Occurrence and congener profiles of polybrominated diphenyl ethers (PBDEs) in environmental samples from coastal British Columbia, Canada

Environmental levels and detailed congener profiles (31 congeners and 3 coeluting congener groups) of polybrominated diphenyl ethers (PBDEs) were assessed in a number of biota samples taken over a large geographic range covering harbours and industrial sites on Canada's West Coast. Additionally, PBDE congener profiles were determined using semipermeable membrane devices (SPMDs) deployed in the Fraser River, the river in Western Canada with the largest industrial activity. PBDE levels detected in biota were between 4 and 2300 ng/g lipid and these levels were compared with those reported in selected European biota to provide a wider perspective on PBDE contamination on Canada's West Coast. Thirteen-congener PBDE patterns in the environmental samples were examined using principal component analysis (PCA), and additionally, comparisons were made between the PBDE profiles in the sample groups and commercially used PBDE technical mixtures (e.g., Bromkals) on a percent composition basis. PCA on congener specific data revealed that PBDE patterns are remarkably similar over a wide geographical range in Western Canada, however, the general pattern in environmental samples varies significantly from those of the predominant technical mixtures. Finally, correlations between PBDE and other persistent and toxic co-occurring contaminants found in Dungeness crab were determined.     

Non-polar halogenated natural products bioaccumulated in marine samples. I. 2,3,3',4,4',5,5'-Heptachloro-1'-methyl-1,2'-bipyrrole (Q1)

This presentation adds new spectroscopic and analytical data on the natural product Q1 that was recently identified by synthesis as 2,3,3('),4,4('),5,5(')-heptachloro-1(')-methyl-1,2(')-bipyrrole. Solid state magic angle spinning 13C NMR data of Q1 is presented as an option for structural proof. Furthermore, the UV spectrum of neat Q1 (absorption maximum at 223 nm) was recorded and, with NMR spectroscopic data, confirmed a twisted bipyrrole ring system. A quantitative standard of Q1 was prepared which allowed to correct previous concentration estimates relative to the electron capture detector response factor of trans-nonachlor. As a result, the actual Q1 response was only 0.65+/-15% of the response factor of trans-nonachlor. Therefore, actual Q1 levels are about 50% higher than the previous estimates. With this result the highest (corrected) Q1 concentration determined to date in the blubber of marine mammals from Australia is 14 mg/kg lipid. Analysis of Q1 and trans-nonachlor in specimens from the German North Sea coast suggests that harbor seals are more able to metabolize Q1 than harbor porpoises. Finally, we calculated that 79 congeners of Q1 (i.e. lower chlorinated 1(')-methyl-1,2(')-bipyrroles) are theoretically possible and present their structures.     

Application of SMR to Modeling Watersheds in the Catskill Mountains

Very few hydrological models commonly used in watershed management are appropriate for simulating the saturation excess runoff. The Soil Moisture Routing model (SMR) was developed specifically to predict saturation excess runoff from variable source areas, especially for areas where shallow interflow controls saturation. A recent version of SMR was applied to two rural catchments in the Catskill Mountains to evaluate its ability to simulate the hydrology of these systems. Only readily available meteorological, topographical, and landuse information from published literature and governmental agencies was used. Measured and predicted streamflows showed relatively good agreement; the average Nash–Sutcliffe efficiency for the two watersheds were R ²=72% and R ²=63%. Distributed soil moisture contents and the locations of hydrologically sensitive areas were also predicted well.     

Life Cycle Assessment as Part of Sustainability Assessment for Chemicals (5 pp)

