Assessing inter-laboratory comparability and limits of determination for the analysis of cyclic volatile methyl siloxanes in whole Rainbow Trout (Oncorhynchus mykiss)

Cyclic volatile methyl siloxanes (cVMS) are high volume production chemicals used in a wide range of industrial and consumer products. Three cVMS compounds (D4, D5, and D6) have and are undergoing environmental risk evaluations in several countries and have been proposed for legal regulation in Canada. As interest in monitoring concentrations of these chemicals in the environment increase, there is a need to evaluate the analytical procedures for cVMS in biological matrices in order to assess the quality of data produced. The purpose of this study was to determine laboratory testing performance for measuring residues of D4, D5, and D6 in a standard set of fish homogenate samples and to estimate limits of determination for each substance. The samples sent to each laboratory consisted of homogenized whole body tissues of hatchery raised rainbow trout which were fed food fortified with D4, D5, and D6 (dosed) and trout that were fed standard food rations (control). The participants analyzed each sample using their analytical method of choice using their own standards and procedures for quantification and quality control. With a few exceptions, participating laboratories generated comparable results for D4, D5, and D6 in both the dosed and control samples having z-scores between 2 and −2. Method detection limits for the whole fish matrix were on average 2.4 ng g⁻¹ ww for D4, 2.3 ng g⁻¹ ww for D5, and 1.8 ng g⁻¹ ww for D6.     

An international survey of decabromodiphenyl ethane (deBDethane) and decabromodiphenyl ether (decaBDE) in sewage sludge samples

Decabromodiphenyl ethane (deBDethane) is an additive flame retardant marketed as a replacement for decabromodiphenyl ether (decaBDE). The structures of the two chemicals are similar, and hence deBDethane may also become an environmental contaminant of concern. Environmental data on deBDethane are scarce. Since sewage sludge is an early indicator of leakage of these chemicals into the environment, an international survey of deBDethane and decaBDE levels in sludge was conducted. Samples were collected from 42 WWTPs in 12 different countries and analyzed with GC/LRMS. DeBDethane was present in sludge from all countries and may therefore be a worldwide concern. The levels of deBDethane in sludge samples from the Ruhr area of Germany were the highest so far reported in the literature (216 ng g⁻¹ d.wt.). The [deBDethane]/[decaBDE] quotient for the whole data set ranged from 0.0018 to 0.83. High ratios were found in and around Germany where deBDethane imports are known to have been high and substitution of decaBDE with deBDethane is likely to have occurred. Low ratios were found in the USA and the UK, countries that have traditionally been large users of decaBDE. An estimate of the flux of deBDEthane from the technosphere via WWTPs to the environment within the European Union gave 1.7 ± 0.34 mg annually per person. The corresponding value for decaBDE was 41 ± 22 mg annually per person.     

How Do River Nitrate Concentrations Respond to Changes in Land-use? A Modelling Case Study of Headwaters in the River Derwent Catchment,North Yorkshire,UK

A combined semi-distributed hydrological model (CASCADE/QUESTOR) is used to evaluate the steady-state that may be achieved after changes in land-use or management and to explore what additional factors need to be considered in representing catchment processes. Two rural headwater catchments of the River Derwent (North Yorkshire, UK) were studied where significant change in land-use occurred in the 1990s and the early 2000s. Much larger increases in mean nitrate concentration (55%) were observed in the catchment with significant groundwater influence (Pickering Beck) compared with the surface water-dominated catchment (13% increase). The increases in Pickering Beck were considerably greater than could be explained by the model in terms of land-use change. Consequently, the study serves to focus attention on the long-term increases in nitrate concentration reported in major UK aquifers and the ongoing and chronic impact this trend is likely to be having on surface water concentrations. For river environments, where groundwater is a source, such trends will mask the impact of measures proposed to reduce the risk of nitrate leaching from agricultural land. Model estimates of within-channel losses account for 15–40% of nitrate entering rivers.     

The relationships between awareness of consequences,environmental concern,and value orientations

Different people become engaged in environmental issues and perform proenvironmental behavior because they believe in and are concerned about adverse consequences of environmental problems for themselves (egoistic beliefs and concerns), others (social-altruistic beliefs and concerns), or the biosphere (biospheric beliefs and concerns). These different beliefs and concerns are assumed to derive from corresponding value orientations. Yet, distinguishing egoistic, social-altruistic, and biospheric value orientations has proved difficult in previous research. Based on a survey of 494 Swedish residents between 18 and 69 years old, the present study provides empirical support for that egoistic, social-altruistic, and biospheric environmental concerns are related to corresponding awareness-of-consequences beliefs, and that both the beliefs and environmental concerns are related to the three value types power, benevolence, and universalism.     

