Groundwater chemistry of Al under Dutch sandy soils: Effects of land use and depth

Aluminium has received great attention in the second half of the 20th century, mainly in the context of the acid rain problem mostly in forest soils. In this research the effect of land use and depth of the groundwater on Al, pH and DOC concentration in groundwater under Dutch sandy soils has been studied. Both pH and DOC concentration play a major role in the speciation of Al in solution. Furthermore, the equilibrium with mineral phases like gibbsite, amorphous Al(OH)₃ and imogolite, has been considered. Agricultural and natural land use were expected to have different effects on the pH and DOC concentration, which in turn could influence the total Al concentration and the speciation of Al in groundwater at different depths (phreatic, shallow and deep). An extensive dataset (n = 2181) from the national and some provincial monitoring networks on soil and groundwater quality was used. Land use type and groundwater depth did influence the pH, and Al and DOC concentrations in groundwater samples. The Al concentration ranged from <0.4 μmol L⁻¹ at pH > 7 to 1941 μmol L⁻¹ at pH < 4; highest Al concentrations were found for natural-phreatic groundwater. The DOC concentration decreased and the median pH increased with depth of the groundwater. Natural-phreatic groundwater showed lower pH than the agricultural-phreatic groundwater. Highest DOC concentrations were found for the agricultural-phreatic groundwater, induced by the application of organic fertilizers. Besides inorganic complexation, the NICA-Donnan model was used to calculate Al³⁺ concentrations for complexation with DOC. Below pH 4.5 groundwater samples were mainly in disequilibrium with a mineral phase. This disequilibrium is considered to be the result of kinetic constraints or equilibrium with organic matter. Log K values were derived by linear regression and were close to theoretical values for Al(OH)₃ minerals (e.g. gibbsite or amorphous Al(OH)₃), except for natural-phreatic groundwater for which lower log K values were found. Complexation of Al with DOC is shown to be an important factor for the Al concentrations, especially at high DOC concentrations as was found for agricultural-phreatic groundwater.     

Transport and thermodynamics constrain belowground carbon turnover in a northern peatland

Rates of anaerobic respiration are of central importance for the long-term burial of carbon (C) in peatlands, which are a relevant sink in the global C cycle. To identify constraints on anaerobic peat decomposition, we determined detailed concentration depth profiles of decomposition end-products, i.e. methane (CH₄) and dissolved inorganic carbon (DIC), along with concentrations of relevant decomposition intermediates at an ombrotrophic Canadian peat bog. The magnitude of in situ net production rates of DIC and CH₄ was estimated by inverse pore-water modeling. Vertical transport in the peat was slow and dominated by diffusion leading to the buildup of DIC and CH₄ with depth (5500 μmol L⁻¹ DIC, 500 μmol L⁻¹ CH₄). Highest DIC and CH₄ production rates occurred close to the water table (decomposition constant k_d ∼ 10⁻³-10⁻⁴ a⁻¹) or in some distinct zones at depth (k_d ∼ 10⁻⁴ a⁻¹). Deeper into the peat, decomposition proceeded very slowly at about k_d = 10⁻⁷ a⁻¹. This pattern could be related to thermodynamic and transport constraints. The accumulation of metabolic end-products diminished in situ energy yields of acetoclastic methanogenesis to the threshold for microbially mediated processes (−20 to −25 kJ mol⁻¹ CH₄). The methanogenic precursor acetate also accumulated (150 μmol L⁻¹). In line with these findings, CH₄ was formed by hydrogenotrophic methanogenesis at Gibbs free energies of −35 to −40 kJ mol⁻¹ CH₄. This was indicated by an isotopic fractionation α_CO2-CH4 of 1.069-1.079. Fermentative degradation of acetate, propionate and butyrate attained Gibbs free energies close to 0 kJ mol⁻¹ substrate. Although methanogenesis was apparently limited by some other factor in some peat layers, transport and thermodynamic constraints likely impeded respiratory processes in the deeper peat. Constraints on the removal of DIC and CH₄ may thus slow decomposition and contribute to the sustained burial of C in northern peatlands.     

