Simplified determination of lipophilic metabolites of nonylphenol ethoxylates: method development and application in aqueous samples from Buenos Aires, Argentina

In the present work we have developed an analytical methodology for the determination of nonylphenol (NP) and nonylphenol mono- and di-ethoxylates (NP1EO and NP2EO) in water samples. The applicability of this methodology was proved by means of the analysis of environmentally relevant aqueous samples from Buenos Aires. This constitutes a starting point for a rigorous assessment of the incidence of NPnEO surfactants in Argentina, as only very few, qualitative or semi-quantitative data on the occurrence of these compounds in local systems were available up to this time. Enrichment of the analytes was carried out by solid-phase extraction on a C-18 sorbent, followed by elution with ethyl acetate. Normal-phase high performance liquid chromatography on an amino-silica column and fluorescence detection at excitation-emission wavelengths of 230-300 nm were employed for separation and quantification of the analytes. Confirmation of peak assignment in selected real samples was performed by off-line coupling HPLC with GC-MS analysis. A non-polar GC capillary column was used, and a characteristic peak pattern was obtained for the alkyl chain isomers of each ethoxylated homologue and NP. GC-MS analyses yielded in all cases purity levels higher than 80% for the HPLC collected fractions. The elevated concentrations found for the estrogenic metabolites of NPnEO are in accordance with an unrestricted use of this class of non-ionic surfactants in the country.     

A Sensitivity Analysis of an Integrated Modelling Approach to Assess the Risk of Wind-borne Spread of Foot-and-mouth Disease Virus from Infected Premises

The sensitivity of an integrated model to assess the potential for wind-borne spread of foot-and-mouth disease (FMD) to variations in key parameters controlling different physical and biological processes was evaluated. The estimated number of farms at risk is sensitive to the virus strain used and the accompanying effective contact rate. The C Noville strain increased the estimated number of exposed farms ranked as high and medium risk of being infected by a factor of 5, compared to the baseline, based on the O UKG 2001 strain. The inclusion of a model for biological ageing of the virus can also have a significant effect on the concentration patterns arising from transport and dispersion of the virus. Its inclusion has the practical advantage of markedly reducing the time required for the calculations. The estimated number of farms affected by exposure to high and medium virus concentrations is not grossly sensitive to attenuation caused by temperature or relative humidity effects. Changes in susceptibility to infection, as determined by the parameter θ in the exposure-risk model, does not change the configuration of the virus plumes, but it does change the distribution of farms at risk by risk category. These findings suggest that a good understanding of characteristics (excretion rates from infected animals, susceptibility of different species to infection, virus survival, etc.) of the virus strain involved in an FMD outbreak is necessary to provide a reliable assessment of the risk of wind-borne spread. In the event of an incursion of FMD, provision for laboratory studies on the virus will be an essential component of the disease response and should be factored into contingency plans.

Assessing benthic community condition in Chesapeake Bay: does the use of different benthic indices matter?

Federal and state environmental agencies conduct several programs to characterize the environmental condition of Chesapeake Bay. These programs use different benthic indices and survey designs, and have produced assessments that differ in the estimate of the extent of benthic community degradation in Chesapeake Bay. Provided that the survey designs are unbiased, differences may exist in the ability of these indices to identify environmental degradation. In this study we compared the results of three indices calculated on the same data, and the assessments of two programs: the Chesapeake Bay Program and the Mid-Atlantic Integrated Assessment (MAIA). We examined the level of agreement of index results using site-based measures of agreement, evaluated sampling designs and statistical estimation methods, and tested for significant differences in assessments. Comparison of ratings of individual sites was done within separate categories of water and sediment quality to identify which indices summarize best pollution problems in Chesapeake Bay. The use of different benthic indices by these programs produced assessments that differed significantly in the estimate of degradation. A larger fraction of poor sites was classified as good by the Environmental Monitoring and Assessment Program’s Virginian Province and MAIA benthic indices compared to the Chesapeake Bay benthic index of biotic integrity, although overall classification efficiencies were similar for all indices. Differences in survey design also contributed to differences in assessments. The relative difference between the indices remained the same when they were applied to an independent dataset, suggesting that the indices can be calibrated to produce consistent results.     

