Pyrite-induced hydroxyl radical formation and its effect on nucleic acids

Background  

Pyrite, the most abundant metal sulphide on Earth, is known to spontaneously form hydrogen peroxide when exposed to water. In this study the hypothesis that pyrite-induced hydrogen peroxide is transformed to hydroxyl radicals is tested.     

Comparison of dissolved and particulate arsenic distributions in shallow aquifers of Chakdaha, India, and Araihazar, Bangladesh

Background  

The origin of the spatial variability of dissolved As concentrations in shallow aquifers of the Bengal Basin remains poorly understood. To address this, we compare here transects of simultaneously-collected groundwater and aquifer solids perpendicular to the banks of the Hooghly River in Chakdaha, India, and the Old Brahmaputra River in Araihazar, Bangladesh.     

Calculation of the relative metastabilities of proteins using the CHNOSZ software package

Background  

Proteins of various compositions are required by organisms inhabiting different environments. The energetic demands for protein formation are a function of the compositions of proteins as well as geochemical variables including temperature, pressure, oxygen fugacity and pH. The purpose of this study was to explore the dependence of metastable equilibrium states of protein systems on changes in the geochemical variables.     

Raman and SEM analysis of a biocolonised hot spring travertine terrace in Svalbard,Norway

Background  

A profile across 8 layers from a fossil travertine terrace from a low temperature geothermal spring located in Svalbard, Norway has been studied using both Raman spectroscopy and SEM (Scanning Electron Microscopy) techniques to identify minerals and organic life signals.     

Biologically induced mineralization of dypingite by cyanobacteria from an alkaline wetland near Atlin,British Columbia,Canada

Background  

This study provides experimental evidence for biologically induced precipitation of magnesium carbonates, specifically dypingite (Mg₅(CO₃)₄(OH)₂·5H₂O), by cyanobacteria from an alkaline wetland near Atlin, British Columbia. This wetland is part of a larger hydromagnesite (Mg₅(CO₃)₄(OH)₂·4H₂O) playa. Abiotic and biotic processes for magnesium carbonate precipitation in this environment are compared.     

Surface complexation modeling of Cu(II) adsorption on mixtures of hydrous ferric oxide and kaolinite

Background  

The application of surface complexation models (SCMs) to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids.     

The effect of tidal forcing on biogeochemical processes in intertidal salt marsh sediments

Background  

Early diagenetic processes involved in natural organic matter (NOM) oxidation in marine sediments have been for the most part characterized after collecting sediment cores and extracting porewaters. These techniques have proven useful for deep-sea sediments where biogeochemical processes are limited to aerobic respiration, denitrification, and manganese reduction and span over several centimeters. In coastal marine sediments, however, the concentration of NOM is so high that the spatial resolution needed to characterize these processes cannot be achieved with conventional sampling techniques. In addition, coastal sediments are influenced by tidal forcing that likely affects the processes involved in carbon oxidation.     

Arsenic species in weathering mine tailings and biogenic solids at the Lava Cap Mine Superfund Site,Nevada City,CA

Background  

A realistic estimation of the health risk of human exposure to solid-phase arsenic (As) derived from historic mining operations is a major challenge to redevelopment of California's famed "Mother Lode" region. Arsenic, a known carcinogen, occurs in multiple solid forms that vary in bioaccessibility. X-ray absorption fine-structure spectroscopy (XAFS) was used to identify and quantify the forms of As in mine wastes and biogenic solids at the Lava Cap Mine Superfund (LCMS) site, a historic "Mother Lode" gold mine. Principal component analysis (PCA) was used to assess variance within water chemistry, solids chemistry, and XAFS spectral datasets. Linear combination, least-squares fits constrained in part by PCA results were then used to quantify arsenic speciation in XAFS spectra of tailings and biogenic solids.     

A method for generating uniform size-segregated pyrite particle fractions

Background  

Standardized sample preparation techniques allow comparison of pyrite dissolution experiments under diverse conditions. Our objective was to assess dry and wet sieving preparation methodologies, and to develop a reproducible technique that yields uniformly size-distributed material within a limited size range of interest.     

Description of an aerodynamic levitation apparatus with applications in Earth sciences

Background  

In aerodynamic levitation, solids and liquids are floated in a vertical gas stream. In combination with CO₂-laser heating, containerless melting at high temperature of oxides and silicates is possible. We apply aerodynamic levitation to bulk rocks in preparation for microchemical analyses, and for evaporation and reduction experiments.     