Carbon dioxide degassing and thermal energy release in the Monte Amiata volcanic-geothermal area (Italy)

The quaternary volcanic complex of Mount Amiata is located in southern Tuscany (Italy) and represents the most recent manifestation of the Tuscan Magmatic Province. The region is characterised by a large thermal anomaly and by the presence of numerous CO₂-rich gas emissions and geothermal features, mainly located at the periphery of the volcanic complex. Two geothermal systems are located, at increasing depths, in the carbonate and metamorphic formations beneath the volcanic complex. The shallow volcanic aquifer is separated from the deep geothermal systems by a low permeability unit (Ligurian Unit). A measured CO₂ discharge through soils of 1.8 × 10⁹ mol a⁻¹ shows that large amounts of CO₂ move from the deep reservoir to the surface. A large range in δ¹³C_TDIC (−21.07 to +3.65) characterises the waters circulating in the aquifers of the region and the mass and isotopic balance of TDIC allows distinguishing a discharge of 0.3 × 10⁹ mol a⁻¹ of deeply sourced CO₂ in spring waters. The total natural CO₂ discharge (2.1 × 10⁹ mol a⁻¹) is slightly less than minimum CO₂ output estimated by an indirect method (2.8 × 10⁹ mol a⁻¹), but present-day release of 5.8 × 10⁹ mol a⁻¹ CO₂ from deep geothermal wells may have reduced natural CO₂ discharge. The heat transported by groundwater, computed considering the increase in temperature from the infiltration area to the discharge from springs, is of the same order of magnitude, or higher, than the regional conductive heat flow (>200 mW m⁻²) and reaches extremely high values (up to 2700 mW m⁻²) in the north-eastern part of the study area. Heat transfer occurs mainly by conductive heating in the volcanic aquifer and by uprising gas and vapor along fault zones and in those areas where low permeability cover is lacking. The comparison of CO₂ flux, heat flow and geological setting shows that near surface geology and hydrogeological setting play a central role in determining CO₂ degassing and heat transfer patterns.     

Exploring sustainability of aquifers based on predictive modeling of sorption characteristics of arsenic enriched Holocene sediments in Bangladesh

The importance of accessing safe aquifers in areas with high As is being increasingly recognized. The present study aims to investigate the sorption and mobility of As at the sediment-groundwater interface to identify a likely safe aquifer in the Holocene deposit in southwestern Bangladesh. The upper, shallow aquifer at around 18 m depth, which is composed mainly of very fine, grey, reduced sand and contains 24.3 μg/g As, was found to produce highly enriched groundwater (190 μg/L As). In contrast, deeper sediments are composed of partly oxidized, brownish, medium sand with natural adsorbents like Fe- and Al-oxides; they contain 0.76 μg/g As and impart low As concentrations to the water (4 μg/L). These observations were supported by spectroscopic studies with SEM, TEM, XRD and XRF, and by adsorption, leaching, column tests and sequential extraction. A relatively high in-situ dissolution rate (R_r) of 1.42 × 10⁻¹⁶ mol/m²/s was derived for the shallower aquifer from the inverse mass-balance model. The high R_r may enhance As release processes in the upper sediment. The field-based reaction rate (K_r) was extrapolated to be roughly 1.23 × 10⁻¹³ s⁻¹ and 6.24 × 10⁻¹⁴ s⁻¹ for the shallower and deeper aquifer, respectively, from the laboratory-obtained adsorption/desorption data. This implies that As is more reactive in the shallower aquifer. The partition coefficient for the distribution of As at the sediment-water interface (K_d-As) was found to range from 5 to 235 L/kg based on in-situ, batch adsorption, and flow-through column techniques. Additionally, a parametric equation for K_d-As (R² = 0.67) was obtained from the groundwater pH and the logarithm of the leachable Fe and Al concentrations in sediment. A one-dimensional finite-difference numerical model incorporating K_d and K_r showed that the shallow, leached As can be immobilized and prevented from reaching the deeper aquifer (∼150 m) after 100 year by a natural filter of oxidizing sand and adsorbent minerals like Fe and Al oxides; in this scenario, 99% of the As in groundwater is reduced. The deeper aquifer appears to be an adequate source of sustainable, safe water.     