Background LCA is the only internationally standardized environmental assessment tool (ISO 14040-43) for product systems, including services and processes. The analysis is done ‘from cradle-to-grave’, i.e. over the whole life cycle. LCA is essentially a comparative method: different systems fulfilling the same function (serving the same purpose) are compared on the basis of a ‘functional unit’ - a quantitative measure of this function or purpose. It is often believed that LCA can be used for judging the (relative) sustainability of product systems. This is only partly true, however, since LCA is restricted to the environmental part of the triad ‘environment/ecology - economy - social aspects (including intergenerational fairness)’ which constitutes sustainability. Standardized assessment tools for the second and the third part are still lacking, but Life Cycle Costing (LCC) seems to be a promising candidate for the economic part. Social Life Cycle Assessment still has to be developed on the basis of known social indicators.Method and Limitations LCA is most frequently used for the comparative assessment or optimization analysis of final products. Materials and chemicals are difficult to analyse from cradle-to-grave, since they are used in many, often innumerable product systems, which all would have to be studied in detail to give a complete LCA of a particular material or substance! This complete analysis of a material or chemical is evidently only possible in such cases where one main application exists. But even if one main application does exist, e.g. in the case of surfactants (chemicals) and detergents (final products), the latter may exist in a great abundance of compositions. Therefore, chemicals and materials are better analysed ‘from cradle-to-factory gate’, leaving the analysis of the final product(s), the use phase and the ‘end-of-life’ phases to specific, full LCAs.Conclusion A comparative assessment of production processes is possible, if the chemicals (the same is true for materials) produced by different methods have exactly the same properties. In this case, the downstream phases may be considered as a ‘black box’ and left out of the assessment. Such truncated LCAs can be used for environmental comparisons, but less so for the (environmental) optimization analysis of a specific chemical: the phases considered as ‘black box’ and left out may actually be the dominant ones. A sustainability assessment should be performed at the product level and contain the results of LCC and social assessments. Equal and consistent system boundaries will have to be used for these life cycle tools which only together can fulfil the aim of assessing the sustainability of product systems.     

Responses to projected changes in climate and UV-B at the species level

Environmental manipulation experiments showed that species respond individualistically to each environmental-change variable. The greatest responses of plants were generally to nutrient, particularly nitrogen, addition. Summer warming experiments showed that woody plant responses were dominant and that mosses and lichens became less abundant. Responses to warming were controlled by moisture availability and snow cover. Many invertebrates increased population growth in response to summer warming, as long as desiccation was not induced. CO2 and UV-B enrichment experiments showed that plant and animal responses were small. However, some microorganisms and species of fungi were sensitive to increased UV-B and some intensive mutagenic actions could, perhaps, lead to unexpected epidemic outbreaks. Tundra soil heating, CO2 enrichment and amendment with mineral nutrients generally accelerated microbial activity. Algae are likely to dominate cyanobacteria in milder climates. Expected increases in winter freeze-thaw cycles leading to ice-crust formation are likely to severely reduce winter survival rate and disrupt the population dynamics of many terrestrial animals. A deeper snow cover is likely to restrict access to winter pastures by reindeer/caribou and their ability to flee from predators while any earlier onset of the snow-free period is likely to stimulate increased plant growth. Initial species responses to climate change might occur at the sub-species level: an Arctic plant or animal species with high genetic/racial diversity has proved an ability to adapt to different environmental conditions in the past and is likely to do so also in the future. Indigenous knowledge, air photographs, satellite images and monitoring show that changes in the distributions of some species are already occurring: Arctic vegetation is becoming more shrubby and more productive, there have been recent changes in the ranges of caribou, and "new" species of insects and birds previously associated with areas south of the treeline have been recorded. In contrast, almost all Arctic breeding bird species are declining and models predict further quite dramatic reductions of the populations of tundra birds due to warming. Species-climate response surface models predict potential future ranges of current Arctic species that are often markedly reduced and displaced northwards in response to warming. In contrast, invertebrates and microorganisms are very likely to quickly expand their ranges northwards into the Arctic.     

Statistical evaluation of the influence of flow conditions and sampling techniques on water quality data.

The purpose of this study is to statistically evaluate the influence of various sampling methodologies and flow conditions on the quality and comparability of total phosphorus concentration data collected over the course of 27 months at the South Florida Water Management District (SFWMD) S-65E structure. The data was obtained from the following sampling methodologies: U.S. Geological Survey (USGS) (Reston, Virginia) equal width increment spatially composite grab samples, USGS replicate samples, SFWMD grab samples, and SFWMD autosampler samples. Both significant and insignificant differences were reported from these comparisons. Parametric and nonparametric standard statistical tests for significance were carried out to evaluate the differences between the data. To avoid invalid conclusions of insignificant differences, we conducted tests for equivalence of the means and variances. The results from the data analysis revealed that both flow conditions and sampling methodology affected the water quality data.     