The relative influence of nutrients and habitat on stream metabolism in agricultural streams

Stream metabolism was measured in 33 streams across a gradient of nutrient concentrations in four agricultural areas of the USA to determine the relative influence of nutrient concentrations and habitat on primary production (GPP) and respiration (CR-24). In conjunction with the stream metabolism estimates, water quality and algal biomass samples were collected, as was an assessment of habitat in the sampling reach. When data for all study areas were combined, there were no statistically significant relations between gross primary production or community respiration and any of the independent variables. However, significant regression models were developed for three study areas for GPP (r ² = 0.79–0.91) and CR-24 (r ² = 0.76–0.77). Various forms of nutrients (total phosphorus and area-weighted total nitrogen loading) were significant for predicting GPP in two study areas, with habitat variables important in seven significant models. Important physical variables included light availability, precipitation, basin area, and in-stream habitat cover. Both benthic and seston chlorophyll were not found to be important explanatory variables in any of the models; however, benthic ash-free dry weight was important in two models for GPP.     

Techniques for the stabilization and assessment of treated copper-, chromium-, and arsenic-contaminated soil

Remediation mainly based on excavation and burial of the contaminated soil is impractical with regard to the large numbers of sites identified as being in need of remediation. Therefore, alternative methods are needed for brownfield remediation. This study was conducted to assess a chemical stabilization procedure of CCA-contaminated soil using iron (Fe)-containing blaster sand (BS) or oxygen-scarfing granulate (OSG). The stabilization technique was assessed with regard to the feasibility of mixing ameliorants at an industrial scale and the efficiency of the stabilization under different redox conditions. The stability was investigated under natural conditions in 1-m3 lysimeters in a field experiment, and the effect of redox conditions was assessed in a laboratory experiment (10 L). The treatments with high additions of ameliorant (8% and 17%) were more successful in both the laboratory and field experiments, even though there was enough Fe on a stochiometric basis even at the lowest addition rates (0.1% and 1%). The particle size of the Fe and the mixing influenced the stabilization efficiency. The development of anaerobic conditions, simulated by water saturation, increases the fraction of arsenic (AsIII) and, consequently, As mobility. The use of high concentrations of OSG under aerobic conditions increased the concentrations of nickel (Ni) and copper (Cu) in the pore water. However, under anaerobic conditions, it decreased the As leaching compared with the untreated soil, and Ni and Cu leaching was not critical. The final destination of the treated soil should govern the amendment choice, that is, an OSG concentration of approximately 10% may be suitable if the soil is to be landfilled under anaerobic conditions. Alternatively, the soil mixed with 1% BS could be kept under aerobic conditions in a landfill cover or in situ at a brownfield site. In addition, the treatment with BS appeared to produce better effects in the long term than treatment with OSG.     

Monobromo and higher brominated congeners of the marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1)

The marine halogenated natural product 2,3,3',4,4',5,5'-heptachloro-1'-methyl-1,2'-bipyrrole (Q1) is widely distributed in the environment. In this study, we screened samples which have previously been found to contain remarkably high residues of Q1 (blubber of marine mammals from Australia, samples from Antarctica, human milk from the Faroe Island) for the additional presence of mixed chlorinated and brominated congeners. Using GC/ECNI-MS, all samples tested were positive and many contained four out of five possible bromohexachloro congeners (BrCl6-MBPs), five out of 14 possible dibromopentachloro congeners (Br2Cl5-MBPs), five of 21 possible tribromotetrachloro-congeners (Br3Cl4-MBPs), as well as several higher brominated congeners. About 20 heptahalo congeners of Q1 are described for the first time in the scientific literature. Isomers eluted within about one minute, respectively. Hence it is possible, that the peak clusters identified may be composed of more, co-eluting congeners. Similarities in the GC/ECNI-MS mass spectra with polychlorinated biphenyls (PCBs) were addressed. We also suggest an acronym system similar to that in use for polychlorinated biphenyls that may simplify the use of this substance class in scientific papers. In the samples from Australia, BrCl6-MBPs and Br2Cl5-MBPs amounted for 7-27.5% and 0.4-4.2% of Q1, respectively whereas Br3Cl4-MBPs and higher brominated MBPs were found in the range of <1% of Q1 or less.     

