Sulfur isotope fractionation during growth of sulfate-reducing bacteria on various carbon sources

Stable sulfur isotope fractionation during microbial sulfate reduction is a potential tool to estimate sulfate reduction rates at field sites. However, little is known about the influence of the utilized carbon source on the magnitude of sulfur isotope fractionation. To investigate this effect, both a pure culture (strain PRTOL1) and enrichment cultures from a petroleum hydrocarbon (PHC)-contaminated aquifer were used and grown in batch cultures on various carbon sources with an initial sulfate concentration of 1 mmol/L. As sole carbon sources the PHC components naphthalene, 1,3,5-trimethylbenzene, and heating oil (enrichment culture) and the organic acids acetate, pyruvate, benzoate, and 3-phenylpropionate (enrichment culture and PRTOL1) were used. Sulfate reduction rates of all cultures ranged from 6 ± 1 nmol cm⁻³ d⁻¹ (enrichment culture grown on 1,3,5-trimethylbenzene) to 280 ± 6 nmol cm⁻³ d⁻¹ (enrichment culture grown on pyruvate). Cell-specific sulfate reduction rates ranged from 1.1 × 10⁻¹⁴ mol cell⁻¹ d⁻¹ (PRTOL1 grown on pyruvate) to 1.5 × 10⁻¹³ mol cell⁻¹ d⁻¹ (PRTOL1 grown on acetate). Sulfur isotope enrichment factors (ε) for the enrichment culture ranged from 16.1‰ (3-phenylpropionate) to 34.5‰ (1,3,5-trimethylbenzene) and for PRTOL1 from 30.0‰ (benzoate) to 36.0‰ (pyruvate). Cultures of PRTOL1 always showed higher ε values than the enrichment culture when grown on the same carbon source due to culture-specific properties. Higher ε values were obtained when the enrichment culture was grown on PHC components than on organic acids. No relationship between ε values and cell-specific sulfate reduction rate existed when all data were combined. When comparing the magnitude of ε values determined in this laboratory study with ε values measured at contaminated and uncontaminated field sites, it becomes evident that a multitude of factors influences ε values at field sites and complicates their interpretation. The results of this study help us assess some of the general parameters that govern the magnitude of ε in sulfate-reducing environments.     

Urban land transformation for pro-poor economies

The transformation of land into a setting for clustering local economies can become an important cornerstone of poverty policy. This transformation has several functional aspects, which in turn have important institutional and political aspects. Underlying both the functional and institutional factors is the role of local government and local democracy. Such a conceptualization puts to center stage several paradoxes: A terrain that seems “slum-like” turns out to be highly productive and employment generating. Complex tenure forms and mixed land use seen as “unplanned” turn out to be pre-requisites for economic development. There are institutional paradoxes that contrast efforts at “transparency” and managerial “best practices”. Here, the messiness of local bureaucracies in municipal government turns out to be critical for poor groups to influence interventions in their favor. Influencing the public process may be more effective in stealth-like ways rather taking a more visible approach. Most fundamentally these issues remind us that the potential of cities to reinforce or reduce poverty moved far beyond projects and programs and the normative frameworks used by planners and administrators. Instead, it is the transformative process of turning land into economic settings that might be at the center stage. This is a stage where poor groups are the central actors who stealth-like draw on complex alliances across ethnic and class lines to shapes cities in their interests.     

Field and petrological evidence for a Late Palaeozoic (Upper Carboniferous–Permian) age of the Erfaulet orthogneiss (Gran Paradiso,western Alps)

In the Gran Paradiso massif (western Alps), the boundary between the Erfaulet orthogneiss and the overlying metasediments (Money Complex) is interpreted as a Late Palaeozoic intrusive contact. Major arguments in favour of this hypothesis are: (i) the obliquity of the sedimentary layering with respect to the contact; (ii) the presence of aplitic dykes within the Money Complex; (iii) the lack of a mylonitic zone; and (iv) rare relics of an early generation of garnet in the Money metasediments, interpreted as evidence of the contact metamorphism of the Erfaulet granite. To cite this article: B. Le Bayon, M. Ballèvre, C. R. Geoscience 336 (2004).     

