Trace element and molecular markers of organic carbon dynamics along a shelf–basin continuum in sediments of the western Arctic Ocean

Molecular organic biomarkers together with trace element composition were investigated in sediments east of Barrow Canyon in the western Arctic Ocean to determine sources and recycling of organic carbon in a continuum from the shelf to the basin. Algal biomarkers (polyunsaturated and short-chain saturated fatty acids, 24-methylcholesta-5,24(28)-dien-3β-ol, dinosterol) highlight the substantial contribution of organic matter from water column and sea-ice primary productivity in shelf environments, while redox markers such as acid volatile sulfide (AVS), Mn, and Re indicate intense metabolism of this material leading to sediment anoxia. Shelf sediments also receive considerable inputs from terrestrial organic carbon, with biomarker composition suggesting the presence of multiple pools of terrestrial organic matter segregated by age/lability or hydrodynamic sorting. Sedimentary metabolism was not as intense in slope sediments as on the shelf; however, sufficient labile organic matter is present to create suboxic and anoxic conditions, at least intermittently, as organic matter is focused towards the slope. Basin sediments also showed evidence for episodic delivery of labile organic carbon inputs despite the strong physical controls of water depth and sea-ice cover. Principal components analysis of the lipid biomarker data was used to estimate fractions of preserved recalcitrant (of terrestrial origin) and labile (of marine origin) organic matter in the sediments, with ranges of 12–79%, 14–45%, and 37–66% found for the shelf, slope, and basin cores, respectively. On average, the relative preserved terrestrial organic matter in basin sediments was 56%, suggesting exchange of organic carbon between nearshore and basin environments in the western Arctic.     

Size Fractionation (Dissolved, Colloidal and Particulate) of Trace Metals in the Thur River, Switzerland

The distribution of some trace metals (Cu, Zn, Ni, Co,Fe, Mn) and of DOC over a particulate (> 1 m),a colloidal (size < 0.45 m and molecular weight > 10 kD) and an ultrafiltered fraction (< 10 kD)was determined at several sites on the Thur River,Switzerland, at various times of the year. Thecomplexation of Cu by strong ligands in theultrafiltrate and in the conventional filtrate (<0.45 m) was compared using a ligand-exchange/CSV method.The <0.45 m concentrations of Cu (from anaverage of 7 nM to 24 nM), Zn (<5–23 nM), Ni (5–13 nM),Co (1.5–3 nM) and Mn (7–92 nM)increased downstream. The major part of Cu, Zn, Niand Co usually occurred in the ultrafiltratefraction at all sites, whereas Fe and Mn were mostlyin the particulate fraction, under conditions of lowsuspended matter content (< 10 mg L^-1) in theriver. The percentage of metal in the colloidalfraction, with respect to the 0.45-m filtrate,decreased in the order: Cu (median 11%) > Zn Ni(median 5–6%) > Mn Co (median < 5%). DOCalso consisted mostly of molecules in the < 10 kDrange.Cu was strongly complexed by natural organic ligandsin all filtrate and ultrafiltrate samples. A largepart of the strong Cu binding ligands consisted ofcompounds in the < 10 kD range, but colloidalligands with similar properties also occurred. Cu wasdistributed among the dissolved and the colloidalligands, roughly in proportion to organic carbon.The colloidal fraction (as defined here) did notincrease in its proportional amount downstream and wasonly of limited significance in transporting traceelements in the Thur River under low discharge conditions.     

The rank evaluation of South Brazilian Gondwana coals on the basis of different chemical and physical parameters

Rank evaluation of South Brazilian Gondwana coals according to the American (American Society for Testing and Materials, ASTM) and German (Deutsche Industrie Normen, DIN) standard specifications or on the basis of Alpern's Universal Classification has too often led to conflicting results.When any attempt is made to determine the rank of Brazilian coals by using methods established for the Northern Hemisphere coals, two sorts of difficulties arise: namely, (1) the reflectence measurements do not indicate the real degree of coalification of the organic matter because of the liptinitic impregnations of the vitrinites, and (2) random reflectance values (R_ran, moisture, volatile-matter and carbon contents as well as the calorific value do not correlate when plotted on the ASTM and DIN classification schemes.In addition, when rank determinations are carried out by using fluorescence measurements and geochemical analyses the results are at variance in relation to those determined by the conventional chemical and physical parameters.It is suggested that the rank evaluation of South Brazilian coals is far more meaningful if carried out by reflectance measurements on vitrinites along with fluorescence measurements on sporinites, alginites and coal extracts.     