Radium uptake during barite recrystallization at 23 ± 2 °C as a function of solution composition: An experimental Ba and Ra tracer study

High-purity synthetic barite powder was added to pure water or aqueous solutions of soluble salts (BaCl₂, Na₂SO₄, NaCl and NaHCO₃) at 23 ± 2 °C and atmospheric pressure. After a short pre-equilibration time (4 h) the suspensions were spiked either with ¹³³Ba or ²²⁶Ra and reacted under constant agitation during 120-406 days. The pH values ranged from 4 to 8 and solid to liquid (S/L) ratios varied from 0.01 to 5 g/l. The uptake of the radiotracers by barite was monitored through repeated sampling of the aqueous solutions and radiometric analysis. For both ¹³³Ba and ²²⁶Ra, our data consistently showed a continuous, slow decrease of radioactivity in the aqueous phase.Mass balance calculations indicated that the removal of ¹³³Ba activity from aqueous solution cannot be explained by surface adsorption only, as it largely exceeded the 100% monolayer coverage limit. This result was a strong argument in favor of recrystallization (driven by a dissolution-precipitation mechanism) as the main uptake mechanism. Because complete isotopic equilibration between aqueous solution and barite was approached or even reached in some experiments, we concluded that during the reaction all or substantial fractions of the initial solid had been replaced by newly formed barite.The ¹³³Ba data could be successfully fitted assuming constant recrystallization rates and homogeneous distribution of the tracer into the newly formed barite. An alternative model based on partial equilibrium of ¹³³Ba with the mineral surface (without internal isotopic equilibration of the solid) could not reproduce the measured activity data, unless multistage recrystallization kinetics was assumed. Calculated recrystallization rates in the salt solutions ranged from 2.8 × 10⁻¹¹ to 1.9 × 10⁻¹⁰ mol m⁻² s⁻¹ (2.4-16 μmol m⁻² d⁻¹), with no specific trend related to solution composition. For the suspensions prepared in pure water, significantly higher rates (∼5.7 × 10⁻¹⁰ mol m⁻² s⁻¹ or ∼49 μmol m⁻² d⁻¹) were determined.Radium uptake by barite was determined by monitoring the decrease of ²²⁶Ra activity in the aqueous solution with alpha spectrometry, after filtration of the suspensions and sintering. The evaluation of the Ra uptake experiments, in conjunction with the recrystallization data, consistently indicated formation of non-ideal solid solutions, with moderately high Margules parameters (W_AB = 3720-6200 J/mol, a₀ = 1.5-2.5). These parameters are significantly larger than an estimated value from the literature (W_AB = 1240 J/mol, a₀ = 0.5).In conclusion, our results confirm that radium forms solid solutions with barite at fast kinetic rates and in complete thermodynamic equilibrium with the aqueous solutions. Moreover, this study provides quantitative thermodynamic data that can be used for the calculation of radium concentration limits in environmentally relevant systems, such as radioactive waste repositories and uranium mill tailings.     

Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.     

Effect of groundwater pH and ionic strength on strontium sorption in aquifer sediments: Implications for Sr mobility at contaminated nuclear sites

Strontium-90 is a beta emitting radionuclide produced during nuclear fission, and is a problem contaminant at many nuclear facilities. Transport of ⁹⁰Sr in groundwaters is primarily controlled by sorption reactions with aquifer sediments. The extent of sorption is controlled by the geochemistry of the groundwater and sediment mineralogy. Here, batch sorption experiments were used to examine the sorption behaviour of ⁹⁰Sr in sediment–water systems representative of the UK Sellafield nuclear site based on groundwater and contaminant fluid compositions. In experiments with low ionic strength groundwaters (<0.01 mol L⁻¹), pH variation is the main control on sorption. The sorption edge for ⁹⁰Sr was observed between pH 4 and 6 with maximum sorption occurring (K_d ∼ 10³ L kg⁻¹) at pH 6–8. At ionic strengths above 10 mmol L⁻¹, and at pH values between 6 and 8, cation exchange processes reduced ⁹⁰Sr uptake to the sediment. This exchange process explains the lower ⁹⁰Sr sorption (K_d ∼ 40 L kg⁻¹) in the presence of artificial Magnox tank liquor (IS = 29 mmol L⁻¹). Strontium K-edge EXAFS spectra collected from sediments incubated with Sr²⁺ in either HCO₃-buffered groundwater or artificial Magnox tank liquor, revealed a coordination environment of ∼9 O atoms at 2.58–2.61 Å after 10 days. This is equivalent to the Sr²⁺ hydration sphere for the aqueous ion and indicates that Sr occurs primarily in outer sphere sorption complexes. No change was observed in the Sr sorption environment with EXAFS analysis after 365 days incubation. Sequential extractions performed on sediments after 365 days also found that ∼80% of solid associated ⁹⁰Sr was exchangeable with 1 M MgCl₂ in all experiments. These results suggest that over long periods, ⁹⁰Sr in contaminated sediments will remain primarily in weakly bound surface complexes. Therefore, if groundwater ionic strength increases (e.g. by saline intrusion related to sea level rise or by design during site remediation) then substantial remobilisation of ⁹⁰Sr is to be expected.     