Geochemistry and geochronology of pre-Brasiliano rocks from the Transversal Zone, Borborema Province, Northeast Brazil

Proterozoic metamorphosed sequences are identified in the Transversal Zone (TZ) domain of the Borborema geological province, Northeast Brazil. This TZ domain is located between the well-known E–W Patos and Pernambuco continental shear zones. In its eastern part, in the Taquaritinga region, a large mass of augen gneisses with a conspicuous horizontal to subhorizontal tectonic foliation forms one of the most important rock types in the region that displays U–Pb zircon ages ca. 1.52 Ga. Paleoproterozoic orthogneisses dated by U–Pb on zircon at ca. 1.97 Ga and older paragneisses and banded gneisses represent basement rocks, which were cross-cut by these Mesoproterozoic augen gneisses, and have been in turn intruded by plutonic rocks in upper Neoproterozoic (U–Pb and Rb–Sr, ca. 0.6 Ga) times.Chemical analyses of major, minor, and trace elements (including REE) for the basement orthogneisses indicate calcalkaline affinities and a signature very similar to volcanic arc granites, representing crustal accretion during the Paleoproterozoic Transamazonian/Eburnean orogenesis in the region. In turn, the chemical data for augen gneisses indicate that they are relatively homogeneous and evolved metaluminous metaplutonic rocks with characteristics very similar to A-type granites generated and emplaced in an extensional anorogenic setting. Relatively high ⁸⁷Sr/⁸⁶Sr initial ratio and negative _Nd(t) are signatures of crustal components in these rocks.Based on geochemical, geochronological, and structural data, the Taquaritinga region is composed of Paleoproterozoic (>1.97 Ga) rocks intruded by Mesoproterozoic (ca. 1.5 Ga) anorogenic granites and Neoproterozoic granites (ca. 0.6 Ga). These data also suggest that the tectonometamorphic structures displayed by Meso and Neoproterozoic suites were developed by the Brasiliano/Pan-African orogeny and that the record of Transamazonian/Eburnean orogeny is restricted to basement rocks. This means that there is no evidence for a compressional event in Mesoproterozoic times (Cariris Velhos=Grenville) as suggested for the central and western part of the TZ. It is important to remark that the Taquaritinga augen gneisses are, up to now, the only unit that represents magmatic pulses associated with extensional episodes with this age (ca. 1.5 Ga) in the TZ and in the whole Borborema Province.

Resumen

A zona Transversal da Província Borborema está geologicamente situada entre os lineamentos Pernambuco e Patos. Na sua parte oriental, na região de Taquaritinga (PE), dominam augen gnaisses com uma penetrativa e proeminente foliação tectônica subhorizontal, com idade de cristalização de 1.52 Ga obtida em zircão. Estas rochas são intrusivas em ortognaisses e paragnaisses do embasamento com idade mínima em torno de 1.97 Ga, e são intrudidas por rochas plutônicas associadas ao Ciclo Brasiliano (ca. 0.6 Ga).Análises de elementos maiores, menores e traços (incluindo terras raras) nos augen gnaisses mostram caráter metaluminoso para esta suíte ígnea e fortes semelhanças com os granitos tipo-A gerados em ambiente anorogênico. Razões iniciais ⁸⁷Sr/⁸⁶Sr relativamente altas e _Nd(t) negativos são assinaturas indicadoras de forte contribuição crustal nestes augen gnaisses.A conjunção dos dados geoquímicos, geocronológicos e de campo indicam que na região de Taquaritinga onde são identificadas rochas de idades paleo (>1.95 Ga), meso (ca. 1.5 Ga) e neoproterozóicas (ca. 0.6 Ga), o ciclo orogênico Transamazônico é restrito às rochas do embasamento, e que todas as estruturas dúcteis identificadas nas rochas meso e neoproterozóicas foram desenvolvidas durante o Ciclo orogênico Brasiliano. Não foram encontradas evidências que atestem a existência do Ciclo Cariris Velhos nesta parte da Província Borborema. Contudo, está bem marcado que nesta Zona Transversal e na Província Borborema, os augen gnaisses de Taquaritinga são, até o momento, os únicos marcadores de pulsos magmáticos associados com eventos extensionais crustais datados do Mesoproterozóico inferior.     

Trace metal speciation in sea and pore water of the Gotland Deep,Baltic Sea, 1994

Studies on the speciation (particulate, colloidal, anionic and cationic forms) of trace metals (Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Zn) in the water column and in pore waters of the Gotland Deep following the 1993/94 salt-water inflows showed dramatic changes in the total “dissolved” metal concentrations and in the ratios between different metal species in the freshly re-oxygenated waters below 125 m. Changes in concentrations were greatest for those metals for which the solubility differs with the redox state (Fe, Mn, Co) but were also noted for those metals which form insoluble sulphides (Cd, Pb, Cu, Zn) and/or stable complexes with natural ligands (Cu). Pore water data from segmented surface muds (0–200 mm) indicated that significant redox and related metal speciation changes took place in the surface sediments only a few weeks after the inflow of the oxygenated sea water into the Gotland Deep.     

