Bulk modulus of Fe-rich olivines corrected for non-hydrostaticity

In situ X-ray diffraction was used to measure the isothermal bulk modulus at room conditions (K_T0) of synthetic olivines with different iron contents. The chemical formulae of the olivine samples were ${({\mathrm{Fe}}_x,{\mathrm{Mg}}_{1?x})}_2\mathrm{Si}{\mathrm{O}}_4$ with x = 0.45; 0.64; 0.82; 1, with 1% standard deviation (referenced as Fa45, Fa64, Fa82 and Fa100, respectively). All experiments were performed in the multi-anvil apparatus installed at NSLS beamline X17B2, to pressures up to about 7 GPa. Unit-cell volumes under hydrostatic conditions and differential stresses present in the samples were calculated using the method developed by Singh et al. (1998), and pressures measured using NaCl as a standard were then corrected for these stresses. Using a second-order Birch–Murnaghan equation of state, we obtained the isothermal bulk modulus of each composition: $K_{T0}^{\mathrm{Fa45}}=131.4\pm 2.6$ GPa, $K_{T0}^{\mathrm{Fa64}}=132.1\pm 3.1$ GPa, $K_{T0}^{\mathrm{Fa82}}=136.3\pm 1.7$ GPa and $K_{T0}^{\mathrm{Fa100}}=134.8\pm 1.4$ GPa. These values combined with data available in the literature show that the K_T0 of Fe-rich olivines increases very slowly with the Fe content, but possibly not in a simple linear trend.     

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.     

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.     

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.     

Model reconstruction of nitrate pollution of riverbank filtration using 15N and 18O data,Karany, Czech Republic

Stable isotopes of O (δ¹⁸O) in water and N (δ¹⁵N) in ${\text{NO}}_3^{-}$ have been used as natural indigenous groundwater tracers for sources of water and of ${\text{NO}}_3^{-}$ at two riverbank filtration (RBF) water supply systems. Both RBF systems (Skorkov and Sojovice) have wells in unconsolidated Quaternary sediments close to the Jizera River (Czech Republic) that have been affected by increasing ${\text{NO}}_3^{-}$ concentrations. The area is underlain by Turonian sandstones and marls that form a deeper bedrock aquifer. Sources of ${\text{NO}}_3^{-}$ are local sewerage systems and landfills (point sources) and seasonal application of manure and inorganic fertilizers (diffuse sources).At RBF Skorkov recharge to wells can be modelled using a two-component model with 60% river water contribution and 40% of very shallow groundwater with an average residence time of one month. During periods of abundant precipitation, groundwater originates entirely from the unsaturated zone of the Quaternary aquifer; extensive pumping for over 40 a has created new, bypassing flow paths that preferentially drain the contaminated unsaturated zone. During dry periods, wells are recharged by longer residence time groundwater from the Quaternary aquifer.At RBF Sojovice there is an additional recharge component of groundwater from the Turonian aquifer, which is sandier at this locality; this contains denitrified ${\text{NO}}_3^{-}$ with highly positive δ¹⁵N values.     

The fate of major constituents and chromium and other trace elements when acid waters from the derelict Libiola mine (Italy) are mixed with stream waters

Geochemical modeling was used to investigate the fate of major constituents and Cr and other trace elements when acid waters from the derelict Libiola mine are mixed with the Gromolo creek waters, and related processes. This was carried out in two steps: (1) Mixing between acid waters and stream waters was simulated using the EQ3/6 software package; the results showed that mixing brings about the precipitation of some secondary solid phases, mainly a ferrihydrite-rich solid mixture of hydroxides and basaluminite. (2) The sorption of cations (Cr³⁺, Cu²⁺, Zn²⁺, Mn²⁺, Ni²⁺, Ca²⁺, and Mg²⁺) and anions (${\mathrm{CrO}}_4^{2-}$ and ${\mathrm{SO}}_4^{2-}$) on ferrihydrite was modeled by means of the code MINTEQA2, treating the concentrations of relevant solutes and the moles of ferrihydrite (computed by means of EQ3/6) as input data.The results of this two-step geochemical modeling generally agree with analytical data, supporting the following conclusions: (a) dissolved Mg, Ca, Na, SO₄, Cl, HCO₃ and SiO₂ are mainly controlled by acid water–stream water mixing; (b) Fe is mainly incorporated into ferrihydrite and subordinately in schwertmannite and jarosite; (c) Al is chiefly sequestered in basaluminite and alunite; (d) K is temporarily incorporated into jarosite and alunite and is released into the aqueous solution upon their dissolution; (e) the mobility of Cu, Zn, Ni, Mn, and Cr(VI) is mainly controlled by sorption on precipitating ferrihydrite; (f) Cr(III) is immobilised by both incorporation into ferrihydrite and sorption on its surface.The effects of acid mine waters on the Gromolo aqueous system are not ameliorated to an acceptable extent by natural attenuation through dilution and related processes.