Influence of phosphate on the oxidation kinetics of nanomolar Fe(II) in aqueous solution at circumneutral pH

The oxygenation kinetics of nanomolar concentrations of Fe(II) in aqueous solution have been studied in the absence and presence of millimolar concentrations of phosphate over the pH range 6.0-7.8. At each phosphate concentration investigated, the overall oxidation rate constant varied linearly with pH, and increased with increasing phosphate concentration. A model based on equilibrium speciation of Fe(II) was found to satisfactorily explain the results obtained. From this model, the rate constants for oxygenation of the Fe(II)-phosphate species FeH₂PO₄⁺, FeHPO₄ and FePO₄⁻ have been determined for the first time. FePO₄⁻ was found to be the most kinetically reactive species at circumneutral pH with an estimated oxygenation rate constant of (2.2 ± 0.2) × 10 M⁻¹ s⁻¹. FeH₂PO₄⁺ and FeHPO₄ were found to be less reactive with oxygen, with rate constants of (3.2 ± 2) × 10⁻² M⁻¹ s⁻¹ and (1.2 ± 0.8) × 10⁻¹ M⁻¹ s⁻¹, respectively.     

Oxygen isotope fractionation of dissolved oxygen during reduction by ferrous iron

The oxygen isotope fractionation factor of dissolved oxygen gas has been measured during inorganic reduction by aqueous FeSO₄ at 10−54 °C under neutral (pH 7) and acidic (pH 2) conditions, with Fe(II) concentrations ranging up to 0.67 mol L⁻¹, in order to better understand the geochemical behavior of oxygen in ferrous iron-rich groundwater and acidic mine pit lakes. The rate of oxygen reduction increased with increasing temperature and increasing Fe(II) concentration, with the pseudo-first-order rate constant k ranging from 2.3 to 82.9 × 10⁻⁶ s⁻¹ under neutral conditions and 2.1 to 37.4 × 10⁻⁷ s⁻¹ under acidic conditions. The activation energy of oxygen reduction was 30.9 ± 6.6 kJ mol⁻¹ and 49.7 ± 13.0 kJ mol⁻¹ under neutral and acidic conditions, respectively. Oxygen isotope enrichment factors (ε) become smaller with increasing temperature, increasing ferrous iron concentration, and increasing reaction rate under acidic conditions, with ε values ranging from −4.5‰ to −11.6‰. Under neutral conditions, ε does not show any systematic trends vs. temperature or ferrous iron concentration, with ε values ranging from −7.3 to −10.3‰. Characterization of the oxygen isotope fractionation factor associated with O₂ reduction by Fe(II) will have application to elucidating the process or processes responsible for oxygen consumption in environments such as groundwater and acidic mine pit lakes, where a number of possible processes (e.g. biological respiration, reduction by reduced species) may have taken place.     