Analysis of aquifer vulnerability and water quality using SINTACS and geographic weighted regression

Aquifer vulnerability and water quality were assessed in the Central Valleys of Oaxaca (Mexico) using the SINTACS method, based on a geographic information system. SINTACS layers were prepared using data such as climate (rainfall and temperature), water table, hydraulic conductivity, geology, soil type and topographic model. Maps for water quality index (WQI), contamination index and pollution sources index (PSI) were also obtained by this work. Groundwater quality in the Central Valleys may be affected by two factors, those with an anthropogenic origin and those with natural origin. High vulnerability values are located in the valleys of the basin, where granular sediments are exposed. Low vulnerability values are distributed in the basin??s ranges, where metamorphic rocks are found. Given that many of the zones with the highest groundwater vulnerability values correspond to zones with the greatest PSI values, there is great risk of groundwater contamination for the area of study because external (indicated by PSI) and internal (indicated by SINTACS) factors that cause pollution can be frequently observed in the same place. Geographic weighted regression (GWR) is used to test the dependency between WQI as dependent variable and SINTACS, PSI, Urban localities, Agriculture, Pastures and Rivers as predictors. The results indicate the non-stationary behavior of the dependent variable with respect to the predictors. While the obtained GWR models used to model WQI cannot be used in practical situations to predict the behavior of said variable, they can be used to estimate the degree to which the predictors influence the variable of interest.     

Experimental investigation of the effects of temperature and ionic strength on Mo isotope fractionation during adsorption to manganese oxides

The Mo stable isotope system is being applied to study changes in ocean redox. Such applications implicitly assume that Mo isotope fractionation in aqueous systems is relatively insensitive to frequently changing environmental variables such as temperature (T) and ionic strength (I). A major driver of fractionation is the adsorption of Mo to Mn oxyhydroxide surfaces [Barling J. and Anbar A. D. (2004) Molybdenum isotope fractionation during adsorption by manganese oxides. Earth Planet. Sci. Lett.217(3-4), 315-329]. Here, we report the results of experiments that determine the extent to which Mo isotope fractionation during adsorption of Mo to the Mn oxyhydroxide mineral birnessite is sensitive to T and I. The results are compared to new predictions from quantum chemical computations. We measured fractionation from 1 to 50 °C at I = 0.1 m and found that Δ^97/95Mo_{dissolved-adsorbed} varies from 1.9‰ to 1.6‰ over this temperature range. Experiments were also performed at 25 °C in synthetic seawater (I = 0.7); fractionation at this condition was the same within analytical error as in low ionic strength experiments. These findings confirm that the Mo isotope fractionation during adsorption to Mn oxyhydroxides is relatively insensitive to variations and T and I over environmentally relevant ranges. To relate these findings to potential mechanisms of Mo isotope fractionation, we also report results for density functional theory computations of the fractionation between and various possible structures of molybdic acid as a function of temperature. Because no plausible species fractionates from with a magnitude matching the experiments, we are left with three possibilities to explain the fractionation: (1) solvation effects on the vibrational frequencies of aqueous species considered thus far are significant, such that our calculations in vacuo yield inaccurate fractionations; (2) a trace aqueous species not yet considered fractionates from and then adsorbs to birnessite; or (3) a surface complex not present in solution forms on birnessite in which Mo is not tetrahedrally coordinated. Our findings help validate assumptions underlying paleoceanographic applications of the Mo isotope system and also lead us closer to understanding the mechanism of isotope fractionation during adsorption of Mo to Mn oxyhydroxides.     

