Biogeochemical processes in ethanol stimulated uranium-contaminated subsurface sediments

A laboratory incubation experiment was conducted with uranium-contaminated subsurface sediment to assess the geochemical and microbial community response to ethanol amendment. A classical sequence of terminal electron-accepting processes (TEAPs) was observed in ethanol-amended slurries, with NO3- reduction, Fe(III) reduction, SO4(2-) reduction, and CH4 production proceeding in sequence until all of the added 13C-ethanol (9 mM) was consumed. Approximately 60% of the U(VI) content of the sediment was reduced during the period of Fe(III) reduction. No additional U(VI) reduction took place during the sulfate-reducing and methanogenic phases of the experiment Only gradual reduction of NO3-, and no reduction of U(VI), took place in ethanol-free slurries. Stimulation of additional Fe(III) or SO4(2-) reduction in the ethanol-amended slurries failed to promote further U(VI) reduction. Reverse transcribed 16S rRNA clone libraries revealed major increases in the abundance of organisms related to Dechloromonas, Geobacter, and Herbaspirillum in the ethanol-amended slurries. Phospholipid fatty acids (PLFAs) indicative of Geobacter showed a distinct increase in the amended slurries, and analysis of PLFA 13C/12C ratios confirmed the incorporation of ethanol into these PLFAs. A increase in the abundance of 13C-labeled PLFAs indicative of Desulfobacter, Desulfotomaculum, and Desulfovibrio took place during the brief period of sulfate reduction that followed the Fe(III) reduction phase. Our results show that major redox processes in ethanol-amended sediments can be reliably interpreted in terms of standard conceptual models of TEAPs in sediments. However, the redox speciation of uranium is complex and cannot be explained based on simplified thermodynamic considerations.     

Spatial and seasonal trends in biogenic secondary organic aerosol tracers and water-soluble organic carbon in the southeastern United States

Twenty-four hour integrated filter samples of fine particulate matter (PM2.5) were collected from May 2004 to April 2005 at one rural site and three urban sites located in the southeastern United States. Filters were extracted and analyzed for both biogenic secondary organic aerosol (SOA) tracers via gas chromatography-mass spectrometry (GC-MS), and water-soluble organic carbon (WSOC) concentrations. The tracers reported in this study include isoprene-derived 2-methylthreitol and 2-methylerythritol, as well as pinene-derived cis-pinonic acid. The mean ambient concentrations ranged from 21.7 to 94.3 ng/m3, 5.31 to 17.9 ng/m3, and 1.87 to 3.18 microgC/m3 for 2-methyltetrols (sum of 2-methylerythritol and 2-methylthreitol), cispinonic acid and WSOC, respectively. Distinct spatial distributions were observed for all tracers with the highest concentration at the rural site and the lowest level at a coastal site. Although 2-methyltetrols were small fractions of WSOC, varying from 0.35% at an urban site to highest fractions of 1.09% at the rural site, WSOC exhibited significant correlation with 2-methyltetrols during summer, suggesting isoprene SOA makes an important contribution to WSOC. 2-Methyltetrols had the highest concentrations during the summer,when high temperature, intense solar radiation, and high ozone level occurred. However, no obvious seasonal variation was found for cispinonic acid. Between inland sites WSOC was more spatially homogeneous than the 2-methyltetrols, suggesting that WSOC was produced from a variety of mechanisms.     

Proxies and measurement techniques for mineral dust in Antarctic ice cores

To improve quantitative interpretation of ice core aeolian dust records, a systematic methodological comparison was made. This involved methods for water-insoluble particle counting (Coulter counter and laser-sensing particle detector), soluble ion analysis (ion chromatography and continuous flow analysis), elemental analysis (inductively coupled plasma mass spectroscopy at pH 1 and after full acid digestion), and water-insoluble elemental analysis (proton induced X-ray emission). Antarctic ice core samples covering the last deglaciation from the EPICA Dome C (EDC) and the EPICA Dronning Maud Land (EDML) cores were used. All methods correlate very well among each other, but the ratios of glacial age to Holocene concentrations, which are typically a factor approximately 100, differ between the methods by up to a factor of 2 with insoluble particles showing the largest variability. The recovery of ICP-MS measurements depends on the digestion method and is differentfor different elements and during different climatic periods. EDC and EDML samples have similar dust composition, which suggests a common dust source or a common mixture of sources for the two sites. The analyzed samples further reveal a change of dust composition during the last deglaciation.     