The continental shelf benthic iron flux and its isotope composition

Benthic iron fluxes from sites along the Oregon-California continental shelf determined using in situ benthic chambers, range from less than 10 μmol m⁻² d⁻¹ to values in excess of ∼300 μmol m⁻² d⁻¹. These fluxes are generally greater than previously published iron fluxes for continental shelves contiguous with the open ocean (as opposed to marginal seas, bays, or estuaries) with the highest fluxes measured in the regions around the high-sediment discharge Eel River and the Umpqua River. These benthic iron fluxes do not covary with organic carbon oxidation rates in any systematic fashion, but rather seem to respond to variations in bottom water oxygen and benthic oxygen demand. We hypothesize that the highest rates of benthic iron efflux are driven, in part, by the greater availability of reactive iron deposited along these river systems as compared to other more typical continental margin settings. Bioirrigation likely plays an important role in the benthic Fe flux in these systems as well. However, the influence of bottom water oxygen concentrations on the iron flux is significant, and there appears to be a threshold in dissolved oxygen (∼60-80 μM), below which sediment-ocean iron exchange is enhanced. The isotope composition of this shelf-derived benthic iron is enriched in the lighter isotopes, and appears to change by ∼3‰ (δ⁵⁶Fe) during the course of a benthic chamber experiment with a mean isotope composition of −2.7 ± 1.1‰ (2 SD, n = 9) by the end of the experiment. This average value is slightly heavier than those from two high benthic Fe flux restricted basins from the California Borderland region where δ⁵⁶Fe is −3.4 ± 0.4‰ (2 SD, n = 3). These light iron isotope compositions support previous ideas, based on sediment porewater analyses, suggesting that sedimentary iron reduction fractionates iron isotopes and produces an isotopically light iron pool that is transferred to the ocean water column. In sum, our data suggest that continental shelves may export a higher efflux of iron than previously hypothesized, with the likelihood that along river-dominated margins, the benthic iron flux could well be orders of magnitude larger than non-river dominated shelves. The close proximity of the continental shelf benthos to the productive surface ocean means that this flux is likely to be essential for maintaining ecosystem micronutrient supply.     

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.     

Landscape scale controls on the vascular plant component of dissolved organic carbon across a freshwater delta

Lignin phenol concentrations and compositions were determined on dissolved organic carbon (DOC) extracts (XAD resins) within the Sacramento-San Joaquin River Delta (the Delta), the tidal freshwater portion of the San Francisco Bay Estuary, located in central California, USA. Fourteen stations were sampled, including the following habitats and land-use types: wetland, riverine, channelized waterway, open water, and island drains. Stations were sampled approximately seasonally from December, 1999 through May, 2001. DOC concentrations ranged from 1.3 mg L⁻¹ within the Sacramento River to 39.9 mg L⁻¹ at the outfall from an island drain (median 3.0 mg L⁻¹), while lignin concentrations ranged from 3.0 μg L⁻¹ within the Sacramento River to 111 μg L⁻¹ at the outfall from an island drain (median 11.6 μg L⁻¹). Both DOC and lignin concentrations varied significantly among habitat/land-use types and among sampling stations. Carbon-normalized lignin yields ranged from 0.07 mg (100 mg OC)⁻¹ at an island drain to 0.84 mg (100 mg OC)⁻¹ for a wetland (median 0.36 mg (100 mg OC)⁻¹), and also varied significantly among habitat/land-use types. A simple mass balance model indicated that the Delta acted as a source of lignin during late autumn through spring (10-83% increase) and a sink for lignin during summer and autumn (13-39% decrease). Endmember mixing models using S:V and C:V signatures of landscape scale features indicated strong temporal variation in sources of DOC export from the Delta, with riverine source signatures responsible for 50% of DOC in summer and winter, wetland signatures responsible for 40% of DOC in summer, winter, and late autumn, and island drains responsible for 40% of exported DOC in late autumn. A significant negative correlation was observed between carbon-normalized lignin yields and DOC bioavailability in two of the 14 sampling stations. This study is, to our knowledge, the first to describe organic vascular plant DOC sources at the level of localized landscape features, and is also the first to indicate a significant negative correlation between lignin and DOC bioavailability within environmental samples. Based upon observed trends: (1) Delta features exhibit significant spatial variability in organic chemical composition, and (2) localized Delta features appear to exert strong controls on terrigenous DOC as it passes through the Delta and is exported into the Pacific Ocean.     

