54 ppm, and this quantity is enough to provide the Cr concentrations observed in groundwater. Groundwaters from the monitoring wells proved to be stratified, with the highest concentrations of Cr(VI) (0.13 mg L⁻¹) being associated with high redox and pH values (over 10) and high concentrations of Na. Geochemical reactions that may explain the release of Cr from the solid phase to groundwater involve the release of Cr(III) from minerals (like chrome-diopside and Cr-Fe hydroxide), followed by oxidation of Cr(III) to Cr(VI), probably related to the reduction of Mn oxides present in the aquifer. Then cation exchange occurs and dissolution of carbonates which increases the pH of groundwater, resulting in the desorption and mobilization of Cr(VI) into groundwater.     

Fluorapatite surface composition in aqueous solution deduced from potentiometric, electrokinetic, and solubility measurements, and spectroscopic observations

The surface chemistry of fluorapatite in aqueous solution was investigated using electrokinetic techniques, potentiometric titrations, solubility measurements, and attenuated total reflection infrared spectroscopy. All methods indicate the formation of Ca/F depleted, P enriched altered layer via exchange reactions between H⁺ and Ca²⁺, and OH⁻ and F⁻ at the fluorapatite (FAP) surface. Observations suggest that this leached layer has a di-calcium phosphate (CaHPO₄) composition and that it controls the apparent solubility of FAP. Electrokinetic measurements yield an iso-electric point value of 1 ± 0.5 consistent with a negatively charged FAP surface at pH > 1. In contrast, surface titrations give an apparent pH of point of zero charge of ∼7.7, consistent with a positively charged surface at pH < 7.7. These differences are shown to stem from proton consumption by both proton exchange and dissolution reactions at the FAP surface. After taking account for these effects, FAP surface charge is shown to be negative to at least pH 4 by surface titration analysis.     

Surface heat flow and CO2 emissions within the Ohaaki hydrothermal field,Taupo Volcanic Zone,New Zealand

Carbon dioxide emissions and heat flow have been determined from the Ohaaki hydrothermal field, Taupo Volcanic Zone (TVZ), New Zealand following 20 a of production (116 MW_e). Soil CO₂ degassing was quantified with 2663 CO₂ flux measurements using the accumulation chamber method, and 2563 soil temperatures were measured and converted to equivalent heat flow (W m⁻²) using published soil temperature heat flow functions. Both CO₂ flux and heat flow were analysed statistically and then modelled using 500 sequential Gaussian simulations. Forty subsoil CO₂ gas samples were also analysed for stable C isotopes. Following 20 a of production, current CO₂ emissions equated to 111 ± 6.7 T/d. Observed heat flow was 70 ± 6.4 MW, compared with a pre-production value of 122 MW. This 52 MW reduction in surface heat flow is due to production-induced drying up of all alkali–Cl outflows (61.5 MW) and steam-heated pools (8.6 MW) within the Ohaaki West thermal area (OHW). The drying up of all alkali–Cl outflows at Ohaaki means that the soil zone is now the major natural pathway of heat release from the high-temperature reservoir. On the other hand, a net gain in thermal ground heat flow of 18 MW (from 25 MW to 43.3 ± 5 MW) at OHW is associated with permeability increases resulting from surface unit fracturing by production-induced ground subsidence. The Ohaaki East (OHE) thermal area showed no change in distribution of shallow and deep soil temperature contours despite 20 a of production, with an observed heat flow of 26.7 ± 3 MW and a CO₂ emission rate of 39 ± 3 T/d. The negligible change in the thermal status of the OHE thermal area is attributed to the low permeability of the reservoir beneath this area, which has limited production (mass extraction) and sheltered the area from the pressure decline within the main reservoir. Chemistry suggests that although alkali–Cl outflows once contributed significantly to the natural surface heat flow (∼50%) they contributed little (<1%) to pre-production CO₂ emissions due to the loss of >99% of the original CO₂ content due to depressurisation and boiling as the fluids ascended to the surface. Consequently, the soil has persisted as the major (99%) pathway of CO₂ release to the atmosphere from the high temperature reservoir at Ohaaki. The CO₂ flux and heat flow surveys indicate that despite 20 a of production the variability in location, spatial extent and magnitude of CO₂ flux remains consistent with established geochemical and geophysical models of the Ohaaki Field. At both OHW and OHE carbon isotopic analyses of soil gas indicate a two-stage fractionation process for moderate-flux (>60 g m⁻² d⁻¹) sites; boiling during fluid ascent within the underlying reservoir and isotopic enrichment as CO₂ diffuses through porous media of the soil zone. For high-flux sites (>300 g m⁻² d⁻¹), the δ¹³CO₂ signature (−7.4 ± 0.3‰ OHW and −6.5 ± 0.6‰ OHE) is unaffected by near-surface (soil zone) fractionation processes and reflects the composition of the boiled magmatic CO₂ source for each respective upflow. Flux thresholds of <30 g m⁻² d⁻¹ for purely diffusive gas transport, between 30 and 300 g m⁻² d⁻¹ for combined diffusive–advective transport, and ?300 g m⁻² d⁻¹ for purely advective gas transport at Ohaaki were assigned. δ¹³CO₂ values and cumulative probability plots of CO₂ flux data both identified a threshold of ∼15 g m⁻² d⁻¹ by which background (atmospheric and soil respired) CO₂ may be differentiated from hydrothermal CO₂.