Effect of the dilution process on the attenuation of contaminants in aquifers

This paper discusses the effects of the dilution process on levels of aquifer contamination attenuation, developing analytical equations for application in theoretical and practical cases. The key finding is that, in aquifers, the dilution process causes a reduction of the contaminant concentration. Analytical equations for the assessment of the contaminant attenuation capacity, by means of the dilution process in an aquifer, are put forward. In particular, the attenuation of the contaminant concentration in an aquifer, and thus the dilution, is described by the volumetric flow rate per unit width perpendicular to the flow direction (q _u). Moreover, a classification of q _u was developed, considering six classes of attenuation capacity due to dilution. For the equations validation, nitrate contamination attenuation due to dilution was analysed in two sample areas in Piedmont (North-West Italy). The results confirmed the hypothesis, evidencing high nitrate concentrations in areas with low q _u values, connected to low dilution rate of the contaminant in the groundwater; vice versa, low nitrate concentrations were evidenced in areas with high q _u values, due to a high nitrate dilution rate.     

Paleoecology and radiocarbon dating of the Pleistocene megafauna of the Brazilian Intertropical Region

During the Pleistocene a fauna composed of large (biomass > 44 kg) and giant mammals (biomass > 1000 kg) that are usually associated with open environments lived in the Brazilian Intertropical Region. We present here new information concerning the paleoecology and chronology of some species of this megafauna. Carbon isotope analyses were performed for a better understanding of the paleoecology of the species Eremotherium laurillardi (Lund, 1842), Notiomastodon platensis (Ameghino, 1888) and Toxodon platensis (Owen, 1849). The δ¹³C data allow attributing a generalist diet to these species, which varied according to the kind of habitat in which they lived. In more open habitats all species were grazers; in mixed habitats E. laurillardi and T. platensis were mixed feeders, and N. platensis was grazer; and in more closed habitats all species were mixed feeders.     

Assessment to the potential mobility and toxicity of metals and metalloids in soils contaminated by old Sb–Au and As–Au mines (NW Portugal)

The main purpose of this study is to assess arsenic and antimony availability in soils, as well as Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn availability in soils derived from the schist–metagraywacke complex close to old Sb–Au mines and in soils developed from Ordovician slates and close to an old As–Au mine in Portugal. The availability was determined using a European certified sequential extraction procedure (BCR). The results demonstrated that metalloids are not readily bioavailable, because they are mainly associated with the residual fraction. Arsenic and antimony proportions in exchangeable fractions are up to 3 and 1%, respectively. However, arsenic is up to 24% in oxy-hydroxide fractions, while antimony is up to 4% in them, demonstrating the highest bioavailability of arsenic compared to that of antimony, as metalloids are weakly bound to the soils in that fraction. Therefore, arsenic tends to be more toxic than antimony in all soils studied. However, the pseudo-total contents show that both metalloids are above the Italian and Dutch guidelines. Therefore, if physico-chemical changes occur arsenic and antimony will show higher potential environmental risk than evidenced by Co, Cr, Cu, Fe, Mn, Ni, Pb and Zn.     

Seal integrity and feasibility of CO<Subscript>2</Subscript> sequestration in the Teapot Dome EOR pilot: geomechanical site characterization

This paper reports a preliminary investigation of CO₂ sequestration and seal integrity at Teapot Dome oil field, Wyoming, USA, with the objective of predicting the potential risk of CO₂ leakage along reservoir-bounding faults. CO₂ injection into reservoirs creates anomalously high pore pressure at the top of the reservoir that could potentially hydraulically fracture the caprock or trigger slip on reservoir-bounding faults. The Tensleep Formation, a Pennsylvanian age eolian sandstone is evaluated as the target horizon for a pilot CO₂ EOR-carbon storage experiment, in a three-way closure trap against a bounding fault, termed the S1 fault. A preliminary geomechanical model of the Tensleep Formation has been developed to evaluate the potential for CO₂ injection inducing slip on the S1 fault and thus threatening seal integrity. Uncertainties in the stress tensor and fault geometry have been incorporated into the analysis using Monte Carlo simulation. The authors find that even the most pessimistic risk scenario would require ∼10 MPa of excess pressure to cause the S1 fault to reactivate and provide a potential leakage pathway. This would correspond to a CO₂ column height of ∼1,500 m, whereas the structural closure of the Tensleep Formation in the pilot injection area does not exceed 100 m. It is therefore apparent that CO₂ injection is not likely to compromise the S1 fault stability. Better constraint of the least principal stress is needed to establish a more reliable estimate of the maximum reservoir pressure required to hydrofracture the caprock.