Sorption and mass fluxes of sulfonated naphthalene formaldehyde condensates in aquifers

Sulfonated naphthalene formaldehyde condensates (SNFC) and their monomeric analogues were used as superplasticizers for cement suspension injections at two tunnel construction sites that are in direct contact with groundwater. Because in one case the aquifer is an important drinking water resource, the behavior of SNFC in the groundwater was carefully investigated. Chemical analyses showed that SNFC leached to the groundwater in concentrations of up to 58 microg/l of total SNFC at a distance of about 60 m down-gradient from the construction site. Of the individual SNFC components, only monomers and oligomers with up to four units could be detected in the groundwater. Oligomers with more than four units did not leach from the cement paste. The leached oligomers were transported in the groundwater at different velocities, which can be explained by sorption experiments. Mass fluxes of SNFC used at the tunnel construction sites were evaluated. Most SNFC were immobilized in the cement, but 5% (w/w) of the applied SNFC were found to leach into the aquifer. This corresponds to a total amount of leached SNFC of approximately 100 kg, of which about 80% are biodegraded in the aquifer and 20% (20 kg) still remain in the groundwater.     

THE IMPACT OF RUNOFF GENERATION MECHANISMS ON THE LOCATION OF CRITICAL SOURCE AREAS1

ABSTRACT: Identifying phosphorus (P) source areas and transport pathways is a key step in decreasing P loading to natural water systems. This study compared the effects of two modeled runoff generation processes ‐ saturation excess and infiltration excess ‐ on total phosphorus (TP) and soluble reactive phosphorus (SRP) concentrations in 10 catchment streams of a Catskill mountain watershed in southeastern New York. The spatial distribution of runoff from forested land and agricultural land was generated for both runoff processes; results of both distributions were consistent with Soil Conservation Service‐Curve Number (SCS‐CN) theory. These spatial runoff distributions were then used to simulate stream concentrations of TP and SRP through a simple equation derived from an observed relation between P concentration and land use; empirical results indicate that TP and SRP concentrations increased with increasing percentage of agricultural land. Simulated TP and SRP stream concentrations predicted for the 10 catchments were strongly affected by the assumed runoff mechanism. The modeled TP and SRP concentrations produced by saturation excess distribution averaged 31 percent higher and 42 percent higher, respectively, than those produced by the infiltration excess distribution. Misrepresenting the primary runoff mechanism could not only produce erroneous concentrations, it could fail to correctly locate critical source areas for implementation of best management practices. Thus, identification of the primary runoff mechanism is critical in selection of appropriate models in the mitigation of nonpoint source pollution. Correct representation of runoff processes is also critical in the future development of biogeochemical transport models, especially those that address nutrient fluxes.     

ESTIMATION OF STREAMFLOW,BASE FLOW,AND NITRATE‐NITROGEN LOADS IN IOWA USING MULTIPLE LINEAR REGRESSION MODELS1

Nineteen variables, including precipitation, soils and geology, land use, and basin morphologic characteristics, were evaluated to develop Iowa regression models to predict total streamflow (Q), base flow (Qb), storm flow (Qs) and base flow percentage (%Qb) in gauged and ungauged watersheds in the state. Discharge records from a set of 33 watersheds across the state for the 1980 to 2000 period were separated into Qb and Qs. Multiple linear regression found that 75.5 percent of long term average Q was explained by rainfall, sand content, and row crop percentage variables, whereas 88.5 percent of Qb was explained by these three variables plus permeability and floodplain area variables. Qs was explained by average rainfall and %Qb was a function of row crop percentage, permeability, and basin slope variables. Regional regression models developed for long term average Q and Qb were adapted to annual rainfall and showed good correlation between measured and predicted values. Combining the regression model for Q with an estimate of mean annual nitrate concentration, a map of potential nitrate loads in the state was produced. Results from this study have important implications for understanding geomorphic and land use controls on streamflow and base flow in Iowa watersheds and similar agriculture dominated watersheds in the glaciated Midwest.