Temporal dynamics of AVS and SEM in sediment of shallow freshwater floodplain lakes

Acid volatile sulfide (AVS) is an operationally defined sulfide fraction, which is considered important for trace metal fate in reduced sediments. Understanding AVS formation rates is important for the management of metal polluted sediment. However, little is known about the fate and dynamics of AVS in spatially and seasonally variable freshwater environments. The authors monitored in situ AVS formation and degradation and simultaneously extracted metals (SEM) in two floodplain lakes and compared this to AVS formation rates in laboratory experiments with the same sediment. In the laboratory experiments, the formation rates of AVS were studied at 20 °C for initially oxidized sediments that were: (a) untreated; (b) enriched with extra ${\mathrm{SO}}_4^{2-}$; and (c) treated with sodium-azide (biocide). In the field, AVS concentrations were highly variable and were significantly correlated to surface water temperature and O₂ concentrations as well as to sediment composition. Between February and August, AVS formation was approximately linear at a rate of 0.07 μmol g⁻¹ d⁻¹. Degradation rates differed drastically between the lakes due to different degradation mechanisms. In one lake AVS removal was caused by reworking and oxygenation of the sediments by bream (Abrami brama), at a rate of 0.25 μmol g⁻¹ d⁻¹. In the other lake AVS removal was caused by desiccation, at a rate of ±2.6 μmol g⁻¹ d⁻¹. This illustrates the large differences that can be found between similar lakes, and the importance of biological processes. In the laboratory, concentrations of AVS with and without ${\mathrm{SO}}_4^{2-}$ addition were similar during the first weeks, and increased at a rate of 0.15 μmol g⁻¹ d⁻¹. However, ${\mathrm{SO}}_4^{2-}$ addition increased the AVS concentration at the end of the experiment, whereas sodium-azide eliminated AVS formation, as expected. This suggests that AVS formation was ${\mathrm{SO}}_4^{2-}$-limited in the laboratory as well as in these shallow freshwater lakes.     

Geochemistry of surface and ground water in Guiyang,China: Water/rock interaction and pollution in a karst hydrological system

The chemical compositions of the surface/ground water of Guiyang, the capital city of Guizhou Province, China are dominated by Ca²⁺, Mg²⁺, ${\text{HCO}}_3^{-}\text{and}{\text{SO}}_4^{2-}$, which have been derived largely from chemical weathering of carbonate rocks (limestone and dolomite). The production of ${\text{SO}}_4^{2-}$ has multiple origins, mainly from dissolution of sulfate evaporites, oxidation of sulfide minerals and organic S in the strata, and anthropogenic sources. Most ground water is exposed to soil CO₂ and, therefore, the H₂CO₃ which attacks minerals contains much soil C. In addition, the H₂SO₄ produced as a result of the oxidation of sulfides in S-rich coal seams and/or organic S, is believed to be associated with the chemical weathering of rocks. The major anthropogenic components in the surface and ground water include K⁺, Na⁺, Cl⁻, ${\text{SO}}_4^{2-}\text{and}{\text{NO}}_3^{-}$, with Cl⁻ and ${\text{NO}}_3^{-}$ being the main contributors to ground water pollution in Guiyang and its adjacent areas. The seasonal variations in concentrations of anthropogenic components demonstrate that the karst ground water system is liable to pollution by human activities. The higher content of ${\text{NO}}_3^{-}$ in ground water compared to surface water during the summer and winter seasons, indicates that the karstic ground water system is not capable of denitrification and therefore does not easily recover once contaminated with nitrates.     

Surface chemistry and reactivity of plant phytoliths in aqueous solutions

In order to better understand the reactivity of plant phytoliths in soil solutions, we determined the solubility, surface properties (electrophoretic mobilities and surface charge) and dissolution kinetics of phytoliths extracted from fresh biomass of representative plant species (larch tree and elm, horsetail, fern, and four grasses) containing significant amount of biogenic silica. The solubility product of larch, horsetail, elm and fern phytoliths is close to that of amorphous silica and soil bamboo phytoliths. Electrophoretic measurements yield isoelectric point pH_IEP = 0.9, 1.1, 2.0 and 2.2 for four grasses, elm, larch and horsetail phytoliths respectively, which is very close to that of quartz or amorphous silica. Surface acid–base titrations allowed generation of a 2-pK surface complexation model (SCM) for larch, elm and horsetail phytoliths. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 1 ≤ pH ≤ 8, were found to be very similar among the species, and close to those of soil bamboo phytoliths. Mechanistic treatment of all plant phytoliths dissolution rates provided three-parameters equation sufficient to describe phytoliths reactivity in aqueous solutions:$R(\text{mol}/{\text{cm}}^2/\text{s})=6?{10}^{?16}?a_{\text{H+}}+5.0?{10}^{?18}+3.5?{10}^{?13}?a_{\text{OH}?}^{0.33}$Alternatively, the dissolution rate dependence on pH can be modeled within the concept of surface coordination theory assuming the rate proportional to concentration of > SiOH₂⁺, > SiOH⁰ and > SiO^? species. In the range of Al concentration from 20 to 5000 ppm in the phytoliths, we have not observed any correlation between their Al content and solubility, surface acid–base properties and dissolution kinetics.It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ～ 3. Mass-normalized dissolution rates are similar among all four types of plant species studied and these rates are an order of magnitude higher than those of typical soil clay minerals. The minimal half life time of larch and horsetail phytoliths in the interstitial soil solution ranges from 10–12 years at pH = 2–3 to < 1 year at pH above 6, comparable with mean residence time of phytoliths in soil from natural observations.     

