Natural-abundance radiocarbon as a tracer of assimilation of petroleum carbon by bacteria in salt marsh sediments

The natural abundance of radiocarbon (¹⁴C) provides unique insight into the source and cycling of sedimentary organic matter. Radiocarbon analysis of bacterial phospholipid lipid fatty acids (PLFAs) in salt-marsh sediments of southeast Georgia (USA)—one heavily contaminated by petroleum residues—was used to assess the fate of petroleum-derived carbon in sediments and incorporation of fossil carbon into microbial biomass. PLFAs that are common components of eubacterial cell membranes (e.g., branched C₁₅ and C₁₇, 10-methyl-C₁₆) were depleted in ¹⁴C in the contaminated sediment (mean Δ¹⁴C value of +25 ± 19‰ for bacterial PLFAs) relative to PLFAs in uncontaminated “control” sediment (Δ¹⁴C = +101 ± 12‰). We suggest that the ¹⁴C-depletion in bacterial PLFAs at the contaminated site results from microbial metabolism of petroleum and subsequent incorporation of petroleum-derived carbon into bacterial membrane lipids. A mass balance calculation indicates that 6-10% of the carbon in bacterial PLFAs at the oiled site could derive from petroleum residues. These results demonstrate that even weathered petroleum may contain components of sufficient lability to be a carbon source for biomass production by marsh sediment microorganisms. Furthermore, a small but significant fraction of fossil carbon is assimilated even in the presence of a much larger pool of presumably more-labile and faster-cycling carbon substrates.     

Some Observations on the Determination of Gold and the Platinum-Group Elements in Black Shales

This research compares various ways of applying oxidative chemical decomposition to the analysis of gold-bearing black shale ores from the Russian Natalka and Sukhoj Log deposits. This study was conducted as part of the certification program for the Russian candidate black shale reference materials SLG-1 and SCHS-1 and also because of the paucity of data available on the determination of the platinum group elements (PGE) in analogous sample types. We report direct evidence of PGE volatilisation from black shale materials when processed in the presence of oxygen. We also developed a comprehensive analytical scheme for the quantitative determination of PGE in all phases (gaseous and ash) produced during slow combustion of carbonaceous materials in oxygen.
This study has shown that during combustion in oxygen at 600 °C, PGE contained in the Natalka black shale ores are lost as gaseous reaction products. Thus, the volatilized PGE (recovered in traps) account for up to 14% Pt, 40% Pd, 40% Ru and 10 % Ir relative to their total concentrations in a carbonaceous concentrate. It was also established that in the process of combustion, Au quantitatively remains in the ash cake.
In order to avoid the deleterious effects of oxygen on the volatility of the PGE, we propose a new comprehensive sample decomposition method based on the application of fluoroxidants such as BrF₃ and KBrF₄. This method was validated using samples of black shale ores and their processing products by comparing our results with those obtained independently using sealed autoclave processing of the same materials. It was shown that PGE in black shale ores and their processing products not only exist in commercially exploitable quantities but that a small proportion of PGE compounds are soluble in alcohol. We propose that in gold-bearing black shale ores, PGE are present as organometallic compounds.     

Arsenic Speciation in a Contaminated Gold Processing Tailings Dam

Gold recovery in ores containing arsenopyrite releases significant amounts of arsenic into the environment due to mineral processing and oxidation during storage. The extent of arsenic weathering in a tailings dam has been investigated. Speciation of As in surface and pore waters and pond sediments showed that for gold tailings in the dam, As enrichment took place in the pore water relative to the surface water. In pond sediments As was predominantly present as residual arsenopyrite and partly as a substance co-precipitated with iron hydroxide. The arsenic release from the sediment results from a reductive dissolution of the arsenopyrite and Fe oxides. In the surface water, arsenate and arsenite are the main arsenic species (arsenate is dominant), but in the pore waters methylation processes play a significant role. Arsenic transport is accompanied by the transformation of As into the less toxic compounds (methylated species) co-existing with the most toxic species (arsenite).     

Microphytobenthic primary production as C uptake in sublittoral sediments of the Gulf of Trieste (northern Adriatic Sea): Methodological aspects and data analyses

From January 2003 to December 2004 microphytobenthic primary production was estimated both from in situ (MPPs) and in the laboratory (MPPp) ¹⁴C-incubation of slurries collected in a coastal site of the Gulf of Trieste (northern Adriatic Sea). MPPs values varied from −7.54 ± 3.12 to 34.59 ± 7.66 mg C m⁻² h⁻¹ over the whole period. The lowest MPPs were observed in November 2003 and August 2004, while the highest MPPs in July 2003 and May 2004, in correspondence with high PAR at the bottom. Significant correlations between MPPs and the microphytobenthic biomass (BIOM) (r = 0.75, p < 0.001), between MPPs and PAR at the bottom (r = 0.54, p < 0.01) and between MPPs and OXY (r = 0.50, p < 0.05) were revealed. MPPp values were higher than MPPs ones in 15 out of 23 observations, with the highest MPPp recorded in July 2003. At 17 m depth a seasonal pattern of sampling months was revealed by the cluster analysis. The role of abiotic parameters in determining this seasonal pattern was highlighted by the PCA, with the first axis correlated with MPPs and PAR, and the second one with temperature. Applying the fuzzy sets it resulted that spring months showed a higher degree of membership with MPPs, summer months with temperature and autumn–winter months with OXY. The microphytobenthic community did not seem to be photosynthetically active throughout the study period. From August–September to December low or negative MPPs values were recorded. We infer that during these months a shift from the autotrophic to heterotrophic metabolism of the benthic microalgae occurred in correspondence with low PAR and/or high temperature at the bottom. Despite the progressive lowering of the trophy of the study area occurred during the last 20 years, we found higher primary production values than those estimated two decades earlier.     

