Pyrolysis of permethrin and formation of precursors of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) under non-oxidative conditions

This article reports the computational and experimental results of the thermal decomposition of permethrin, a potential source of dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF). We have performed a quantum chemical analysis by applying density functional theory to obtain the decomposition pathways of permethrin and the formation mechanism of dibenzofuran. We have conducted the pyrolysis experiments in a tubular reactor and identified the pyrolysis products to demonstrate the agreement between the experimental measurements and quantum chemical calculations. The initiation of the decomposition of permethrin involves principally the aromatisation of permethrin into 3-phenoxyphenylacetic acid, 2-methylphenyl ester (J) and concomitant loss of 2HCl. This rearrangement is followed by the rupture of the O–CH₂ linkage in J, with a rate constant derived from the quantum chemical results of 1 × 10¹⁵ exp(−68 kcal/mol/RT) s⁻¹ for temperatures between 700 and 1300 K. This is confirmed by finding that the rate constant for unimolecular rearrangement of permethrin into J is 1.2 × 10¹² exp(−53 kcal/mol/RT) s⁻¹ over the same range of temperatures and exceeds the direct fission rate constant at all temperatures up to 850 ± 120 °C as well as by the experimental detection of J prior to the detection of the initial products incorporating diphenyl ether, 1-methyl-3-phenoxybenzene, 3-phenoxybenzaldehyde and 1-chloromethyl-3-phenoxybenzene. As the temperature increases, we observe a rise in secondary products formed directly or indirectly (via phenol/phenoxy) including aromatics (naphthalene), biphenyls (biphenyl, 4-methyl-1,1′-biphenyl) and dibenzofuran (DF). In particular, we discover by means of quantum chemistry a direct route from 2-phenoxyphenoxy to naphthalene. We detect no polychlorinated dibenzo-p-dioxins and dibenzofurans. Unlike the case of oxidative pyrolysis [Tame, N.W., Dlugogorski, B.Z., Kennedy, E.M., 2007b. Formation of dioxins in fires of arsenic-free treated wood: Role of organic preservatives. Environ. Sci. Technol. 41, 6425–6432] where significant yields of both PCDD and PCDF were obtained, under non-oxidative conditions the thermal decomposition of permethrin does not form appreciable amounts of PCDD or PCDF and the presence of oxygen (and/or a sizable radical pool) appears necessary for the formation of dibenzo-p-dioxin itself or PCDD/F from phenol/phenoxy.     

Impact of water saturation level on arsenic and metal mobility in the Fe-amended soil

The impact of water saturation level (oxidizing-reducing environment) on As and metal solubility in chromium, copper, arsenic (CCA)-contaminated soil amended with Fe-containing materials was studied. The soil was mixed with 0.1 and 1 wt% of iron grit (Fe(0)) and 1, 7 and 15 wt% of oxygen scarfing granulate (OSG, a by-product of steel processing). Solubility of As and metals was evaluated by a batch leaching test and analysis of soil pore water. Soil saturation with water greatly increased As solubility in the untreated as well as in the Fe-amended soil. This was related to the reductive dissolution of Fe oxides and increased concentration of As(III) species. Fe amendments showed As reducing capacity under both oxic and anoxic conditions. The cytotoxicity of the soil pore water correlated with the concentration of As(III). The Fe-treatments as well as water saturation of soil were less significant for the solubility of Cu, Cr and Zn than for As. The batch leaching test used for waste characterization substantially underestimated As solubility that could occur under water-saturated (anaerobic) conditions. In the case of soil landfilling, other techniques than Fe-stabilization of As containing soil should be considered.     

Transport of fecal bacteria by boots and vehicle tires in a rural Alaskan community

People living without piped water and sewer can be at increased risk for diseases transmitted via the fecal-oral route. One rural Alaskan community that relies on hauling water into homes and sewage from homes was studied to determine the pathways of fecal contamination of drinking water and the human environment so that barriers can be established to protect health. Samples were tested for the fecal indicator, Escherichia coli, and the less specific indicator group, total coliforms. Shoes transported fecal contamination from outside to floor material inside buildings. Contamination in puddles on the road, in conjunction with contamination found on all-terrain vehicle (ATV) tires, supports vehicle traffic as a mechanism for transporting contamination from the dumpsite or other source areas to the rest of the community. The abundance of fecal bacteria transported around the community on shoes and ATV tires suggests that centralized measures for waste disposal as well as shoe removal in buildings could improve sanitation and health in the community.     

Development of a Quantitative Pasture Phosphorus Management Tool Using the SWAT Model1

Abstract: Assessment tools to evaluate phosphorus loss from agricultural lands allow conservation planners to evaluate the impact of management decisions on water quality. Available tools to predict phosphorus loss from agricultural fields are either: (1) qualitative indices with limited applicability to address offsite water quality standards, or (2) models which are prohibitively complex for application by most conservation planners. The purpose of this research was to develop a simple interface for a comprehensive hydrologic/water quality model to allow its usage by farmers and conservation planners. The Pasture Phosphorus Management (PPM) Calculator was developed to predict average annual phosphorus (P) losses from pastures under a variety of field conditions and management options. PPM Calculator is a vastly simplified interface for the Soil and Water Assessment Tool (SWAT) model that requires no knowledge of SWAT by the user. PPM Calculator was validated using 33 months of data on four pasture fields in northwestern Arkansas. This tool has been extensively applied in the Lake Eucha/Spavinaw Basin in northeastern Oklahoma and northwestern Arkansas. PPM Calculator allows conservation planners to take advantage of the predictive capacity of a comprehensive hydrologic water quality model typically reserved for use by hydrologists and engineers. This research demonstrates the applicability of existing water quality models in the development of user friendly P management tools.     

Assessing Landscape Condition Relative to Water Resources in the Western United States: A Strategic Approach

The Environmental Monitoring and Assessment Program (EMAP) is proposing an ambitious agenda to assess the status of streams and estuaries in a 12-State area of the western United States by the end of 2003. Additionally, EMAP is proposing to access landscape conditions as they relate to stream and estuary conditions across the west. The goal of this landscape project is to develop a landscape model that can be used to identify the relative risks of streams and estuaries to potential declines due to watershed-scale, landscape conditions across the west. To do so, requires an understanding of quantitative relationships between landscape composition and pattern metrics and parameters of stream and estuary conditions. This paper describes a strategic approach for evaluating the degree to which landscape composition and pattern influence stream and estuary condition, and the development and implementation of a spatially-distributed, landscape analysis approach.     

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.     

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.