24 h diffusive sampling of toxic VOCs in air onto Carbopack X solid adsorbent followed by thermal desorption/GC/MS analysis-laboratory studies

Diffusive sampling of a mixture of 42 volatile organic compounds (VOCs) in humidified, purified air onto the solid adsorbent Carbopack X was evaluated under controlled laboratory conditions. The evaluation included variations in sample air temperature, relative humidity and ozone concentration. Linearity of samples with loading was examined both for a constant concentration with time varied up to 24 h and for different concentrations over 24 h. Reverse diffusion and its increase with accumulation of sample were determined for all compounds. Tubes were examined for blank levels, change of blanks with storage time, and variability of blanks. Method detection limits were determined based on seven replicate samples. Based on this evaluation, 27 VOCs were selected for quantitative monitoring in the concentration range from approximately 0.1 to 4 ppbv. Comparison results of active and diffusive samples taken over 24 h and under the same simulated ambient conditions at a constant 2 ppbv were interpreted to estimate the effective diffusive sampling rates (ml min(-1)) and their uncertainties and to calculate the corresponding diffusive uptake rates (ng ppmv(-1) min(-1)).     

Spatial contaminant heterogeneity: quantification with scale of measurement at contrasting sites

Material within the terrestrial environment is rarely homogeneously distributed, either spatially or temporally. One consequence of heterogeneity is that uncertainty is usually generated in measurements that are taken with the aim of characterising the environment. For example, a measurement of analyte concentration within soil taken from one sampling location on contaminated land can vary substantially when compared against another sample taken at effectively the same nominal location. The measurement uncertainty arising from the heterogeneity can substantially limit the reliability of the interpretations made upon environmental investigations. The sampling uncertainty usually outweighs the analytical uncertainty from the laboratory, often by a factor of 20 or more. One approach to reducing the uncertainty is to design a more suitable sampling strategy. This might be achieved by predicting the degree of heterogeneity prior to the investigation, but this is often difficult to achieve accurately. Another approach, which was investigated here, is to actually characterise the heterogeneity prior to the main investigation using rapid and inexpensive technology, such as in situ measurement techniques. In situ portable X-ray fluorescence (PXRF) and X-ray microprobe (XMP) techniques were employed to test the feasibility of this approach. Two contrasting contaminated land sites were chosen to characterise the two-dimensional spatial heterogeneity of heavy metal contamination in topsoil at a range of scales (50 m to 0.001 m). The spatial heterogeneity of contaminants, expressed as relative standard deviations, was found to differ between the two sites by a factor of two, largely due to the mode of deposition of pollution. The study also indicated that the heterogeneity did not change systematically with the scale of measurement between sampling locations at either site.     

Pool of Dust Particles over the Asian Continent: Balloon-borne Optical Particle Counter and Ground-based Lidar Measurements at Dunhuang, China

Measurements of aerosols were made in 2001 and 2002 at Dunhuang (40 degrees 00'N, 94 degrees 30'E), China to understand the nature of atmospheric particles over the desert areas in the Asian continent. Balloon-borne measurements with an optical particle counter suggested that particle size and concentration had noticeable peaks in super micron size range not only in the boundary mixing layer but also in the free troposphere. Super-micron particle concentration largely decreased in the mid tropopause (from 5 to 10 km; above sea level, a.s.l.). Lidar measurements made during August 2002 at Dunhuang suggested the possibility that mixing of dust particles occurred from near the ground to about 6 km even under calm weather conditions, and a large depolarization ratio of particulate matter was found in the aerosol layer. The top of the aerosol layer was found at heights of nearly 6 km (a.s.l.). It is strongly suggested that nonspherical dust particles (Kosa particles) frequently diffused in the free atmosphere over the Taklamakan desert through small-scale turbulences and are possible sources of dust particles of weak Kosa events that have been identified in the free troposphere not only in spring but also in summer over Japanese archipelago. Electron microscopic experiments of the particles collected in the free troposphere confirmed that coarse and nonspherical particles observed by the mineral particle were major components of coarse mode (diameter larger than 1 microm) below about 5 km over Dunhuang, China.     

Sediment quality in the Douro river estuary based on trace metal contents, macrobenthic community and elutriate sediment toxicity test (ESTT)

The aim of this study was to evaluate the sediment quality in the mesotidal Douro River estuarine environment, in order to identify areas where sediment contamination could cause ecosystem degradation. Samples were obtained in five locations and sediment characterised for grain size, total organic matter, total-recoverable metals (Al, Fe, Cu, Pb, Cr, Ni, Cd, Zn and Mn), as well as acid volatile sulfide (AVS) and simultaneously extracted metals (SEM). In situ effects were evaluated by examining the macrobenthic community structure. An elutriate sediment toxicity test (ESTT) was used to estimate the amount of metals and nutrients that could be exchanged with the water column through resuspension, and its positive or negative effects on the growth of the micro-alga Emiliania huxleyi in a 10 day test. Anthropogenic metal contamination was identified at the north bank of the Douro estuary, with deleterious effects on the macrobenthic community, namely decrease in number of species and diversity. This contamination could possibly also be toxic for water column organisms, in case of resuspension, as shown by the ESTT. Sediments from the salt marsh at the south bank showed an impoverished macrobenthic community and elutriate toxicity, which appeared to be due to anaerobic conditions. This study clearly shows the usefulness of the ESST approach to assess the biological effect of resuspension of estuarine sediments.     

