An enzyme-linked immunosorbent assay for the determination of dioxins in contaminated sediment and soil samples

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.     

Electrolytic debromination of PBDEs in DE-83 technical decabromodiphenyl ether

Electrochemical debromination of the commercial decabromodiphenyl ether flame retardant DE-83 in partly aqueous tetrahydrofuran (THF) solution gave lower brominated congeners by sequential loss of bromine atoms. Hydrodebromination was most facile for the most heavily brominated congeners. It involves initial electron transfer and proton transfer from water, rather than hydrogen atom abstraction from THF, as shown by experiments with deuterated water. The product distribution from electrolysis involves preferential loss of bromine meta- and para- to the ether linkage, comparable with the products of metabolism of BDE-209 in various organisms. Significantly, the environmentally relevant congeners BDE-47, BDE-99, and BDE-154 were not major products of debromination of BDE-209 by the electron transfer mechanism.     

Structure characterization and thermal stabilities of the isomers of the brominated flame retardant 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane

1,2-Dibromo-4-(1,2-dibromoethyl)cyclohexane (TBECH) is used primarily as an additive flame retardant. 1H NMR spectroscopy and an X-ray structure determination have revealed that a technical mixture consists largely of two (of the four possible) diastereomers, rac-(1R,2R)-1,2-dibromo-(4S)-4-((1S)-1,2-dibromoethyl)cyclohexane (alpha-TBECH) and rac-(1R,2R)-1,2-dibromo-(4S)-4-((1R)-1,2-dibromoethyl)cyclohexane (beta-TBECH), in a mole ratio of approximately 1:1. The two other possible isomers, gamma- and delta-TBECH, were not detected in a technical mixture. The TBECH isomers are thermally sensitive and can easily interconvert at temperatures of 125 degrees C. A thermal equilibrium mixture of alpha-, beta-, gamma- and delta-TBECH consists of approximately 33%, 33%, 17% and 17% of these isomers, respectively. Separation of all four TBECH diastereomers, with minimal thermal interconversion of the isomers, was achieved by careful selection of GC-capillary column length and injector temperature. Although technical TBECH does not contain the gamma- and delta-isomers, they may still be relevant environmental contaminants since manufacturing processes utilize thermal processes which may induce their formation.     

Mixing-controlled biodegradation in a toluene plume--results from two-dimensional laboratory experiments

Various abiotic and biotic processes such as sorption, dilution, and degradation are known to affect the fate of organic contaminants, such as petroleum hydrocarbons in saturated porous media. Reactive transport modeling of such plumes indicates that the biodegradation of organic pollutants is, in many cases, controlled by mixing and therefore occurs locally at the plume's fringes, where electron donors and electron-acceptors mix. Herein, we aim to test whether this hypothesis can be verified by experimental results obtained from aerobic and anaerobic degradation experiments in two-dimensional sediment microcosms. Toluene was selected as a model compound for oxidizable contaminants. The two-dimensional microcosm was filled with quartz sand and operated under controlled flow conditions simulating a contaminant plume in otherwise uncontaminated groundwater. Aerobic degradation of toluene by Pseudomonas putida mt-2 reduced a continuous 8.7 mg L(-1) toluene concentration by 35% over a transport distance of 78 cm in 15.5 h. In comparison, under similar conditions Aromatoleum aromaticum strain EbN1 degraded 98% of the toluene infiltrated using nitrate (68.5+/-6.2 mg L(-1)) as electron acceptor. A major part of the biodegradation activity was located at the plume fringes and the slope of the electron-acceptor gradient was steeper during periods of active biodegradation. The distribution of toluene and the significant overlap of nitrate at the plume's fringe indicate that biokinetic and/or microscale transport processes may constitute additional limiting factors. Experimental data is corroborated with results from a reactive transport model using double Monod kinetics. The outcome of the study shows that in order to simulate degradation in contaminant plumes, detailed data sets are required to test the applicability of models. These will have to deal with the incorporation of existing parameters coding for substrate conversion kinetics and microbial growth.     

Effect of long-term changes in soil chemistry induced by road salt applications on N-transformations in roadside soils

Of several impacts of road salting on roadside soils, the potential disruption of the nitrogen cycle has been largely ignored. Therefore the fates of low-level ammonium-N and nitrate-N inputs to roadside soils impacted by salting over an extended period (decades) in the field have been studied. The use of road salts disrupts the proportional contributions of nitrate-N and ammonium-N to the mineral inorganic fraction of roadside soils. It is highly probable that the degree of salt exposure of the soil, in the longer term, controls the rates of key microbial N transformation processes, primarily by increasing soil pH. Additional influxes of ammonium-N to salt-impacted soils are rapidly nitrified therefore and, thereafter, increased leaching of nitrate-N to the local waterways occurs, which has particular relevance to the Water Framework Directive. The results reported are important when assessing the fate of inputs of ammonia to soils from atmospheric pollution.     

