Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters

Relative kinetic studies have been performed on the reactions of Cl atoms with a series of methyl alkyl esters in a 405-liter borosilicate glass chamber at (298 ± 3) K and one atmosphere of synthetic air using in situ FTIR spectroscopy to monitor the reactants. Rate coefficients (in units of cm³ molecule^?1 s^?1) were determined for the following compounds: methyl acetate (2.48 ± 0.58) × 10^?12; methyl propanoate (1.68 ± 0.36) × 10^?11; methyl butanoate (4.77 ± 0.87) × 10^?11; methyl pentanoate (7.84 ± 1.15) × 10^?11; methyl hexanoate (1.09 ± 0.31) × 10^?10; methyl heptanoate (1.56 ± 0.37) × 10^?10; methyl cyclohexane carboxylate (3.32 ± 0.76) × 10^?10; methyl-2-methyl butanoate (9.41 ± 1.39) × 10^?11.In addition rate coefficients (in units of 10^?11 cm³ molecule^?1 s^?1) have been obtained for the reactions of OH radicals with the following compounds: methyl butanoate (3.55 ± 0.71), methyl pentanoate (5.41 ± 1.08), and methyl-2-methyl butanoate (4.08 ± 0.82).Using the kinetic rate data tropospheric lifetimes for the methyl alkyl esters with respect to their reactions with OH, and Cl have been estimated for typical ambient air concentrations of these oxidants.     

Initial Adjustments Within a New River Channel: Interactions Between Fluvial Processes, Colonizing Vegetation, and Bank Profile Development

A conceptual model of the morphological development of the riparian margins of newly cut river channels is presented, suggesting early feedbacks between vegetation growth and bank form. To test the model, observations of long and cross profiles, bank sediment and seed deposition, and bank vegetation development were collected over the first 2 years of river flows through a reach of the River Cole, West Midlands, UK. The newly created channel had a sinuous planform and varying asymmetric trapezoidal cross section in sympathy with the planform. No imposed bedforms or bank reseeding were included in the design. Over the 2 years, development of bedforms was rapid, with bed sediment sorting and bank profile adjustment occurring more steadily and progressively. Six classes of bank profile were identified by the end of the study period, illustrating close associations with sediment aggradation, vegetation colonization, and growth patterns. Vegetation colonization of the banks was seeded predominantly from local sources during the summer and from hydrochory (transport by the river) during the winter. Colonizing vegetation on the riverbanks appeared to act as a significant propagule source by the second summer and as an increasingly important roughness element, trapping both propagules and sediment, within the second year and providing early feedback into bank evolution. As a result, the time required for riparian margin development in the conceptual model was found to be considerably longer than observed in the study river. In addition, the role of surface wash/bank failure in modifying the bank profile and transporting seeds onto the upper bank face during the first year of bank development was found to be important in initiating rapid bank vegetation colonization and surface stabilization. This set of processes had not been incorporated in the initial conceptual model. In relation to channel restoration, this research illustrates that in small temperate rivers of modest energy the provision of an initial, sinuous corridor is sufficient to induce rapid development of fluvial features and vegetation cover without the need to construct bed forms or to seed the banks.     

The dynamics of mercury around an artisanal and small-scale gold mining area,Camarines Norte,Philippines

Environmental Science and Pollution Research - To elucidate the dynamics of mercury emitted and released by artisanal and small-scale gold mining (ASGM) activity and to estimate its impact on the...     

Habitat Conditions and Correlations of Sediment Quality Triad Indicators in Delaware Bay

This paper summarizes sampling results from NOAA's National Status and Trends (NS&T) Program for marine environmental quality in Delaware Bay. A stratified-random design was used to determine the spatial extent of sediment contamination and toxicity in Delaware Bay from offshore stations in the coastal zone, the lower estuary, the upper estuary, the fresh/salt mixing zone, and tidal fresh areas. Sediment samples were taken for chemical analyses of major classes of environmental contaminants, a suite of toxicity bioassays, and benthic macrofaunal community assessment to identify patterns of resident species. The tidal-fresh areas and portions of the mixing zone of the study area were heavily contaminated. Contaminant concentrations were frequently above the 90th percentile of EMAP Virginian Province levels. PAHs in the sediment were higher than previously documented, with a major component of PAHs being pyrogenic in origin. Bioassay results were highly variable. Toxicity and contaminant levels were correlated when aggregated into indices, but were only marginally correlated with benthic community impacts. High and low abundance stations were found in all zones. Most of the tidal fresh stations were dominated by pollution tolerant species. Species diversity and abundance were generally lowest in the fresh/salt mixing zone.     

Atmospheric Change and the Diversity of Aquatic Invertebrates: Are We Missing the Boat?

The response of natural systems to atmospheric change may depend critically on species diversity and on the genetic diversity (variability) found within their respective populations. Yet, most surveys of aquatic invertebrates account for neither. This may be of particular concern for benthic populations in running waters because of the considerable variability and the fragmentary nature of these habitats (e.g. isolated watersheds). In such habitats, species with limited genetic variability and/or limited dispersal capabilities (genetically differentiated populations) may be unable to track rapid environmental change, and may be more susceptible to climatic perturbations. We present a conceptual framework to illustrate some of the potential problems of ignoring population genetics when considering the impacts of global atmospheric change. We then review a simple method to assess population genetic structure and we evaluate available data on the genetic structure of North American stream invertebrates. These data indicate that benthic taxa often consist of genetically differentiated local populations, or even previously unknown species. Accordingly, our limited knowledge of population structure among benthic invertebrates may result in the unwitting loss of genetic and/or species diversity. Enhanced taxonomic research incorporating molecular techniques is clearly warranted. Conservation strategies based on the preservation and remediation of a diversity of aquatic habitats are likely to be our best means of ensuring species and genetic diversity of invertebrate taxa.     