Diel cycles of arsenic speciation due to photooxidation in acid mine drainage from the Iberian Pyrite Belt (Sw Spain)

Twenty four hours diel cycles of arsenic speciation in Acid Mine Drainage (AMD) due to photooxidation have been reported for the first time. AMD samples were taken during 48 h (31st March and 1st April, 2005) at 6 h intervals from the effluent of a massive abandoned polymetallic sulphide mine of the Iberian Pyrite Belt (Sw Spain). Samples were preserved in situ using cationic exchange prior to analysis by coupled high performance liquid chromatography, hydride generation and atomic fluorescence spectrometry (HPLC-HG-AFS) for arsenic speciation. The results indicated the presence of inorganic arsenic species with daily means of 262mugl(-1) for As(V) and 107 microg l(-1) for As(III). No marked diel trend was observed for As(V). However, a marked diel trend was observed for As(III) in the two studied days, with maximum concentrations during nighttime (141-143 microg l(-1)) and minimum concentrations at daytime (72-77 microg l(-1)). This difference in concentration during daytime and nighttime is ca. 100%. A similar diel cycle was observed for iron. An explanation for the arsenic diel cycles observed is the light induced photooxidation of As(III) and the elimination of As(V) due to its adsorption onto Fe precipitates during the daytime. Furthermore, the diel changes in arsenic speciation emphasize the importance of designing suitable sampling strategies in AMD systems.     

Individual risk analysis of high-pressure natural gas pipelines

Transmission pipelines carrying natural gas are not typically within secure industrial sites, but are routed across land out of the ownership of the pipeline company. If the natural gas is accidentally released and ignited, the hazard distance associated with these pipelines to people and property is known to range from under 20 m for a smaller pipeline at lower pressure to up to over 300 m for a larger pipeline at higher pressure. Therefore, pipeline operators and regulators must address the associated public safety issues.This paper focuses on a method to explicitly calculate the individual risk of a transmission pipeline carrying natural gas. The method is based on reasonable accident scenarios for route planning related to the pipeline's proximity to the surrounding buildings. The minimum proximity distances between the pipeline and buildings are based on the rupture of the pipeline, with the distances chosen to correspond to a radiation level of approximately 32 kW/m². In the design criteria for steel pipelines for high-pressure gas transmission (IGE/TD/1), the minimum building proximity distances for rural areas are located between individual risk values of 10⁻⁵ and 10⁻⁶. Therefore, the risk from a natural gas transmission pipeline is low compared with risk at the building separated minimum distance from chemical industries.     

Carbon deposition in soil rhizosphere following amendments with compost and its soluble fractions, as evaluated by combined soil-plant rhizobox and reporter gene systems

We determined the organic carbon released by roots of maize plants (Zea mays L.) when grown in soils amended with compost and its soluble fractions. In rhizobox systems, soil and roots are separated from the soil of a lower compartment by a nylon membrane. Treatments are applied to the upper compartment, while in the lower compartment luminescent biosensors measure the bioavailable organic carbon released by roots (rhizodeposition). The rhizobox-plants systems were amended with a compost (COM), its water extract (TEA), the hydrophobic (HoDOM) and hydrophilic (HiDOM) fractions of the dissolved organic matter (DOM) extracted from the compost. After root development, the lower untreated compartments were sampled and sliced into thin layers. The bioavailable organic carbon in each layer was assessed with the lux-marked biosensor Pseudomonas fluorescens 10586 pUCD607, and compared with total organic carbon (TOC) analyses. The TOC values ranged between 8.4 and 9.6 g kg(-1) and did not show any significant differences between bulk and rhizosphere soil samples in any treatment. Conversely, the biosensor detected significant differences in available C compounds for rhizosphere soils amended with various organic materials. Concentrations of available organic compounds in the first 2 mm of soil rhizosphere were 1.69 (control), 1.09 (COM), 2.87 (HiDOM), 4.73 (HoDOM) and 2.14 (TEA)micromol Cg(-1) soil g(-1) roots. The applied rhizobox-biosensor integrated method was successful in detecting and quantifying effects of organic amendments on organic carbon released by maize plant roots. This approach may become important in assessing the carbon cycle in agricultural soils and soil-atmosphere compartments.