Clustering and visualization of earthquake data in a grid environment

We present a web client-server service WEB-IS, which we have developed for remote analysis and visualization of seismic data consisting of both small magnitude events and large earthquakes. We show that the problem-solving environment (PSE) intended for prediction of large magnitude earthquakes can be based on this WEB-IS idea. The clustering schemes, feature generation, feature extraction techniques and rendering algorithms form a computational framework of this environment. On the other hand, easy and fast access both to the seismic data distributed among distant computing resources and to computational and visualization resources can be realized in a GRID framework. We discuss the usefulness of NaradaBrokering (iNtegrated Asynchronous Real-time Adaptive Distributed Architecture) as a middleware, allowing for flexibility and high throughput for remote visualization of geophysical data. The WEB-IS functionality was tested both on synthetic and the actual earthquake catalogs. We consider the application of similar methodology for tsunami alerts.     

A model for oxygen and sulfur isotope fractionation in sulfate during bacterial sulfate reduction processes

We present a model of bacterial sulfate reduction that includes equations describing the fractionation relationship between the sulfur and the oxygen isotope composition of residual sulfate (δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}) and the amount of residual sulfate. The model is based exclusively on oxygen isotope exchange between cell-internal sulfur compounds and ambient water as the dominating mechanism controlling oxygen isotope fractionation processes. We show that our model explains δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns observed from natural environments and from laboratory experiments, whereas other models, favoring kinetic isotope fractionation processes as dominant process, fail to explain many (but not all) observed δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} patterns. Moreover, we show that a “typical” δ³⁴S_{SO4_residual} vs. δ¹⁸O_{SO4_residual} slope does not exist. We postulate that measurements of δ³⁴S_{SO4_residual} and δ¹⁸O_{SO4_residual} can be used as a tool to determine cell-specific sulfate reduction rates, oxygen isotope exchange rates, and equilibrium oxygen isotope exchange factors. Data from culture experiments are used to determine the range of sulfur isotope fractionation factors in which a simplified set of equations can be used. Numerical examples demonstrate the application of the equations. We postulate that, during denitrification, the oxygen isotope effects in residual nitrate are also the result of oxygen isotope exchange with ambient water. Consequently, the equations for the relationship between δ³⁴S_{SO4_residual}, δ¹⁸O_{SO4_residual}, and the amount of residual sulfate could be modified and used to calculate the fractionation-relationship between δ¹⁵N_{NO3_residual}, δ¹⁸O_{NO3_residual}, and the amount of residual nitrate during denitrification.     

象牙海岸Issia地区铌钽砂矿的研究(英文)

在西非的象牙海岸Issia地区分布着许多铌钽矿床,包括原生矿和砂矿。原生矿产在分带很好的伟晶岩中。这个地区发育着许多花岗岩和花岗伟晶岩。伟晶岩可分为:(1)分异不好的伟晶岩,无矿化;(2)含Be伟晶岩,分带较好,见绿柱石;(3)含Be-Nb-Ta的伟晶岩,分带很好,是矿体;(4)Be-Nb-Ta-Li伟晶岩,分带很好,是矿体。除了10多个原生矿外,还有许多砂矿。砂矿有两种类型:一种近原生矿的坡积砂矿,另一种是经河流冲刷搬运后的冲积砂矿。我们选择了Etienne-Meguhe砂矿作为近原生矿的坡积砂矿的代表,Bemadi矿作为河流冲积型的砂矿的代表,对这两种类型的砂矿的风化、搬运、沉积机理进行了比较研究。研究发现不同的搬运距离和搬运模式对铌钽砂矿的主要矿物——铌钽铁矿的化学性质没有什么影响,而其物理形态则发生了变化。坡积型砂矿的铌钽铁矿常与石英、长石等矿物连生,其颗粒大小与原生的Nb-Ta伟晶岩中的铌钽铁矿一致;经河流冲积而形成的砂矿中,铌钽铁矿颗粒变小、轮廓变得圆滑,几乎无连生矿物,但矿体集中,常在河流的冲积扇中分布,易开采。     

Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca₅(PO₄)₃.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO₄·H₂O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic–anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce³⁺ ions oxidizing to CeO₂. Reaction product analysis shows the formation of CO₂, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M_4,5 and C-K absorption edges on reacted CePO₄·H₂O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO₄·H₂O and O₂ but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π^* resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ^* region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent with aromatic-ring cleavage and polymerization. These results further substantiate that the presence of catechol, O₂ (aq) causes both the oxidation of structural Ce³⁺ and the transformation of catechol to more complex organic molecules. Scanning Transmission X-Ray Microscopy measurements at the C K and Ce M_4,5 edges indicate three dominant organic species, varying in complexity and association with the inorganic phase. Untransformed catechol is loosely associated with CeO₂, whereas more complex organic molecules that exhibit lower aromaticity and stronger CO π^* resonances of carboxyl-C and carbonyl-C groups are only found in association with the grains. These results further serve as basis to postulate that, in the presence of O₂, CeO₂ can mediate the oxidative polymerization of catechol to form higher molecular weight polymers. The present work provides evidence for a pathway of biologically-induced, non-enzymatic oxidation of cerium and formation of small CeO₂ particles at room temperature. These findings may have implications for carbon cycling in natural and cerium-contaminated soils and aqueous environments.     

Carbon isotope fractionation in phospholipid fatty acid biomarkers of bacteria and fungi native to an acid mine drainage lake

This study identifies isotope signatures associated with autotrophic and heterotrophic microbial communities that may provide a means to determine carbon cycling relationships in situ for acid mine drainage (AMD) sites. Stable carbon isotope ratios (δ¹³C) of carbon sources, bulk cells, and membrane phospholipids (PLFA) were measured for autotrophic and heterotrophic microbial enrichment cultures from a mine tailings impoundment in northern Ontario, Canada, and for pure strains of the sulfur oxidizing bacteria Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans. The autotrophic enrichments had indistinguishable PLFA distributions from the pure cultures, and the PLFA cyc-C_19:0 was determined to be a unique biomarker in this system for these sulfur oxidizing bacteria. The PLFA distributions produced by the heterotrophic enrichments were distinct from the autotrophic distributions and the C_18:2 PLFA was identified as a biomarker for these heterotrophic enrichments. Genetic analysis (16S, 18S rRNA) of the heterotrophic cultures indicated that these communities were primarily composed of Acremonium fungi.Stable carbon isotope analysis revealed that bulk cellular material in all autotrophic cultures was depleted in δ¹³C by 5.6–10.9‰ relative to their atmospheric CO₂ derived carbon source, suggesting that inorganic carbon fixation in these cultures is carbon limited. Individual PLFA from these autotrophs were further depleted by 8.2–14.6‰ compared to the bulk cell δ¹³C, which are among the largest biosynthetic isotope fractionation factors between bulk cell and PLFA reported in the literature. In contrast, the heterotrophic bulk cells were not significantly fractionated in δ¹³C relative to their carbon source and heterotrophic PLFA ranged from 3‰ enriched to 4‰ depleted relative to the isotopic composition of their total biomass. These distinct PLFA biomarkers and isotopic fractionations associated with autotrophic and heterotrophic activity in this laboratory study provide potential biomarkers for delineating autotrophic and heterotrophic carbon cycling in AMD environments.     

Characteristics of carbonaceous particles in Beijing during winter and summer 2003

Campaigns were conducted to measure Organic Carbon (OC) and Elemental Carbon (EC) in PM2.5 during winter and summer 2003 in Beijing. Modest differences of PM2.5 and PM10 mean concentrations were observed between the winter and summer campaigns. The mean PM2.5/PM10 ratio in both seasons was around 60%, indicating PM2.5 contributed significantly to PM10. The mean concentrations of OC and EC in PM2.5 were 11.2±7.5 and 6.0±5.0μg m-3 for the winter campaign, and 9.4±2.1 and 4.3±3.0 μg m-3 for the summer campaign, respectively. Diurnal concentrations of OC and EC in PM2.5 were found high at night and low during the daytime in winter, and characterized by an obvious minimum in the summer afternoon. The mean OC/EC ratio was 1.87±0.09 for winter and Z39±0.49 for summer. The higher OC/EC ratio in summer indicates some formation of Secondary Organic Carbon (SOC). The estimated SOC was 2.8 μg m-3 for winter and 4.2μg m-3 for summer.