Vertical Profiles of Major Organic Geochemical Constituents and Extracellular Enzymatic Activities in Sandy Sediments of Aransas and Copano Bays, TX

Vertical distribution patterns of organic geochemical constituents and the enzymes aminopeptidase and β-glucosidase provide insights about the nature and reactivity of sediment organic matter in the sandy sediments of two shallow “South Texas” estuaries. Sediment total organic carbon (TOC) δ¹³C values indicated that the organic matter (OM) was derived more from a mixture of seagrass and phytoplankton than from terrigenous OM. Down-core amounts of TOC and total nitrogen (TN) were <0.2% of dry weight, respectively. Enzyme activities were highest near surface and ranged from 25 to 1 μM/h for aminopeptidase as compared to 5 to 0.2 μM/h for glucosidase. In Aransas Bay, aminopeptidase activity correlated with sediment TN content (r _s = 0.30) and β-glucosidase with TOC content (r _s = 0.27). In Copano Bay, aminopeptidase correlated with TOC, TN, and carbohydrate content (r _s = 0.89, 0.90, and 0.83, respectively). Variations of glucosidase activity also related positively to TOC, TN, and total carbohydrate content (r _s = 0.68, 0.77, and 0.48, respectively). Overall, enzyme activities in these low OM, sandy sediments resembled those for other benthic marine environments.     

Five-coordinate Cd in the crystal structure of triploidite-type Cd2(AsO4)(OH)

This paper reports on hydrothermal synthesis and crystal structure refinement of dicadmium arsenate hydroxide, Cd₂(AsO₄)(OH), obtained at 220 °C and autogenous pressure. Its crystal structure is monoclinic, space group P2₁/a, with a = 13.097(3), b = 14.089(3), c = 10.566(2) Å, β = 108.38(3)°, V = 1850.2(6) ų (Z = 16). It is isotypic with the members of the triploidite group of minerals and synthetic compounds, and thus shows a close topological relationship with the triplite group. The complex framework contains edge- and corner-sharing CdO₄(OH) and CdO₄(OH)₂ polyhedra, linked via corner-sharing to AsO₄ tetrahedra (average As—O distances range between 1.682 and 1.688 Å). Four five-coordinated Cd sites are at the centers of distorted trigonal bipyramids (average Cd—O distances are between 2.225 and 2.251 Å), whereas the remaining four Cd sites have a distorted octahedral coordination environment (average Cd—O distances are between 2.297 and 2.320 Å). The positions of all the hydrogen atoms were located in a difference-Fourier map and refined with an isotropic displacement parameter. The hydrogen-bonds are weak to very weak. The unusual five-coordination of Cd is briefly discussed in relation to comparable minerals and compounds. Among triploidite-type compounds, Cd₂(AsO₄)(OH) is the member with the largest unit cell reported so far, and the second known arsenate member.     

Potential of the LASH model for water resources management in data-scarce basins: a case study of the Fragata River basin,southern Brazil

ABSTRACT

The objective of this study was to evaluate, based on a data-scarce basin in southern Brazil, the potential of the Lavras Simulation of Hydrology (LASH) model for estimating daily streamflows, annual streamflow indicators and the flow–duration curve. It was also used to simulate the different runoff components and their consistency with the basin physiographical characteristics. The statistical measures indicated that LASH can be considered suitable according to widely used classifications and when compared with other studies involving hydrological models. LASH also showed satisfactory results for annual indicators, especially for maximum and average annual streamflows, as well as for the flow–duration curve. It was found that the model was consistent with the basin characteristics when simulating runoff components. The results obtained in this study allowed us to conclude that the LASH model has the potential to aid practitioners in water resources management of basins with scarce data and similar soil and land-use conditions.

Editor A. Castellarin; Associate editor Y. Gyasi-Agyei     

Classification of low flow and hydrological drought for a river basin

The occurrence of drought is one of the characteristic features of Polish climate. Drought usually lasts for many weeks and covers considerable area causing economic and social losses. Due to the influence which drought has on environment, economy and society, more and more research and implementation works are devoted to issues concerning its occurrence, risk assessment, monitoring, and forecasting. Literature indicates that hydrological droughts are most often associated with low flow periods on rivers. The paper presents analyses of hydrological drought periods on the basis of hydrological drought index (HDI) for selected Nysa K?odzka study basin (SW part of Poland). Analyses were carried out in relation to the Maximum Credible Hydrological Drought (MCHD). In addition, attempts were taken to assess the hydrological drought based on atmospheric drought focused on application in ungauged basins in terms of hydrological monitoring.