Geochemistry and mineralogy of arsenic in (natural) anaerobic groundwaters

Here new data from field bioremediation experiments and geochemical modeling are reported to illustrate the principal geochemical behavior of As in anaerobic groundwaters. In the field bioremediation experiments, groundwater in Holocene alluvial aquifers in Bangladesh was amended with labile water-soluble organic C (molasses) and MgSO₄ to stimulate metabolism of indigenous SO₄-reducing bacteria (SRB). In the USA, the groundwater was contaminated by Zn, Cd and SO₄, and contained <10 μg/L As under oxidized conditions, and a mixture of sucrose and methanol were injected to stimulate SRB metabolism. In Bangladesh, groundwater was under moderately reducing conditions and contained ∼10 mg/L Fe and ∼100 μg/L As. In the USA experiment, groundwater rapidly became anaerobic, and dissolved Fe and As increased dramatically (As > 1000 μg/L) under geochemical conditions consistent with bacterial Fe-reducing conditions. With time, groundwater became more reducing and biogenic SO₄ reduction began, and Cd and Zn were virtually completely removed due to precipitation of sphalerite (ZnS) and other metal sulfide mineral(s). Following precipitation of chalcophile elements Zn and Cd, the concentrations of Fe and As both began to decrease in groundwater, presumably due to formation of As-bearing FeS/FeS₂. By the end of the six-month experiment, dissolved As had returned to below background levels. In the initial Bangladesh experiment, As decreased to virtually zero once biogenic SO₄ reduction commenced but increased to pre-experiment level once SO₄ reduction ended. In the ongoing experiment, both SO₄ and Fe(II) were amended to groundwater to evaluate if FeS/FeS₂ formation causes longer-lived As removal. Because As-bearing pyrite is the common product of SRB metabolism in Holocene alluvial aquifers in both the USA and Southeast Asia, it was endeavored to derive thermodynamic data for arsenian pyrite to better predict geochemical processes in naturally reducing groundwaters. Including the new data for arsenian pyrite into Geochemist’s Workbench, its stability field completely dominates in reducing Eh–pH space and “displaces” other As-sulfides (orpiment, realgar) that have been implied to be important in previous modeling exercises and reported in rare field conditions.     

Considerations for conducting incubations to study the mechanisms of As release in reducing groundwater aquifers

Microbial Fe reduction is widely believed to be the primary mechanism of As release from aquifer sands in Bangladesh, but alternative explanations have been proposed. Long-term incubation studies using natural aquifer material are one way to address such divergent views. This study addresses two issues related to this approach: (1) the need for suitable abiotic controls and (2) the spatial variability of the composition of aquifer sands. Four sterilization techniques were examined using orange-colored Pleistocene sediment from Bangladesh and artificial groundwater over 8 months. Acetate (10 mM) was added to sacrificial vials before sterilization using either (1) 25 kGy of gamma irradiation, (2) three 1-h autoclave cycles, (3) a single addition of an antibiotic mixture at 1× or (4) 10× the typical dose, and (5) a 10 mM addition of azide. The effectiveness of sterilization was evaluated using two indicators of microbial Fe reduction, changes in diffuse spectral reflectance and leachable Fe(II)/Fe ratios, as well as changes in P-extractable As concentrations in the solid phase. A low dose of antibiotics was ineffective after 70 days, whereas autoclaving significantly altered groundwater composition. Gamma irradiation, a high dose of antibiotics, and azide were effective for the duration of the experiment.     

CO<Subscript>2</Subscript> Flux Measurements over the Sea Surface by Eddy Correlation and Aerodynamic Techniques

The measurements of the vertical transport of CO₂ were carried out over the Sea of Japan using the specially designed pier of Kyoto University on September 20 to 22, 2000. CO₂ fluxes were measured by the eddy correlation and aerodynamic techniques. Both techniques showed comparable CO₂ fluxes during sea breeze conditions: −0.001 to −0.08 mg m⁻²s⁻¹ with the mean of −0.05 mg m⁻²s⁻¹. This means that the measuring site satisfies the fetch requirement for meteorological observations under sea breeze conditions. Moreover, the eddy diffusivity coefficient used in the aerodynamic technique is found to be consistent with the coefficient used in the eddy correlation technique. The present result leads us to conclude that the aerodynamic technique may be applicable to underway CO₂ flux measurements over the ocean and may be used in place of the bulk technique. The important point is the need to maintain a measuring accuracy of CO₂ concentration difference of the order of 0.1 ppmv on the research vessels or the buoys.     

Scaling analysis of deposition from turbidity currents

Many oil-bearing sedimentary deposits are formed by the settling of particles from turbidity currents. Modeling sedimentary processes that form these turbidites enables the calculation of properties such as extent, depth, porosity and permeability of hydrocarbon-bearing reservoirs. This paper estimates the extent and thickness of turbidites from the initial conditions of the turbidity flow. This is achieved by the application of scaling analysis of the partial differential equations that govern the dynamics of and deposition from turbidity currents. We apply the results of scaling analysis to five modern submarine fans. The predicted and actual values of the dimensions of the fan deposits match well. We then compare the derived results against tabulated sizes of ancient turbidites. The comparisons are good as long as we correctly identify the flow regimes in which the deposition took place. The good agreements observed in the two cases show that the estimates obtained using scaling analysis can provide useful first-guess values for the dimensions of the deposits.     

Preservation of enzymic activity in marine plankton by low-temperature freezing

The measurement of enzymic activity in plankton communities is useful in the study of marine ecosystems. Such measurements can lead to a clearer understanding of the biological transformations in plankton communities at a particular time. However, the assays are somewhat time-consuming. To facilitate analysis of large numbers of samples, we have developed a method of quick-freezing of whole cells and of cell-free extracts of the diatom, Skeletonema costatum, followed by storage at ?60°C for up to one week. No loss in either the electron transport system (ETS) or the glutamate dehydrogenase (GDH) activity occurs. Similar conditions of storage can be used for the preservation of ETS activity in the marine copepod Calanus pacificus. Also, no measurable loss in either the GDH or the ETS activity is detectable after the quick-frozen whole cells of S. costatum have been kept frozen for over a year.     

Simple determination of dimethylsulfide (DMS) and dimethylsulfoniopropionate (DMSP) using solid-phase microextraction and gas chromatography-mass spectrometry

Solid-phase microextraction (SPME) is a simple, sensitive and less destructive method for the determination of dimethylsulfide (DMS) in seawater. Combined with detection by gas chromatography-mass spectrometry (GC-MS), the method had sufficient sensitivity (minimum detectable concentration of DMS was 0.05 nM), and practical levels of reproducibility (relative standard deviation ≤7%) and linearity (r ² > 0.995) over a wide concentration range (0.5 to 910 nM). The protocol developed was applied to a Sagami Bay water sample to determine concentrations of DMS and DMSP, and in situ DMSP-lyase activity.     

Computational modeling of cyclic mobility and post-liquefaction site response

Under seismic excitation, liquefied clean medium to dense cohesionless soils may regain a high level of shear resistance at large shear strain excursions. This pattern of response, known as a form of cyclic mobility, has been documented by a large body of laboratory sample tests and centrifuge experiments. A plasticity-based constitutive model is developed with emphasis on simulating the cyclic mobility response mechanism and associated pattern of shear strain accumulation. This constitutive model is incorporated into a two-phase (solid–fluid), fully coupled finite element code. Calibration of the constitutive model is described, based on a unique set of laboratory triaxial tests (monotonic and cyclic) and dynamic centrifuge experiments. In this experimental series, Nevada sand at a relative density of about 40% is employed. The calibration effort focused on reproducing the salient characteristics of dynamic site response as dictated by the cyclic mobility mechanism. Finally, using the calibrated model, a numerical simulation is conducted to highlight the effect of excitation frequency content on post-liquefaction ground deformations.     

Les dykes basiques du massif ancien de l'Ourika (Atlas de Marrakech,Maroc) : géochimie et significationThe basic dykes of the Ourika old massif (High Atlas of Marrakech): Geochemistry and significance

The Precambrian massif of Ourika is crosscut by two systems of basic dykes, striking N40°E and N90–120°E. Using incompatible trace elements, the two systems form two distinct chemical groups, displaying a continental tholeiitic affinity. The composition variations between the two defined groups can be due to heterogeneities of mantle sources and to contamination, during the magma ascent, by the continental crust. The emplacement of these basic dykes, before the late-PIII formations, can be related to the Neoproterozoic distension generalised to the Anti-Atlas chain. To cite this article: A. Barakat et al., C. R. Geoscience 334 (2002) 827–833.