Elevated naturally occurring arsenic in a semiarid oxidizing system, Southern High Plains aquifer, Texas, USA

High groundwater As concentrations in oxidizing systems are generally associated with As adsorption onto hydrous metal (Al, Fe or Mn) oxides and mobilization with increased pH. The objective of this study was to evaluate the distribution, sources and mobilization mechanisms of As in the Southern High Plains (SHP) aquifer, Texas, relative to those in other semiarid, oxidizing systems. Elevated groundwater As levels are widespread in the southern part of the SHP (SHP-S) aquifer, with 47% of wells exceeding the current EPA maximum contaminant level (MCL) of 10 μg/L (range 0.3–164 μg/L), whereas As levels are much lower in the north (SHP-N: 9%  As MCL of 10 μg/L; range 0.2–43 μg/L). The sharp contrast in As levels between the north and south coincides with a change in total dissolved solids (TDS) from 395 mg/L (median north) to 885 mg/L (median south). Arsenic is present as arsenate (As V) in this oxidizing system and is correlated with groundwater TDS (Spearman’s ρ = 0.57). The most likely current source of As is sorbed As onto hydrous metal oxides based on correlations between As and other oxyanion-forming elements (V, ρ = 0.88; Se, ρ = 0.54; B, ρ = 0.51 and Mo, ρ = 0.46). This source is similar to that in other oxidizing systems and constitutes a secondary source; the most likely primary source being volcanic ashes in the SHP aquifer or original source rocks in the Rockies, based on co-occurrence of As and F (ρ = 0.56), oxyanion-forming elements and SiO₂ (ρ = 0.41), which are found in volcanic ashes. High groundwater As concentrations in some semiarid oxidizing systems are related to high evaporation. Although correlation of As with TDS in the SHP aquifer may suggest evaporative concentration, unenriched stable isotopes (δ²H: −65 to −27; δ¹⁸O: −9.1 to −4.2) in the SHP aquifer do not support evaporation. High TDS in the SHP aquifer is most likely related to upward movement of saline water from the underlying Triassic Dockum aquifer. Mobilization of As in other semiarid oxidizing systems is caused by increased pH; however, pH in the SHP aquifer is near neutral (10–90 percentiles, 7.0–7.6). Although many processes, such as competitive desorption with SiO₂, VO₄, or PO₄, could be responsible for local mobilization of As in the SHP aquifer, the most plausible explanation for the regional As distribution and correlation with TDS is the counterion effect caused by a change from Ca- to Na-rich, water as shown by the high correlation between As and Na/(Ca)^0.5 ratios (ρ = 0.57). This change in chemistry is related to mixing with saline water that moves upward from the underlying Dockum aquifer. This counterion effect may mobilize other anions and oxyanion-forming elements that are correlated with As (F, V, Se, B, Mo and SiO₂). Competition among the oxyanions for sorption sites may enhance As mobilization. The SHP case study has similar As sources to those of other semiarid, oxidizing systems (original volcanic ash source followed by sorption onto hydrous metal oxides) but contrasts with these systems by showing lack of evaporative concentration and pH mobilization of As but counterion mobilization of As instead in the SHP-S aquifer.     

Trace metals in Antarctic ecosystems: Results from the Larsemann Hills,East Antarctica

Sediments, mosses and algae, collected from lake catchments of the Larsemann Hills, East Antarctica, were analysed to establish baseline levels of trace metals (Ag, As, Cd, Co, Cr, Cu, Ni, Sb, Pb, Se, V and Zn), and to quantify the extent of trace metal pollution in the area. Both impacted and non-impacted sites were included in the study. Four different leaching solutions (1 M MgCl₂, 1 M CH₃COONH₄, 1 M NH₄NO₃, and 0.3 N HCl) were tested on the fine fraction (<63 μm) of the sediments to extract the mobile fraction of trace metals derived from human impact and from weathering of basement lithologies. Results of these tests indicate that dilute HCl partly dissolves primary minerals present in the sediment, thus leading to an overestimate of the mobile trace metal fraction. Concentrations of trace metals released using the other 3 procedures indicate negligible levels of anthropogenic contribution to the trace metal budget. Data derived from this study and a thorough characterisation of the site allowed the authors to define natural baseline levels of trace metals in sediments, mosses and algae, and their spatial variability across the area. The results show that, with a few notable exceptions, human activities at the research stations have contributed negligible levels (lower than natural variability) of trace metals to the Larsemann Hills ecosystem. This study further demonstrates that anthropogenic sources of trace metals can be correctly identified and quantified only if natural baselines, their variability, and processes controlling the mobility of trace metals in the ecosystem, have been fully characterised.     