Remediation of coal-mine drainage by a sulfate-reducing bioreactor: A case study from the Illinois coal basin,USA

This study reports changes in coal-mine drainage constituent concentrations through an anaerobic SO₄-reducing bioreactor monitored over a 3-a period. The purpose of the study was to identify and monitor over time the biogeochemical mechanisms that control the attenuation of toxic compounds in the mine drainage. This information is needed to investigate bioreactor performance and longevity. The water treated at the case example site, the Tab-Simco Mine, was highly acidic with an average pH of 2.9, a net acidity of 1674 mg/L CaCO₃ equivalent-CCE, and high levels of dissolved ${\text{SO}}_4^{2-}$, Al, Fe and Mn. The results of this study indicated that the treatment system increased the pH of the acid mine drainage (AMD) to 6.2 and decreased the median acidity to 22.7 mg/L CCE, ${\text{SO}}_4^{2-}$ from 2981 to 1750 mg/L, Fe from 450.6 to 1.76 mg/L, Al from 113 to 0.42 mg/L, and Mn from 36.4 to 23.3 mg/L. Geochemical modeling indicates that the bioreactor discharge is saturated with respect to the minerals alunite, gibbsite, siderite, rhodochrosite, jarosite, and Fe hydroxide precipitates. The observed trends also include seasonal variations in ${\text{SO}}_4^{2-}$ reduction and a general decline in the amount of alkalinity produced. The average δ³⁴S value of the ${\text{SO}}_4^{2-}$ in the untreated AMD was +7.3‰. In the bioreactor, δ³⁴S value of ${\text{SO}}_4^{2-}$ increased from an average of +6.9‰ to +9.2‰, suggesting the presence of bacterial SO₄ reduction processes. Preliminary results of a bacterial community analysis show that DNA sequences corresponding to bacteria capable of SO₄ reduction were present in the bioreactor outflow sample. However, these sequences were outnumbered by sequences similar to bacteria capable of reoxdizing reduced sulfur species. This study illustrates the dynamic nature of metal removal in SO₄-reducing bioreactor-based treatment systems.     

Isotopic tracing of perchlorate sources in groundwater from Pomona,California

The groundwater of Pomona, California, is contaminated with perchlorate (${\text{ClO}}_4^{-}$). This water is treated to reduce the ${\text{ClO}}_4^{-}$ concentration to less than 6 μg L⁻¹ for compliance with California Department of Public Health drinking water regulations. A study of the isotopic composition of oxygen and chlorine in ${\text{ClO}}_4^{-}$ has been conducted to determine the source of the contamination. Isotopic compositions were measured for ${\text{ClO}}_4^{-}$ samples extracted from 14 wells, yielding ranges of δ¹⁸O values from −10.8‰ to −8.0‰, Δ¹⁷O values from +4.6‰ to +7.5‰, and δ³⁷Cl values from −12.8‰ to −8.9‰. Evaluation of mixing proportions using published isotopic data for three ${\text{ClO}}_4^{-}$ end-members (synthetic, Atacama, and indigenous natural ${\text{ClO}}_4^{-}$) indicates that contamination is dominantly (85–89%) Atacama ${\text{ClO}}_4^{-}$ derived from past use of imported Chilean nitrate fertilizer in citrus cultivation. This interpretation is consistent with (1) aerial photography archives showing extensive citrus fields surrounding Pomona in the early- to mid-20th century, (2) mass-balance estimates for ${\text{ClO}}_4^{-}$, and (3) numerical hydrologic models yielding travel-times for ${\text{ClO}}_4^{-}$ from fields to wells that are in the range of 15 to >100 years. The hydrologic models predict that ${\text{ClO}}_4^{-}$ contamination of Pomona groundwater will persist for decades into the future.