Arsenic incorporation into FeS2 pyrite and its influence on dissolution: A DFT study

FeS₂ pyrite can incorporate large amounts of arsenic (up to ca. 10 wt%) and hence has a strong impact on the mobility of this toxic metalloid. Focussing on the lowest arsenic concentrations for which the incorporation occurs in solid solution, the substitution mechanisms involved have been investigated by assuming simple incorporation reactions in both oxidising and reducing conditions. The solution energies were calculated by Density Functional Theory (DFT) calculations and we predict that the formation of AsS dianion groups is the most energetically favourable mechanism. The results also suggest that the presence of arsenic will accelerate the dissolution and thus the generation of acid drainage, when the crystal dissolves in oxidising conditions.     

The origin of groundwater arsenic and fluorine in a volcanic sedimentary basin in central Mexico: a hydrochemistry hypothesis

A groundwater sampling campaign was carried out in the summer of 2013 in a low-temperature geothermal system located in Juventino Rosas (JR) municipality, Guanajuato State, Mexico. This groundwater presents high concentrations of As and F^? and high Rn counts, mainly in wells with relatively higher temperature. The chemistry of major elements was interpreted with different methods, like Piper and D’Amore diagrams. These diagrams allowed for classification of four groundwater types located in three hydrogeological environments. The aquifers are hosted mainly in alluvial-lacustrine sediments and volcanic rocks in interaction with fault and fracture systems. The subsidence, faults and fractures observed in the study area can act as preferential channels for recharge and also for the transport of deep fluids to the surface, especially in the basin plain. The formation of a piezometric dome and the observed hydrochemical behavior of groundwater suggest a possible origin of the As and F^?. Geochemical processes occurring during water–rock interaction are related to high concentrations of As and F^?. High temperatures and alteration processes (like rock weathering) induce dissolution of As and F^?-bearing minerals, increasing the content of these elements in groundwater.     

Simultaneous oxidation of arsenic and antimony at low and circumneutral pH,with and without microbial catalysis

Arsenic and Sb are common mine-water pollutants and their toxicity and fate are strongly influenced by redox processes. In this study, simultaneous Fe(II), As(III) and Sb(III) oxidation experiments were conducted to obtain rates under laboratory conditions similar to those found in the field for mine waters of both low and circumneutral pH. Additional experiments were performed under abiotic sterile conditions to determine the biotic and abiotic contributions to the oxidation processes. The results showed that under abiotic conditions in aerated Fe(III)–H₂SO₄ solutions, Sb(III) oxidizes slightly faster than As(III). The oxidation rates of both elements were accelerated by increasing As(III), Sb(III), Fe(III), and Cl⁻ concentrations in the presence of light. For unfiltered circumneutral water from the Giant Mine (Yellowknife, NWT, Canada), As(III) oxidized at 15–78 μmol/L/h whereas Sb(III) oxidized at 0.03–0.05 μmol/L/h during microbial exponential growth. In contrast, As(III) and Sb(III) oxidation rates of 0.01–0.03 and 0.01–0.02 μmol/L/h, respectively, were obtained in experiments performed with acid unfiltered mine waters from the Iberian Pyritic Belt (SW Spain). These results suggest that the Fe(III) formed from microbial oxidation abiotically oxidized As(III) and Sb(III). After sterile filtration of both mine water samples, neither As(III), Sb(III), nor Fe(II) oxidation was observed. Hence, under the experimental conditions, bacteria were catalyzing As and Sb oxidation in the Giant Mine waters and Fe oxidation in the acid waters of the Iberian Pyrite Belt.     

Illite authigenesis in sandstones of the Guaritas Allogroup (Early Paleozoic): Implications for the depositional age,stratigraphy and evolution of the Camaquã Basin (Southern Brazil)

Several analytical studies performed on alluvial-eolian sandstones of the Early Paleozoic Guaritas Allogroup (Camaquã Basin, southern Brazil) indicate illite to be abundant, showing different morphologies as authigenic grain rims and pore-bridging filaments. Authigenic illite separates of variable grain sizes from distinct stratigraphic intervals of the Guaritas Allogroup yielded ⁴⁰K–⁴⁰Ar ages from 521.7 ± 10.3 to 473.7 ± 9.4 Ma. These ages, interpreted to record the timing of illite authigenesis, are coincident with the age of emplacement of the Rodeio Velho andesites (470 ± 19 Ma). Moreover, field structures suggest interaction between hot, andesite lava flows and wet, poorly consolidated sediments of the Pedra Pintada Alloformation (lower strata of the Guaritas Allogroup). This set of data indicates that the Rodeio Velho volcanism could have been responsible for a widespread remobilization of interstitial fluids and consequent authigenic illite precipitation in the sandstones of the Guaritas Allogroup.     