High-resolution monitoring of nitrate variations in a typical subterranean karst stream, Chongqing, China

Globally, it is possible that up to 25% of the world’s population depends on karst water supplies. In karst areas, a high degree of groundwater and surface water linkage often results in the direct recharge of groundwater with polluted run-off following rainfall. In order to reveal the hydrochemical variations after rainfall, especially real-time variation of pollutants, high-resolution auto-monitoring techniques were used at the outlet of Qingmuguan subterranean stream (QSS), which is influenced by agricultural activities. In addition to rainfall, high-resolution measurements of pH, water level, electrical conductivity (Ec) and NO₃ ⁻ concentration were recorded in the monsoon season and fertilizer application period using a data logger with time intervals of 15 min. In the six observed rainfall events, the pH value was mainly controlled by acidic rainfall inputs. The pH showed sharp decline after the rainfall event, and then increased. The Ec was impacted by the rainfall chemistry, dilution effect of rainfall and agricultural wastewater. NO₃ ⁻ derived from agricultural activities was less impacted by rain chemistry; and its variations were mainly affected by the dilution effect of rainfall and agricultural wastewater. Under the influences of the R1 rainfall, the rapid changes of Ec and NO₃ ⁻ were opposite in direction. As the rain continued, both the Ec and NO₃ ⁻ rapidly changed in synchronization within the shortest period of 5 h and the longest of 27 h because of the impact of the agricultural wastewater. The groundwater quality changed due to the influx of agricultural wastewater over the entire monitoring period. According to the National Groundwater Quality Standard, People’s Republic of China (GB/T14848-9), the groundwater quality of the QSS moved through the following grades during the monitoring period: Grade III → Grade IV → Grade V → Grade IV → Grade V → Grade IV → Grade V → Grade IV → Grade III. Traditional sampling methods did not reveal accurate hydrochemistry changes of the QSS, and even generated misleading results. Consequently, the high-resolution auto-monitoring technique is necessary for the future protection and sustainable use of karst aquifer in Southwest China.     

新疆可可托海稀有金属矿床矿物和岩石热红外光谱特征

当前新型材料、新能源在各个领域应用不断深化,稀有金属矿床迎来了世界范围内的研究与勘探热潮。新疆可可托海稀有金属矿床是我国最早开发利用稀有金属矿产资源的重要基地,但对其典型矿物和围岩的热红外反射光谱的认识还很缺乏,制约了对同类型矿床开展遥感地质调查和遥感地质学研究工作的推进。本文采用便携式热红外光谱仪,对可可托海3号脉的典型矿物岩石开展热红外光谱特征研究。结果表明:热红外光谱可以有效识别锂辉石、锂云母、绿柱石、电气石等典型的稀有金属矿物。其中,与锂云母相比,含锂云母伟晶岩产生了新的特征峰;含锂辉石伟晶岩、含电气石伟晶岩相比于各自单晶矿物,其反射特征峰均明显向短波方向偏移;含绿柱石伟晶岩光谱曲线反射特征峰比绿柱石单晶反射特征峰明显向长波方向偏移。本文初步建立了可可托海典型矿物和岩石热红外光谱特征数据库,总结了以锂辉石、锂云母等稀有金属矿床矿物、含矿伟晶岩及围岩的热红外光谱特征,可为热红外光谱进行稀有金属矿物的识别及花岗伟晶岩型矿床的勘探提供必要的基础数据支撑。     

Assessing Cd,Co, Cu,Ni, and Pb Sorption on montmorillonite using surface complexation models

Cadmium, Co, Cu, Ni and Pb adsorption is measured on montmorillonite as a function of pH (3–11), ionic strength (0.001–0.1 M NaNO₃), and sorbate concentration (0.1–10 μM metal on 0.5 g/L solid). Sorption of all metals shows strong dependence on ionic strength and sorbate concentration, as well as a break in the slope of the edge, indicative of a 2-site interaction with montmorillonite. The resulting adsorption edges are used to parameterize diffuse layer surface complexation models (DLMs) for each metal. A 2-site DLM with a bidentate variable charge surface hydroxyl site and a bidentate permanent charge exchange site produced good fits for the individual experiments, but lacked the robustness to accurately predict adsorption across the entire experimental range. Other models, such as CCM, TLM, or CD-MUSIC may be required for more accurate predictions across broad ranges of solution conditions.     

Heat capacity, entropy, and magnetic properties of jarosite-group compounds

Jarosite phases are common minerals in acidic, sulfate-rich environments. Here, we report heat capacities (C _p) and standard entropies (S°) for a number of jarosite samples. Most samples are close to the nominal composition AFe₃(SO₄)₂(OH)₆, where A = K, Na, Rb, and NH₄. One of the samples has a significant number of defects on the Fe sites and is called the defect jarosite; others are referred to as A-jarosite. The samples, their compositions, and the entropies at T = 298.15 K are: