Role of extracellular polymeric substances in metal ion complexation on Shewanella oneidensis: Batch uptake, thermodynamic modeling, ATR-FTIR, and EXAFS study

The effect of cell wall-associated extracellular polymeric substances (EPS) of the Gram-negative bacterium Shewanella oneidensis strain MR-1 on proton, Zn(II), and Pb(II) adsorption was investigated using a combination of titration/batch uptake studies, surface complexation modeling, attenuated total reflectance - Fourier transform infrared (ATR-FTIR) spectroscopy, and Zn K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. Both unmodified (wild-type (WT) strain) and genetically modified cells with inhibited production of EPS (ΔEPS strain) were used. Three major types of functional groups (carboxyl, phosphoryl, and amide groups) were identified in both strains using ATR-FITR spectroscopy. Potentiometric titration data were fit using a constant capacitance model (FITEQL) that included these three functional groups. The fit results indicate less interaction of Zn(II) and Pb(II) with carboxyl and amide groups and a greater interaction with phosphoryl groups in the ΔEPS strain than in the WT strain. Results from Zn(II) and Pb(II) batch adsorption studies and surface complexation modeling, assuming carboxyl and phosphoryl functional groups, also indicate significantly lower Zn(II) and Pb(II) uptake and binding affinities for the ΔEPS strain. Results from Zn K-edge EXAFS spectroscopy show that Zn(II) bonds to phosphoryl and carboxyl ligands in both strains. Based on batch uptake and modeling results and EXAFS spectral analysis, we conclude that the greater amount of EPS in the WT strain enhances Zn(II) and Pb(II) uptake and hinders diffusion of Zn(II) to the cell walls relative to the ΔEPS strain.     

150 years of anthropogenic metal input in a Biosphere Reserve: the case study of the Cananéia–Iguape coastal system, Southeastern Brazil

The Cananéia–Iguape system consists of a complex of estuarine and lagoonal channels located in the coastal region of southeastern Brazil known as Lagamar, a Biosphere Reserve recognized by the United Nations Educational, Scientific and Cultural Organization (UNESCO) in 1991. The area suffered dramatic environmental changes along the last ca. 150 years initiated by the 1852 opening of an artificial channel, the Valo Grande, connecting the Ribeira de Iguape River to the estuarine system. Due to Au, Ag, Zn, and Pb mining activities that took place in the upstream regions of the Ribeira de Iguape River since the seventeenth century, the system has acted as a final destination of contaminated sediments. Analysis of cores located along the estuarine system revealed a history of contamination, with an increase of anthropogenic metal input between the decades of 1930 and 1990. The anthropogenic influence can be traced in locations as far as 20 km from the mouth of the artificial channel.     

Determination of Platinum-Group Elements in Geological Reference Materials by High Resolution-ICP-MS after Nickel Sulfide Fire-Assay Collection and Te Co-Precipitation

Inductively coupled plasma-mass spectrometry (ICP-MS) after NiS fire assay-Te co-precipitation was employed in the determination of Ru, Rh, Pd, Os, Ir and Pt at ng g^-1 levels in six platinum-group element (PGE) geological reference materials. In general, the average of several results was in good agreement with the certified values taking into account respective uncertainties. High relative standard deviations were observed for the reference materials GPt-3 and GPt-4. Problems associated with the NiS fire assay procedure and PGE determination at the sub-10 ng g^-1 level are reviewed and discussed.     

Fluid flow through the sedimentary cover in northern Switzerland recorded by calcite–celestite veins (Oftringen borehole,Olten)

Abundant veins filled by calcite, celestite and pyrite were found in the core of a 719 m deep borehole drilled in Oftringen near Olten, located in the north-western Molasse basin, close to the thrust of the Folded Jura. Host rocks are calcareous marl, argillaceous limestone and limestone of the Dogger and Malm. The δ¹⁸O values of vein calcite are lower than in host rock carbonate and, together with microthermometric data from fluid inclusions in vein calcite, indicate precipitation from a seawater-dominated fluid at average temperatures of 56–68°C. Such temperatures were reached at the time of maximum burial of the sedimentary pile in the late Miocene. The depth profile of δ¹³C and ⁸⁷Sr/⁸⁶Sr values and Sr content of both whole-rock carbonate and vein calcite show marked trends towards negative δ¹³C, high ⁸⁷Sr/⁸⁶Sr, and low Sr content in the uppermost 50–150 m of the Jurassic profile (upper Oxfordian). The ⁸⁷Sr/⁸⁶Sr of vein minerals is generally higher than that of host rock carbonate, up to very high values corresponding to Burdigalian seawater (Upper Marine Molasse, Miocene), which represents the last marine incursion in the region. No evidence for internally derived radiogenic Sr (clay minerals) has been found and so an external source is required. S and O isotope composition of vein celestite and pyrite can be explained by bacterial reduction of Miocene seawater sulphate. The available data set suggests the vein mineralization precipitated from descending Burdigalian seawater and not from a fluid originating in the underlying Triassic evaporites.     

The Transfiguration continental red-bed Cu–Pb–Zn–Ag deposit,Quebec Appalachians,Canada

The Transfiguration Cu–Pb–Zn–Ag deposit, enclosed within reduced grey sandstone, is associated with continental red beds of the Lower Silurian Robitaille Formation in the Quebec Appalachians, Canada. The Robitaille Formation rests unconformably on foliated Cambro-Ordovician rocks. The unconformity is locally cut by barite veins. The basal unit of the Robitaille Formation comprises green wacke and pebble conglomerate, which locally contain calcite nodules. The latter have microstructures characteristic of alpha-type calcretes, such as “floating” fabrics, calcite-filled fractures (crystallaria) and circumgranular cracks. Massive, grey sandstone overlies the basal green wacke and pebble conglomerate unit, which is overlain, in turn, by red, fine-grained sandstone. Mineralisation occurred underneath the red sandstone unit, chiefly in the grey sandstone unit, as disseminated and veinlet sulphides. Chalcopyrite, the most abundant Cu sulphide, replaced early pyrite. Calcrete, disseminated carbonate and vein carbonate have stable isotope ratios varying from −7.5‰ to −1.1‰ δ¹³C and from 14.7‰ to 21.3‰ δ¹⁸O. The negative δ¹³C values indicate the oxidation of organic matter in a continental environment. Sulphur isotope ratios for pyrite, chalcopyrite and galena vary from −19‰ to 25‰ δ³⁴S, as measured on mineral concentrates by a conventional SO₂ technique. Laser-assisted microanalyses (by fluorination) of S isotopes in pyrite show an analogous range in δ³⁴S values, from −21‰ to 25‰. Negative and positive δ³⁴S values are compatible with bacterial sulphate reduction (BSR) in systems open and closed with respect to sulphate. We interpret similarly high δ³⁴S values for sulphide concentrates (25.1‰) and for vein barite (26.2‰) to result from rapid and complete thermochemical reduction of pore-water sulphate. Two early to late diagenetic stages of mineralisation best explain the origin of the Transfiguration deposit. The first stage was characterised by the ponding of groundwater over the Taconian unconformity, recorded by calcrete and early pyrite formation via BSR in grey sandstone. Early pyrite contains up to 2 wt.% Pb, which is consistent with Pb fixation by sulphate-reducing bacteria. The second stage (II) is defined by the replacement of early pyrite by chalcopyrite, as well as by sulphide precipitation via either BSR or thermochemical sulphate reduction (TSR) in grey sandstone. This event resulted from the synsedimentary fault-controlled percolation and mixing of (1) an oxidising, sulphate-bearing cupriferous fluid migrating per descensum from the red-bed sequence and (2) a hydrocarbon-bearing fluid migrating per ascensum from the Cambro-Ordovician basement. Mixing between the two fluids led to sulphate reduction, causing Cu sulphide precipitation. The positive correlation between Cu and Fe³⁺/Fe²⁺ bulk rock values suggests that Fe acted as a redox agent during sulphate reduction. Stage II diagenetic fluid migration is tentatively attributed to the Late Silurian Salinic extensional event.     

Annual fossil organic carbon delivery due to mechanical and chemical weathering of marly badlands areas

A key issue in the study of the carbon cycle is constraining the stocks and fluxes in and between C‐reservoirs. Among these, the role and importance of fossil organic carbon (FOC) release by weathering of outcropping sedimentary rocks on continental surfaces is still debated and remains poorly constrained. Our work focuses on FOC fluxes due to chemical and mechanical weathering of marls in two experimental watersheds with typical badlands geomorphology (Draix watersheds, Laval and Moulin, Alpes de Haute Provence, France). Organic matter from bedrock, soil litter and riverine particles are characterized by Rock‐Eval 6 pyrolysis. FOC fluxes due to mechanical weathering are then estimated by monitoring the annual particulate solid exports at the outlets of the watersheds (1985–2005 period). FOC fluxes from chemical weathering were calculated using Ca²⁺ concentrations in dissolved loads (year 2002) to assess the amount of FOC released by the dissolution of the carbonate matrix. Results show that FOC delivery is mainly driven by mechanical weathering, with a yield ranging from 30 to 59 t km^‐2 yr^‐1 in the Moulin (0.08 km²) and Laval (0.86 km²) catchments, respectively, (1985–2005 average). The release of FOC attributed to chemical weathering was 2.2 to 4.2 t km^‐2 for the year 2002. These high FOC fluxes from badlands are similar to those observed in tectonically active mountain catchments. At a regional scale, badland outcropping within the Durance watershed does not exceed 0.25% in area of the Rhône catchment, but could annually deliver 12 000 t yr^‐1 of FOC. This flux could correspond to 27% of the total particulate organic carbon (POC) load exported by the Rhône River to the Mediterranean Sea. At a global scale, our findings suggest that erosion of badlands may contribute significantly to the transfer of FOC from continental surfaces to depositional environments. Copyright © 2012 John Wiley & Sons, Ltd.     