Determining individual mineral contributions to U(VI) adsorption in a contaminated aquifer sediment: A fluorescence spectroscopy study

The adsorption and speciation of U(VI) was investigated on contaminated, fine grained sediment materials from the Hanford 300 area (SPP1 GWF) in simulated groundwater using cryogenic laser-induced U(VI) fluorescence spectroscopy combined with chemometric analysis. A series of reference minerals (montmorillonite, illite, Michigan chlorite, North Carolina chlorite, California clinochlore, quartz and synthetic 6-line ferrihydrite) was used for comparison that represents the mineralogical constituents of SPP1 GWF. Surface area-normalized K_d values were measured at U(VI) concentrations of 5 × 10⁻⁷ and 5 × 10⁻⁶ mol L⁻¹ that displayed the following affinity series: 6-line-ferrihydrite > North Carolina chlorite ≈ California clinochlore > quartz ≈ Michigan chlorite > illite > montmorillonite. Both time-resolved spectra and asynchronous two-dimensional (2D) correlation analysis of SPP1 GWF at different delay times indicated that two major adsorbed U(VI) species were present in the sediment that resembled U(VI) adsorbed on quartz and phyllosilicates. Simulations of the normalized fluorescence spectra confirmed that the speciation of SPP1 GWF was best represented by a linear combination of U(VI) adsorbed on quartz (90%) and phyllosilicates (10%). However, the fluorescence quantum yield for U(VI) adsorbed on phyllosilicates was lower than quartz and, consequently, its fractional contribution to speciation may be underestimated. Spectral comparison with literature data suggested that U(VI) exist primarily as inner-sphere complexes with surface silanol groups on quartz and as surface U(VI) tricarbonate complexes on phyllosilicates.     

Particulate air pollution in a small settlement: The effect of local heating

Mass concentrations of PM₁₀, PM_2.5, and black smoke (BS) were measured in April 2003 during a 3-week campaign in a small village and at a nearby background location in the central part of the Czech Republic. In a pilot analysis, concentrations of selected trace elements (Al, Ti, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Sr, Cd, Sb, Cs, Pb) in the collected aerosol were determined by means of ICP-MS. Average concentrations of both PM fractions and BS were higher in the village (37, 26 and 26 μg m⁻³) than at the background location (26, 19 and 11 μg m⁻³) for PM₁₀, PM_2.5 and BS, respectively. Both PM₁₀ and PM_2.5 were reasonably correlated in the village (r = 0.80) and also at the background location (r = 0.79). Correlation between same fractions from the village and from the background site were even higher (r = 0.97 and r = 0.95 for the PM₁₀ and PM_2.5, respectively) suggesting that most of the aerosol in both locations may be influenced by similar sources. The ratio between PM₁₀ and PM_2.5 showed that sources in the village contributed about 33% and 35% to local aerosol concentration for PM₁₀ and PM_2.5, respectively. When the data from the two rural locations were compared with corresponding 24-h averages of PM₁₀ concentrations obtained for the period of the campaign from fixed site monitors situated near larger towns, the highest concentration was found in Prague the Czech capital (49 μg m⁻³) followed by a district town Beroun (41 μg m⁻³) and the village (37 μg m⁻³). The lowest PM₁₀ concentration was found in the village background (26 μg m⁻³). Elemental analysis revealed higher concentrations for most of the elements characteristic of combustion aerosol (namely Zn, Pb, As, Mn and Ti) in the PM collected in the village. The results support the idea that traditional heating in villages may contribute a great extent to local air pollution and may represent an important problem.     

Geochemical fluxes and weathering of volcanic terrains on high standing islands: Taranaki and Manawatu-Wanganui regions of New Zealand

Sediment fluxes from high standing oceanic islands (HSIs) such as New Zealand are some of the highest known [Milliman J. D. and Syvitski J. P. M. (1992) Geomorphic/tectonic control of sediment discharge to the ocean: the importance of small mountainous rivers. J. Geol.100, 525-544]. Recent geochemical work has suggested that along with their extremely high physical weathering yields, many New Zealand watersheds also have very high chemical weathering yields. In New Zealand, the magnitude of both the physical and chemical weathering yields is related to the lithology of the watershed. Most of the previous work on this topic has been undertaken in Southern Alps watersheds of schist and greywacke and in East Cape watersheds of semi-consolidated marine sediments and greywacke. We recently sampled North Island watersheds in the Taranaki and Manawatu-Wanganui regions which have been subjected to volcanism since the Miocene. We sampled watersheds that contain both volcanic and sedimentary rocks. A series of water and sediment samples was collected and analyzed for major, minor and trace elements. This was done to quantify the weathering intensities in the watersheds and to establish the relationship between physical and chemical weathering yields in volcanic lithologies. Our results reveal distinct chemical signatures for the different regions. Waters draining the Taranaki region volcanics are significantly enriched in K⁺, and depleted in Ca²⁺ and Sr²⁺ compared to waters draining the Manawatu-Wanganui region volcanics, which also traverse expanses of sedimentary siltstones and mudstones. The Ca²⁺ and Sr²⁺ depletions may reflect the relative absence of CaCO₃ in the Taranaki region watersheds. In addition, sediment samples from the Taranaki region show significant enrichment in Ti, Al, Ca, Fe, Mn, Mg, Ca, and P and depletion in Si and Rb compared to those of the Manawatu-Wanganui region. From total dissolved solids concentrations and mean annual water discharge, we calculate chemical weathering yields of 60-240 tons km⁻² a⁻¹. These weathering yields fall within the middle to upper range of those previously documented for the Southern Alps (93-480 tons km⁻² a⁻¹) and East Cape (62-400 tons km⁻² a⁻¹). Calculated silicate weathering yields of 12-33.6 tons km⁻² a⁻¹ and CO₂ consumption of 852-2390 × 10³ mol km⁻² a⁻¹ for the rivers draining the Taranaki volcanic region are higher than those previously reported for watersheds hosted in sedimentary and metamorphosed rock terrains on HSIs. CO₂ consumption is found to be within the range previously measured for the basaltic terrains of the Deccan Traps (580-2450 × 10³ mol km⁻² a⁻¹) and Réunion Island(1300-4400 × 10³ mol km⁻² a⁻¹). Our calculated chemical weathering yields demonstrate the importance of HSIs, particularly those with volcanic terrains, when considering global geochemical fluxes.     

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.     

Trace/minor element:calcium ratios in cultured benthic foraminifera. Part II: Ontogenetic variation

Ontogenetic (developmental stage) measurements of Mg/Ca and Sr/Ca were made on the benthic foraminifer Bulimina aculeata, which were cultured under controlled physicochemical conditions of temperature, pH, alkalinity, salinity, and trace- and minor-element concentrations. We utilized two methods of ontogenetic sampling—whole specimens progressively increasing in length and laser microdissection of a single specimen with subsequent analysis of dissected portions. A novel high-resolution laser-microdissection (HRLM) method allowed for precise (10 μm) cuts of the foraminiferal tests (shells) along the geometrically complex sutures distinguishing individual chambers. This new microdissection method limited sample loss and cross-contamination between foraminiferal chambers. Little or no variation in D_Sr was observed at different foraminiferal developmental stages. Conversely, D_Mg was enriched during a mid-developmental stage of whole-specimen samples (150-225 μm D_Mg = 1.6 × 10⁻³) compared to earlier and later stages (<150 μm, >225 μm D_Mg = 8.3 × 10⁻⁴). Further analysis of HRLM ontogenetic samples showed a larger, age-dependent D_Mg signature variation. This increase in shell Mg/Ca may contribute substantially to the measured inter-individual variability in Mg/Ca temperature prediction for cultured B. aculeata. Due to relatively large Mg/Ca inter- and intra-individual variability, measuring similar-size foraminiferal samples may improve the precision of paleotemperature prediction. Additionally, partial dissolution of the highest ontogenetically Mg-enriched calcite (D_Mg = 1.3 × 10⁻²-1.6 × 10⁻²) may occur in undersaturated bottom-water environments or during reductive cleaning procedures. Thus, the calcite phases remaining after partial dissolution by either natural or laboratory cleaning processes may not accurately represent the calcification environment.     