Comparison of Streambed Sediment and Aquatic Biota as Media for Characterizing Trace Elements and Organochlorine Compounds in the Willamette Basin, Oregon

During 1992–93, 27 organochlorine compounds (pesticides plus total PCB) and 17 trace elements were analyzed in bed sediment and aquatic biota from 20 stream sites in the Willamette Basin as part of the U.S. Geological Survey's National Water-Quality Assessment Program. Data from each medium were compared to evaluate their relative effectiveness for assessing occurrence (broadly defined as documentation of important concentrations) of these constituents. Except for Cd, Hg, Se, and Ag, trace element concentrations generally were higher in bed sediment than in biota. Conversely, although frequencies of detection for organochlorine compounds in biota were only slightly greater than in bed sediment, actual concentrations in biota (normalized to lipid) were as much as 19 times those in sediment (normalized to organic carbon). Sculpin (Cottus spp.) and Asiatic clams (Corbicula fluminea), found at 14 and 7 sites, respectively, were the most widespread taxa collected during the study. Concentrations of trace elements, particularly As and Cu, were typically greater in Asiatic clams than in sculpin. In contrast, almost half of the organochlorine compounds analyzed were found in sculpin, but only DDT and its degradation products were detected in Asiatic clams; this may be related to the lipid content of sculpin, which was about three times higher than for clams. Thus, the medium of choice for assessing occurrence depends largely on the constituent(s) of interest.     

Cost-Effective Mitigation of Diffuse Pollution: Setting Criteria for River Basin Management at Multiple Locations

A case study of the Yorkshire Derwent (UK) catchment is used to illustrate an integrated approach for assessing the viability of policy options for reducing diffuse nitrate losses to waterbodies. For a range of options, modeling methods for simulating river nitrate levels are combined with techniques for estimating the economic costs to agriculture of modifying those levels. By incorporating spatially explicit data and information on catchment residence times (which may span many decades particularly in areas of groundwater discharge) a method is developed for efficient spatial targeting of measures, for example, to the most at-risk freshwater environments. Combining hydrological and economic findings, the analysis reveals that, in terms of cost-effectiveness, the ranking of options is highly sensitive to both (i) whether or not specific stretches of river within a catchment are regarded as a priority for protection, and (ii) the criterion of nitrate concentration deemed most appropriate as an indicator of the health of the environment. Therefore, given the focus under European legislation upon ecological status of freshwaters, these conclusions highlight the need to improve understanding of mechanistic linkages between the chemical and biological dynamics of aquatic systems.     

Biomonitoring with Gammarus pulex at the Meuse (NL), Aller (GER) and Rhine (F) rivers with the online Multispecies Freshwater Biomonitor

Biological early warning systems represent a set of tools that may be able to respond to certain chemical monitoring requirements of recent European legislation, the Water Framework Directive (WFD2000/60/EC), that aims to improve and protect water quality across Europe. In situ biomonitoring was performed along the rivers Meuse (NL), Aller (GER) and Rhine (F) within the frame of the European Union-funded Project SWIFT-WFD. Gammarus pulex was used as a test organism during the evaluation of the Multispecies Freshwater Biomonitor(R) (MFB), an online biomonitor to quantitatively record different behaviour patterns of animals. At the river Meuse G. pulex reacted to pulse exposure of either a mixture of trace metals or of several organic xenobiotics, by showing up to 20% decreased locomotory activity (already at the 1st pulse) and increased mortality (at 2nd or 3rd pulse only). G. pulex deployed within the MFB system were observed to survive well at the monitoring station on the Aller (100%) and monitoring did not result in the measurement of chemical irregularities. In contrast, deployment at the monitoring station on the Rhine river demonstrated that the test organism was able to detect chemical irregularities by up to 20% decreased locomotory activity in the animals. The MFB proved to be an alert system for water quality monitoring at sensitive sites and sites with accidental pollution.     

Modelling PCB bioaccumulation in a Baltic food web

A steady state model is developed to describe the bioaccumulation of organic contaminants by 14 species in a Baltic food web including pelagic and benthic aquatic organisms. The model is used to study the bioaccumulation of five PCB congeners of different chlorination levels. The model predictions are evaluated against monitoring data for five of the species in the food web. Predicted concentrations are on average within a factor of two of measured concentrations. The model shows that all PCB congeners were biomagnified in the food web, which is consistent with observations. Sensitivity analysis reveals that the single most sensitive parameter is log K(OW). The most sensitive environmental parameter is the annual average temperature. Although not identified amongst the most sensitive input parameters, the dissolved concentration in water is believed to be important because of the uncertainty in its determination. The most sensitive organism-specific input parameters are the fractional respiration of species from the water column and sediment pore water, which are also difficult to determine. Parameters such as feeding rate, growth rate and lipid content of organism are only important at higher trophic levels.