Turonian Radiolarians from Karnezeika,Argolis Peninsula,Peloponnesus (Greece)

Near Karnezeika a roughly 140 m thick Upper Cretaceous section consists of interbedded pelagic limestones, cherts and coarse polymict breccias including ophiolites and shallow water limestones. At the base, pink pelagic limestones rest on deeply altered and fractured Lower Jurassic Pantokrator Limestone. This first pelagic facies is dated as middle Turonian, based on planktonic Foraminifera. Over 100 m of coarse ophiolite-carbonate breccias, interpreted as a channel or canyon fill in a pelagic environment, document the erosion of the Late Jurassic nappe edifice along the Cretaceous Pelagonian margin. Above these breccias, we mesured 16 m of principally pink and red pelagic limestones and radiolarian cherts, in which we recovered well-preserved radiolarians discussed here. In this interval, the presence of planktonic Foraminfera allows to state a late Turonian to Coniacian age. More than 40 radiolarian species are described and figured in this work. The radiolarian chronostratigraphy established by 10 different authors in 11 publications was compared for this study and used to establish radiolarian ranges. This exercise shows major discrepancies between authors for the radiolarian ranges of the studied assemblage. Nevertheless, a Turonian age can be stated based on a synthesis of cited radiolarian ranges. This age is consistent with the age based on planktonic foraminifera. In combining the ages of both Radiolaria and planktonic Foraminifera, the studied samples can be restricted to the late Turonian. However, the discrepancies of published radiolarian ranges call for an urgent, major revision of the Late Cretaceous radiolarian biochronology. The integration of planktonic foraminifera with radiolarians may greatly enhance biochronologic resolution in sections where both groups occur.     

Geochemistry of mine waters draining a low-sulfide, gold-quartz vein deposit, Bralorne, British Columbia

The Bralorne and Pioneer mines, now inactive, produced over 4 million ounces of Au from an orogenic lode Au deposit located on the eastern edge of the Coastal Mountains of SW British Columbia. Between 2007 and 2009, drainage from a recently developed exploration adit was investigated in order to better understand and anticipate potential environmental management issues associated with the development of this type of deposit in the future. Portal discharge rate and specific conductance were monitored continuously over a 14-month period during which 36 water samples were collected. Additional samples were collected from flooded workings within the adit. Concentrations of As and Sb at the portal range as high as 1738 and 316 μg/L, respectively, while those in the mine pool reach 3304 and 349 μg/L, respectively. Effluent chemistry is mildly alkaline (pH = 8.7) and is dominated by Na, Ca, Mg, HCO₃ and SO₄. Geochemical inverse modeling of effluent composition indicates weathering of albite (2515 kg/a), ferroan dolomite (718 kg/a), pyrite (456 kg/a), arsenopyrite (23 kg/a) and stibnite (2 kg/a). Modeled sulfide reaction coefficients, normalized by their corresponding host rock concentrations, suggest that oxidation of arsenopyrite is 25 times slower than that of pyrite whereas oxidation of stibnite is 1.5 times faster. Oxidative dissolution of arsenopyrite and stibnite releases 10.6 kg/a of As and 1.1 kg/a of Sb of which 57% and 46%, respectively, are sorbed to ferrihydrite and gibbsite on the bed of the shallow channel through which the mine pool drains to the portal. Although mass balance calculations predict the formation of sufficient ferrihydrite to sorb 100% of the As dissolved in the mine pool, this attenuation process was ineffective possibly because the precipitated sorbents settled to the bottom of the water column or because of competition for sorption sites from Ca and HCO₃. The dissolved Sb/As molar ratio in portal effluent (0.082) is much greater than the Sb/As ratio of the mineralization (0.002) because of slower arsenopyrite oxidation and somewhat lesser sorption of Sb.     

Hydrothermal fluid source constrained by Co/Ni ratios in coexisting arsenopyrite and tourmaline: the auriferous lode of Passagem, Quadrilátero Ferrífero of Minas Gerais, Brazil

The auriferous lode of Passagem de Mariana is characterised by abundant tourmaline, which is intergrown with arsenopyrite. Spot measurements using laser ablation–inductively coupled plasma–mass spectrometry show that Co and Ni are the most abundant trace elements in the arsenopyrite (45–538?ppm Co, 246–828?ppm Ni), with Co/Ni ratios consistently <1. The coexisting tourmaline also has Co/Ni <1, with Co and Ni contents that are ~2 orders of magnitude lower than those in the arsenopyrite. The Co/Ni ratios of tourmaline and arsenopyrite are tightly distributed along a positive linear trend, the angular coefficient of which represents the Co/Ni of the hydrothermal fluid from which these minerals precipitated. The fluid Co/Ni ratio is close to the average Co/Ni value for the upper continental crust. In conjunction with the abundance of lode tourmaline and its B-isotope data (from the literature), the Co/Ni ratios of tourmaline and arsenopyrite fingerprint a continental evaporitic source of B.