Correction to: A novel methodological approach for land subsidence prediction through data assimilation techniques

Computational Geosciences - A Correction to this paper has been published: https://doi.org/10.1007/s10596-021-10079-6     

Fractionation of carbon isotopes in biosynthesis of fatty acids by a piezophilic bacterium Moritella japonica strain DSK1

We examined stable carbon isotope fractionation in biosynthesis of fatty acids of a piezophilic bacterium Moritella japonica strain DSK1. The bacterium was grown to stationary phase at pressures of 0.1, 10, 20, and 50 MPa in media prepared using sterile-filtered natural seawater supplied with glucose as the sole carbon source. Strain DSK1 synthesized typical bacterial fatty acids (C_14-19 saturated, monounsaturated, and cyclopropane fatty acids) as well as long-chain polyunsaturated fatty acids (PUFA) (20:6ω3). Bacterial cell biomass and individual fatty acids exhibited consistent pressure-dependent carbon isotope fractionations relative to glucose. The observed Δδ_FA-glucose (−1.0‰ to −11.9‰) at 0.1 MPa was comparable to or slightly higher than fractionations reported in surface bacteria. However, bulk biomass and fatty acids became more depleted in ¹³C with pressure. Average carbon isotope fractionation (Δδ_FA-glucose) at high pressures was much higher than that for surface bacteria: −15.7‰, −15.3‰, and −18.3‰ at 10, 20, and 50 MPa, respectively. PUFA were more ¹³C depleted than saturated and monounsaturated fatty acids at all pressures. The observed isotope effects may be ascribed to the kinetics of enzymatic reactions that are affected by hydrostatic pressure and to biosynthetic pathways that are different for short-chain and long-chain fatty acids. A simple quantitative calculation suggests that in situ piezophilic bacterial contribution of polyunsaturated fatty acids to marine sediments is nearly two orders of magnitude higher than that of marine phytoplankton and that the carbon isotope imprint of piezophilic bacteria can override that of surface phytoplankton. Our results have important implications for marine biogeochemistry. Depleted fatty acids reported in marine sediments and the water column may be derived simply from piezophilic bacteria resynthesis of organic matter, not from bacterial utilization of a ¹³C-depleted carbon source (i.e., methane). The interpretation of carbon isotope signatures of marine lipids must be based on principles derived from piezophilic bacteria.     

Determination of Gold in Ores by Isobutyl Methyl Ketone Extraction and Electrothermal Atomic Absorption Spectrometry: A Stability Study of the Metal in Organic Media

A method involving gold extraction into isobutyl methyl ketone (IBMK), after partial dissolution with aqua regia , with determination by electrothermal atomic absorption spectrometry is described. The pyrolysis and atomisation temperatures were optimized using a pyrolytic graphite forked platform. The stability study of gold in isobutyl methyl ketone extract indicated that closed polypropylene containers (3% absorbance measurement changes) were better than both open polypropylene and closed glass containers over periods of up to 22 hr. Satisfactory recoveries of 99 and 102% were obtained when Au, in the IBMK extracts from CH-3 and MA-2 reference materials, were determined after storage of the extracts in closed polypropylene containers for 22 hr, respectively.     

Fluctuations of the Fennoscandian Ice Sheet recorded in the anisotropy of magnetic susceptibility of periglacial loess from Ukraine

The azimuth of imbrication of minimum magnetic susceptibility axes in the youngest loess from Ukraine defines prevailing wind directions during aeolian sedimentation. It changes along the studied sections. These changes can be directly correlated with the fluctuations of the Fennoscandian Ice Sheet. The northern and northeastern winds noted in the loess succession separated by a period when southwestern to southeastern winds were predominant may be correlated with two main phases of ice‐sheet advance during the Last Glacial Maximum. The ice‐sheet advances towards the areas of loess deposition generated katabatic winds that influenced aeolian sedimentation in the periglacial zone. A period of relatively stable wind directions during a younger phase of the Last Glacial Maximum was interrupted by periods with more chaotic wind regime most probably caused by fluctuations of the Fennoscandian Ice Sheet during its retreat from the peri‐Baltic part of Europe. These intervals occur where initial soils developed. The distribution of anisotropy of magnetic susceptibility axes defined along the periglacial loess sections from central and eastern Europe can serve to constrain fluctuations of the Fennoscandian Ice Sheet.     

Algal blooms: a perspective from the coasts of India

Algal blooms have been documented along the west and east coasts of India. A review of bloom occurrences in Indian waters from 1908 to 2009 points out that a total of 101 cases have been reported. A comparison of the bloom cases reported before and after the 1950s reveals that there is an increase in the number of bloom occurrences. The reports of algal blooms indicate their predominance along the west coast of India especially the southern part. Majority of the blooms reported along the west coast of India are caused by dinoflagellates, whereas diatom blooms prevail along the east coast. There have been 39 causative species responsible for blooms, of which Noctiluca scintillans and Trichodesmium erythraeum are the most common. Reporting of massive fish mortality in Indian waters has been associated with the blooming of Cochlodinium polykrikoides, Karenia brevis, Karenia mikimotoi, N. scintillans, T. erythraeum, Trichodesmium thiebautii and Chattonella marina. Most of the blooms occurred during withdrawal of the south-west monsoon and pre-monsoon period. In Indian waters, this process is mainly influenced by seasonal upwelling and monsoonal forcing that causes high riverine discharge resulting in nutrient-enriched waters that provides a competitive edge for blooming of phytoplankton species.