On the application of fourier transform infrared spectroscopy to the elucidation of specific interactions in miscible polyester-poly(vinyl chloride) blends

FT-IR spectroscopic studies have been performed in an attempt to elucidate the nature of the specific interactions occurring in miscible poly(?-caprolactone) (PCL)-poly (vinyl chloride) (PVC) blends. Studies of low molecular weight analogues, polymer/solvent mixtures and blends of PCL and α-deuterated PVC are presented. The results strongly suggest that a hydrogen bonding type of interaction between the carbonyl bond of PCL and the α-hydrogen of PVC exists in compatible PCL-PVC blends.     

Neutron reflectivity study of the competitive adsorption of β-casein and water—soluble surfactant at the planar air-water interface

Application of the technique of specular neutron reflection to the study of adsorbed layer structure is illustrated for the case of β-casein at the air—water interface in the presence and absence of nonionic water—soluble surfactant C₁₂E₆. Guinier analysis of reflectivity data for a 5 × 10⁻³ wt% solution of pure β-casein in air-contrast-matched water (8 vol% D₂O) at pH 7.0 gives a time-independent adsorbed amount of 2.05 ± 0.10 mg/m2 and an adsorbed layer thickness of 1.65 ± 0.07 nm; these values are found to increase quite substantially as the pH is reduced towards the protein's isoelectric point. In the presence of surfactant the loss of reflectivity is a direct measure of protein displacement from the interface because the hydrogenated surfactant is almost contrast matched to the aqueous phase. At a C₁₂E₆ concentration in the range 2–2.5 × 10⁻⁴ wt% (surfactant: protein molar ratio, R ≈ 2.2), there is roughly half the protein lost from the interface but little change in adsorbed layer thickness as inferred from the slopes of the Guinier plots. Protein is effectively completely removed from the surface for R 10. These results are in semi-quantitative agreement with complementary competitive adsorption data for β-casein in soya oil-in-water emulsions.     

Mixed finite elements based upon marguerre theory for the study of geometrically nonlinear behavior of thin shells

Simple triangular and quadrangular finite elements based on Marguerre's theory are proposed and are shown to greatly improve the solution over plane shell elements for a small additional computation cost.Several features of the developments are worth noting, namely: The presentation of a dual approach for the derivation of Marguerre's theory of shallow shells with moderate rotations, based on Fraeijs de Veubeke's variational principle, with a precise statement of hypotheses and applicability; the choice of hybrid connectors for solving the compatibility problem generated by Kirchhoff's hypothesis; a treatment of pressure loading, body forces and inextensional bending modes which employs a ‘static approach’ for the membrane; and discussion about the performance of some algorithms used to solve elastic stability problems. Numerical studies indicate that accurate results may be obtained by the approach advocated.     

Effects of dilution on fine particle mass and partitioning of semivolatile organics in diesel exhaust and wood smoke

Experiments were conducted to examine the effects of dilution on fine particle mass emissions from a diesel engine and wood stove. Filter measurements were made simultaneously using three dilution sampling systems operating at dilution ratios ranging from 20:1 to 510:1. Denuders and backup filters were used to quantify organic sampling artifacts. For the diesel engine operating at low load and wood combustion, large decreases in fine particle mass emissions were observed with increases in dilution. For example, the PM2.5 mass emission rate from a diesel engine operating at low load decreased by 50% when the dilution ratio was increased from 20:1 to 350:1. Measurements of organic and elemental carbon indicate that the changes in fine particle mass with dilution are caused by changes in partitioning of semivolatile organic compounds. At low levels of dilution semivolatile species largely occur in the particle phase, but increasing dilution reduces the concentration of semivolatile species, shifting this material to the gas phase in order to maintain phase equilibrium. Emissions of elemental carbon do not vary with dilution. Organic sampling artifacts are shown to vary with dilution because of the combination of changes in partitioning coupled with adsorption of gas-phase organics by quartz filters. The fine particle mass emissions from the diesel engine operating at medium load did not vary with dilution because of the lower emissions of semivolatile material and higher emissions of elemental carbon. To measure partitioning of semivolatile materials under atmospheric conditions, partitioning theory indicates that dilution samplers need to be operated such that the diluted exhaust achieves atmospheric levels of dilution. Too little dilution can potentially overestimate the fine particle mass emissions, and too much dilution (with clean air) can underestimate them.     