A design tool for planning emulsified oil‐injection systems

Emulsified oils have been used to stimulate anaerobic bioremediation at hundreds of sites contaminated with chlorinated solvents, perchlorate, heavy metals, and nitrate. A simple spreadsheet‐based tool has been developed to assist in the design of injection‐only systems for distributing emulsified oils in barriers and area treatments. This tool allows users to quickly compare the relative costs and performance of different injection alternatives and identify a design that is best suited to site‐specific conditions. Contact efficiency is estimated using results of prior numerical model simulations and dimensionless scaling factors that relate the volume of oil and water injected to treatment‐zone dimensions. Sensitivity analysis results indicate that maximum oil retention is one of the most important factors controlling system performance and cost. © 2008 Wiley Periodicals, Inc.     

Attitudes and Perceptions about Ecological Resources and Hazards of People Living Aroung the Savannah River Site

Although considerable attention is devoted to environmental monitoring and assessment with respect to both pollutants and the status of particular plant or animal populations, less attention is devoted to assessing people's attitudes about the relative importance of ecological resources. In this paper we examine the attitudes and perceptions about ecological resources of people living around the Department of Energy's Savannah River Site (SRS), in South Carolina. Our overall hypothesis is that people who are directly affected by the possible outcomes and consequences of a particular hazard (i.e., those people employed at SRS) will undervalue the risks and overvalue the potential benefits from future land uses that favor continued site activity, compared to people who live near but are not employed at SRS. We interviewed 286 people attending the Aiken Trials horse show on 14 March 1997. There were few gender differences, although men hunted and fished more than women, women ranked three environmental concerns as more severe than did men, and women were more concerned about the effect of SRS on property values. Maintenance of SRS as a National Environmental Research Park ranked first as a future land use; nuclear production ranked second, followed by hunting and hiking. Only residential development ranked very low as a future land use. There were many differences as a function of employment history at SRS: 1) people who work at SRS think that the federal government should spend funds to clean up all nuclear facilities, and they think less money should be spent on other environmental problems than did non-employees, 2) people who work at SRS ranked continued current uses of SRS higher than did people who never worked at SRS, and 3) people who work at SRS are less concerned about the storage of nuclear material or accidents at the site than are people who never worked at the site.     

Anti-sense expression of putrescine N-methyltransferase confirms defensive role of nicotine in Nicotiana sylvestris against Manduca sexta

Summary. Several lines of evidence support the defensive function of nicotine production in the Nicotiana genus against a range of herbivores, but the evidence is largely correlative. To suppress nicotine production in planta and to test its defensive function, we expressed DNA of putrescine N-methyl transferase in an anti-sense orientation (AS-PMT) in N. sylvestris and fed leaf material from two lines of transformed and wild type plants to Manduca sexta larvae. Larvae consumed more leaf area and gained more mass on the foliage of plants with low PMT expression and low nicotine levels as compared to plants with high PMT expression and high nicotine levels and wild type plants. Overall, larval consumption and performance were negatively correlated with constitutive nicotine levels. We conclude that nicotine decreases the palatability of N. sylvestris leaves to the nicotine-resistant M. sexta larvae.     

Paternity and paternal care in the polygynandrous Smith's longspur

In species where females copulate with more than one male during a single breeding attempt, males risk investing in offspring that are not their own. In the polygynandrous Smith's longspur (Calcarius pictus), females copulate sequentially with one to three males for each clutch of eggs and most of these males later assist in feeding the young. Using multilocus DNA profiling, we determined that there was mixed paternity in >75% of broods (n=31) but that few offspring (<1% of 114 nestlings) were sired by males outside the polygynandrous group. Male feeding rate increased significantly with the number of young sired, with males siring four nestlings feeding the brood at double the frequency of males siring only a single nestling. However, male Smith's longspurs appear to show a graded adjustment of paternal care in response to paternity only when other males are available to compensate for reduced care: feeding rate did not vary in relation to paternity when only one male provisioned young at the nest. There was no evidence that males could recognise their own offspring within a brood and feed them preferentially. The number of offspring sired by each male was significantly correlated with the number of days spent copulating with the attending female: on average, a male sired one offspring for every 2 days of copulatory access. If males use their access to females to estimate paternity (and thereby decide on their subsequent level of parental investment), a positive relationship is expected between the amount of female access and the subsequent feeding rate to the nestlings. Nonetheless, male feeding effort was only weakly correlated with female access and more study is needed to determine how males estimate their paternity in a brood. Received: 1 June 1997 / Accepted after revision: 1 April 1998