Assessment of Metal Contamination in Doñana National Park (Spain) using Crayfish (Procamburus Clarkii)

Water quality assessment in the Aznalcollar area was attempted using multivariate methods based on heavy metal concentrations in red swamp crayfish (Procamburus clarkii). Trace levels of four heavy metals, copper (Cu), zinc (Zn), cadmium (Cd) and lead (Pb), were detected in crayfish from eleven different stations. Principal component analysis (PCA) highlighted a gradient of contamination between the sampling stations. Cluster analysis (CA) distinguished three groups of stations. Discriminant analysis also differentiated three groups. The group centroids of the first discriminant function were used to devise an index that varies according to the source of the crayfish. These standardized values are proposed for use as a water quality index. The ability of this index to successfully predict environmental quality was proved with random samples.     

Biological complexity confounds the separation of point- and non-point sources of human impact on the natural world

Identifying process from pattern is one of the most vexing tasks inenvironmental monitoring. Given information on the distribution of speciesin a pre-defined area, together with comprehensive data on how environmentalconditions in that area have altered through time, is it possible toidentify the factors controlling the species‘ layout? Here, the practicalsignificance of this quandary is demonstrated using a series ofenvironmentally-degraded coastal lagoons in New South Wales. The TuggerahLakes (33°17′S,151°30′E) have over the last 50 yearsexperienced significant changes in species‘ distributions. Seagrasses,macroalgae, phytoplankton, molluscs, prawns and the jellyfish Catostylus mosaicus have altered in spatial pattern. Two human activitieshave been blamed for these perturbations: (1) agricultural clearance ofnative vegetation from the catchment, with associated input of top-soil andnutrients; (2) the commissioning of a coal-fired power station in 1967, withmassive uptake and recirculation of lake water for cooling purposes. In thispaper, spatial changes in macrophyte distributions over the last 50 yearsare reviewed in an attempt to identify the true source(s) of perturbation.The model adopted assumes that the power station is a point source of impactwhile nutrient inputs from the catchment are a diffuse source of impact;changes in species distributions can hypothetically be related back to thesesources according to whether they are localised or widespread. However,after a comprehensive analysis of available macrophyte data derived frominterviews, aerial photography and line transect methodologyies theconclusion is reached that changes in biogeographical pattern around theTuggerah Lakes cannot be attributed to specific anthropogenic pressures atanything beyond the coarsest of levels. This is considered to be the normfor most coastal management situations where natural background variation(’noise‘) and the complexity of linkages between physical, chemical andbiological components confounds the identification of causal relationships.The practical implications of this conclusion are discussed in the contextof litigation and remedial management design. Emphasis is placed on theneed to adopt an adaptive approach to estuarine management, incorporatingexplicit recognition of the limitations of available data, and to developnew techniques for identifying cause-effect relationships.     

Methods for constructing and balancing ecosystem flux charts: new techniques and software

We describe a general computer program which employs novel techniques to analyze carbon (energy) and nutrient flows in complex food webs. The program uses estimates of metabolic/physiological parameters and ecosystem fluxes to simultaneously calculate the most likely balanced flux charts for carbon and a nutrient. We give an example of how the model can explore the theoretical issues involved with nutrient limitation and recycling.     

Development of a practical forest ecosystem classification from existing biophysical studies: An approach used in northwestern Quebec

While forest ecosystem classification work in Quebec has traditionally concentrated on inventory and mapping, more effort is now being placed on developing field guides similar to those produced in other Canadian provinces. As part of a project to produce a practical forest ecosystem field guide for the Amos Lowlands Ecological Region in northwestern Quebec, existing sub-regional ecological studies were exploited in order to develop a regional classification of forest ecosystems, or forest stations. Review of four fundamental studies provided a list of 107 ecological phases, each representing a particular combination of forest composition, surface deposit type and moisture regime. A series of silvicultural and environmental interpretations were developed and values for each were attributed to the ecological phases. Cluster analysis was then performed to classify phases into 29 broader units. A large, regional biophysical database which became available later in the project provided a means of validating and effectively modifying the classification. The justifications for using the original approach are discussed.     

The efficacy of a limestone doser to mitigate stream acidification in a Maryland coastal plain stream: Implications for migratory fish species

The objective of this two-year study was to determine the efficacy of an automated limestone slurry doser to neutralize acidic pulses and improve water quality conditions for enhancing survival of early life stages of migratory fish species in a Maryland coastal plain stream. Implications for survival of early life stages of migratory fish species such as yellow perch (Perca flavescens), white perch (Morone americana), blueback herring (Alosa aestivalis) and alewife (Alosa pseudoharengus) are discussed based on the improved chemical conditions in the dosed area of the stream. Despite problems with overdosing in 1991 and failure of the stage transducer to work properly in 1992, the doser was generally effective in neutralizing acidic pulses (pH depressions) in the stream during three major rain events in both years. Chemical conditions (pH and inorganic monomeric aluminum) reported in the non-dosed area during major rainfall events were potentially stressful to both alewife and blueback herring although neither species was reported spawning in the stream during either year. Mitigating the potential impact of acidic conditions on early life stages of important migratory fish species was not sufficient to ensure spawning. It is therefore recommended that habitat improvement measures and well designed fish stocking programs be implemented concurrently with doser operations if the goal is to create optimum spawning conditions for migratory species.     

Fractionation of butyltin species during sample extraction and preparation for analysis

Solvent extraction and evaporative concentration steps are often used in procedures for the measurement of butyltins in environmental samples. As part of a larger study utilizing radiolabeled butyltins, the loss and fractionation of butyltins during sample preparation was investigated. TBT, DBT, and MBT were extracted from acidified seawater by hexane with efficiencies of about 95–99, 50–60 and 11% respectively. In addition, losses of about 70% of DBT were found during evaporative concentration of hexane. A variety of sediment extraction procedures were tested and none were found to be highly efficient for total butyltin extraction.