Hurricane Katrina's impact on New Orleans soils treated with low Lead Mississippi River alluvium

Before Hurricane Katrina flooded 80% of New Orleans, 25 heavily Pb contaminated properties were treated with 15 cm of low Pb Mississippi River alluvium from the Bonnet Carré Spillway (BCS). Four phases of soil collection on the properties included pretreatment (phase 1) median surface soil Pb was 1051 mg/kg (range 5-19 627); after BCS cover (phase 2) the median soil Pb decreased to 6.3 mg/ kg (range 3-18); just before Katrina, a soil collection was partially completed (phase 3); and finally, a post-Katrina collection (phase 4) on all 25 properties. Twenty-three properties were flooded. The objective was to compare Pb changes of phases 2 and 3 pre-Katrina with the post-Katrina (phase 4) soil collection. The post-Katrina soil Pb (phase 4) (median of 16.3, range 5.5-1,155) increased significantly (P-value = 3.7 x 10(-10)) from the clean soil, phase 2 results. Matched soil samples collected in phase 3 before flooding and phase 4 after flooding showed that on initially vacant lots the amounts of Pb were not significantly different (P-value = 0.97); but, on properties with homes, the changes were significant (P-value = 0.03). After catastrophic flooding, the clean soil remained relatively undisturbed; the soil Pb changes were small with increases of median Pb of 12 and 6 mg/kg for vacant lots and properties with homes, respectively. Processes accounting for Pb increases include Pb-based paint abatement on one property, home construction on the vacant lots, and resuspension and deposition of Pb dust. As part of the post-Katrina recovery, the combined benefits of Pb-safe paint abatement or renovation and clean soil cover should outweigh the estimated annual cost of Pb poisoning of children returning to New Orleans.     

Competitive adsorption of α-lactalbumin in the molten globule state

The molten globule state of α-lactalbumin is a partially denatured form with native-like secondary structure and disordered tertiary structure. Using circular dichroism measurements, it was demonstrated that the molten globule state was produced by decreasing the pH to 2.0 at 25°C or by removing bound Ca²⁺ by treatment with ethylenediamine—tetraacetic acid (EDTA) at pH 7.5 and 40°C. Tension measurements showed that α-lactalbumin in the molten globule state is more easily unfolded at liquid interfaces than is the native protein. Results of competitive adsorption experiments involving α-lactalbumin and β-lactoglobulin at the oil droplet surface in emulsions are consistent with preferential adsorption of α-lactalbumin during emulsification when it is in the molten globule state. In contrast to the difficulty of exchange between α-lactalbumin and β-lactoglobulin at the oil-water interface in emulsions at 25°C, it has been found that the two whey proteins are able partially to displace one another from the oil—water interface at 40°C. While native α-lactalbumin was found to be readily displaced from the oil—water interface by β-lactoglobulin at 40°C, it was found that α-lactalbumin in the molten globule state in the presence of EDTA at 40°C had itself the capacity for displacing β-lactoglobulin from the interface.     

Possible implications of milk pasteurization on the manufacture and sensory quality of ripened cheese

Cheese made from raw milk represents an important proportion of the traditional cheeses, particularly in South European countries. Besides destruction of pathogenic bacteria, the most significant changes in milk relevant to cheesemaking, which are induced by pasteurization are:

• a partial elimination of the milk microorganisms which may grow in cheese during ripening,

• a partial or total activation or inhibition of the plasmin/plasminogen complex, cathepsin D, lipoprotein lipase and alkaline phosphatase. Enzymes from psychrotrophic bacteria, acid phosphatase and xanthine oxidase, which may be active during ripening, withstand pasteurization.,

• a slight (7%) denaturation of serum proteins and little or no modification of the cheesemaking properties (coagulation, acidification by lactic acid bacteria).

From experimental work carried out on several cheese varieties, comparing pasteurized or microfiltered milk and raw milk cheeses, it was found that facultatively heterofermentative lactobacilli, Micrococcaceae, enterococci, and propionibacteria in Swiss-type cheese, are found at higher levels in raw milk cheese. The main biochemical modification of cheese during ripening concerns the nature and extent of proteolysis. Although there is no clear trend in the breakdown of _s1- and β-caseins, milk pasteurization leads to a significant decrease of the amount of small peptides and free amino acids and to different HPLC profiles. Experiments carried out with sensory analysis show that, in all cases, pasteurized or microfiltered milk cheeses have received lower flavour intensity scores than raw milk cheeses. From this review, it is concluded that the indigenous milk microflora, with its diversity of species and strains, appears to be mainly responsible of the specific sensory properties of raw milk cheeses.