Mass balance of decabromodiphenyl ethane and decabromodiphenyl ether in a WWTP

The additive flame retardant decabromodiphenyl ethane (deBDethane) has been identified in the environment, but little is known about its environmental behaviour. It is structurally similar to decabromodiphenyl ether (decaBDE), making it conceivable that it may also become an environmental contaminant of concern. In this study a mass balance of deBDethane and decaBDE was undertaken in a modern WWTP in Stockholm serving 7.05x10(5) inhabitants. Flow proportional samples of plant influent and effluent as well as daily grab samples of digested sludge were collected during two 7-day periods. All samples were analyzed with GC/HRMS using isotope labelled internal standards. The mean mass flows of deBDethane and decaBDE to the WWTP were 6.0 g per day and 55 g per day, respectively. Of this, less than 1% of both BFRs left the WWTP via the effluent, while the bulk was sequestered into the digested sludge, where the mean concentrations of deBDethane and decaBDE were 81 and 800 ng g(-1)d.wt., respectively. It is concluded that the transfer efficiency of deBDethane from the technosphere to the environment via WWTPs is similar to that of decaBDE.     

Quality control for sampling of PCDD/PCDF emissions from open combustion sources

Both long duration (>6 h) and high temperature (up to 139 °C) sampling efforts were conducted using ambient air sampling methods to determine if either high volume throughput or higher than ambient air sampling temperatures resulted in loss of target polychlorinated dibenzodioxins/dibenzofurans (PCDDs/PCDFs) from a polyurethane foam (PUF) sorbent. Emissions from open burning of simulated military forward operating base waste were sampled using EPA Method TO-9A for 185 min duration using a filter/PUF/PUF in series combination. After a 54 m³ sample was collected, the sampler was removed from the combustion source and the second PUF was replaced with a fresh, clean PUF. An additional 6 h of ambient air sampling (171 m³) was conducted and the second PUF was analyzed to determine if the PCDD/PCDF transferred from the filter and the first PUF. Less than 4.4% of the initial PCDD/PCDF was lost to the second PUF. To assess the potential for blow off of PCDD/PCDF analytes during open air sampling, the mobility of spiked mono- to hepta-PCDD/PCDF standards across a PUF sorbent was evaluated from ambient air temperatures to 145 °C with total volumes between 600 L and 2400 L. Lower molecular weight compounds and higher flow amounts increased release of the spiked standards consistent with vapor pressure values. At 600 L total sampled volume, the release temperature for 1% of the tetra-CDD (the lowest chlorinated homologue with a toxic compound) was 87 °C; increasing the volume fourfold reduced this temperature to 73 °C.     

Polybrominated diphenyl ethers (PBDEs) and their methoxylated derivatives in pike from Swedish waters with emphasis on temporal trends, 1967-2000

Temporal trends of five tetra- to hexabromodiphenyl ethers [BDE47, BDE99, BDE100, BDE153 and BDE154) and two methoxy-tetraBDEs [6-methoxy-2,2',4,4'- tetraBDE (6-MeO-BDE47) and 2'-methoxy-2,3',4,5'- tetraBDE (2'-MeO-BDE68)] in pike from Lake Bolmen for the years 1967-2000, are presented. All BDE congeners show increasing trends up to the mid-1980s (Sigma5PBDE from 60 to 1600 pg/g wet weight in 1989, i.e. a more than 25-fold increase), and then decrease or level off. The decreasing trends of PBDEs after the 1980s were considerably slower in the present study than was found in a study of an environmental matrix from the Baltic Proper covering the same time period. This difference suggests local sources near Lake Bolmen. The MeO-BDEs show initially decreasing concentrations, which for 6-MeO-BDE47 continues until the early 1990s. The concentrations of 6-MeO-BDE47 in herring from five locations along the Swedish coast increased from south to north in the Baltic Sea. No correlation between the concentrations of the BDE congeners and the MeO-BDEs was observed, indicating sources other than PBDEs for these compounds. The presence of MeO-BDEs in fish from lakes with different characteristics suggests a natural production not favoured by eutrophication, or dependent on sampling season and geographical location.     

Resource Selection Probability Functions for Gopher Tortoise: Providing a Management Tool Applicable Across the Species’ Range

The gopher tortoise (Gopherus polyphemus) is protected by conservation policy throughout its range. Efforts to protect the species from further decline demand detailed understanding of its habitat requirements, which have not yet been rigorously defined. Current methods of identifying gopher tortoise habitat typically rely on coarse soil and vegetation classifications, and are prone to over-prediction of suitable habitat. We used a logistic resource selection probability function in an information-theoretic framework to understand the relative importance of various environmental factors to gopher tortoise habitat selection, drawing on nationwide environmental datasets, and an existing tortoise survey of the Ft. Benning military base. We applied the normalized difference vegetation index (NDVI) as an index of vegetation density, and found that NDVI was strongly negatively associated with active burrow locations. Our results showed that the most parsimonious model included variables from all candidate model types (landscape features, topography, soil, vegetation), and the model groups describing soil or vegetation alone performed poorly. These results demonstrate with a rigorous quantitative approach that although soil and vegetation are important to the gopher tortoise, they are not sufficient to describe suitable habitat. More widely, our results highlight the feasibility of constructing highly accurate habitat suitability models from data that are widely available throughout the species’ range. Our study shows that the widespread availability of national environmental datasets describing important components of gopher tortoise habitat, combined with existing tortoise surveys on public lands, can be leveraged to inform knowledge of habitat suitability and target recovery efforts range-wide.