Solubility of nanocrystalline scorodite and amorphous ferric arsenate: Implications for stabilization of arsenic in mine wastes

Solubility experiments were performed on nanocrystalline scorodite and amorphous ferric arsenate. Nanocrystalline scorodite occurs as stubby prismatic crystals measuring about 50 nm and having a specific surface area of 39.88 ± 0.07 m²/g whereas ferric arsenate is amorphous and occurs as aggregated clusters measuring about 50–100 nm with a specific surface area of 17.95 ± 0.19 m²/g. Similar to its crystalline counterpart, nanocrystalline scorodite has a solubility of about 0.25 mg/L at around pH 3–4 but has increased solubilities at low and high pH (i.e. <2 and >6). Nanocrystalline scorodite dissolves incongruently at about pH > 2.5 whereas ferric arsenate dissolution is incongruent at all the pH ranges tested (pH 2–5). It appears that the solubility of scorodite is not influenced by particle size. The dissolution rate of nanocrystalline scorodite is 2.64 × 10⁻¹⁰ mol m⁻² s⁻¹ at pH 1 and 3.25 × 10⁻¹¹ mol m⁻² s⁻¹ at pH 2. These rates are 3–4 orders of magnitude slower than the oxidative dissolution of pyrite and 5 orders of magnitude slower than that of arsenopyrite. Ferric arsenate dissolution rates range from 6.14 × 10⁻⁹ mol m⁻² s⁻¹ at pH 2 to 1.66 × 10⁻⁹ mol m⁻² s⁻¹ at pH 5. Among the common As minerals, scorodite has the lowest solubility and dissolution rate. Whereas ferric arsenate is not a suitable compound for As control in mine effluents, nanocrystalline scorodite that can be easily precipitated at ambient pressure and temperature conditions would be satisfactory in meeting the regulatory guidelines at pH 3–4.     

Arsenic, iron and sulfur co-diagenesis in lake sediments

Profiles of porewater pH and dissolved As, Fe, Mn, sulfate, total sulfide (ΣS^−II), total zero-valent sulfur (ΣS⁰), organic carbon and major ion concentrations, as well as those of solid As, acid-volatile sulfide (AVS), total S, Fe, Mn, Al, organic C, ²¹⁰Pb and ¹³⁷Cs were determined in the sediment of four lakes spanning a range of redox and geochemical conditions. An inverse modeling approach, based on a one-dimensional transport-reaction equation assuming steady-state, was applied to the porewater As profiles and used to constrain the net rates of reactions involving As (). The model defines depth intervals where As is either released to (positive ) or removed from (negative ) the porewaters.At two of the sites, whose bottom water were oxygenated at sampling time, a production zone ( = 12 × 10⁻¹⁸ mol cm⁻³ s⁻¹-71 × 10⁻¹⁸ mol cm⁻³ s⁻¹) is inferred a few cm below the sediment-water interface, coincident with sharp porewater As and Fe peaks that indicate an intense coupled recycling of As and Fe. This process is confirmed by solid As and Fe maxima just below the sediment surface. In these two lakes a zone of As consumption ( = −5 × 10⁻¹⁸ mol cm⁻³ s⁻¹ to −53 × 10⁻¹⁸ mol cm⁻³ s⁻¹), attributed to the slow adsorption of As to authigenic Fe oxyhydroxides, occurs just above the production zone. A second-order rate constant of 0.12 ± 0.03 cm³ mol⁻¹ s⁻¹ is estimated for this adsorption reaction.Such features in the porewater and solid profiles were absent from the two other lakes that develop a seasonally anoxic hypolimnion. Thermodynamic calculations indicate that the porewaters of the four lakes, when sulfidic (i.e., ΣS^−II ? 0.1 μM), were undersaturated with respect to all known solid As sulfides; the calculation also predicts the presence of As^V oxythioanions in the sulfidic waters, as suggested by a recent study. In the sulfidic waters, the removal of As ( = −1 × 10⁻¹⁸ mol cm⁻³ s⁻¹ to −23 × 10⁻¹⁸ mol cm⁻³ s⁻¹) consistently occurred when saturation, with respect to FeS_(s), was reached and when As^V oxythioanions were predicted to be significant components of total dissolved As. This finding has potential implications for As transport in other anoxic waters and should be tested in a wider variety of natural environments.