Large-scale mercury variations in Lake Vänern (Sweden) 1974-98

Lake V?nern, the largest lake in Sweden, has been seriously contaminated with mercury during the 20th century. In the 1970's and 80's the direct load, mainly from a chlor-alkali industry in the area, of mercury was drastically reduced as a response to new legislation, from three to five tons down to between five and ten kg yr(-1). Large amounts of the disposed pollutant have accumulated in the sediments. The question posed in this work is now, is the effect of the drastic load reduction after more than two decades visible in the sediments? The question is relevant as large areas still are blacklisted for fishing, but also as a follow-up of a major remedy action. The lake also serves as a freshwater reservoir for even Sweden's second largest city. This work synthesises and compares data of mercury in the sediments from three major field programs, in 1974, 1984 and 1998. The interest is focused on both spatial heterogeneity and temporal trends. In 1974, the surface concentrations are significantly higher than in subsequent surveys. Significant differences are also found between 1984 and 1998. Significant spatial differences within the lake are found for respective year. The most contaminated area is located in the north, close to the major point source (a former chlor-alkali industry). This is also the area with the largest improvement, as a direct response to the reduction in load. Further from the outlet, the recovery is more affected by burial and transport processes out into the deeper basins.     

The collection of PM10 for toxicological investigation: comparisons between different collecting devices

A positive correlation has been established between increased levels of airborne particulate pollution and adverse health effects, the toxicological mechanisms of which are poorly understood. For toxicologists to unambiguously determine thesemechanisms, truly representative samples of ambient PM₁₀ are required. This presents problems, as PM₁₀ collecting equipment commonly employed, such as the Tapered Element Oscillating Microbalance (TEOM®), heat the inflow toexclude moisture or use fibrous filters, resulting in a PM₁₀sample that may have undergone significant chemical change on thefilter surface or is contaminated by filter fibres. Other systems(i.e. Negretti and Partisol) can successfully collect PM₁₀ without chemical alteration or filter contamination. Comparativecollections from Port Talbot, S. Wales suggest that TEOMs and Negretti/Partisol systems collect different PM₁₀'s; the principle difference arising from the TEOM's heating chamber, which precipitates water-soluble ions and volatilises some organic components. This results in both the mass and compositionof the PM₁₀'s being altered. Particle size distributionsfor Negretti and Partisol collections highlighted differences mainly attributed to different flow rates. The results of thiswork demonstrate that simple correlations between PM₁₀ massand adverse health effects are problematic. Furthermore, elucidation of the complex fractionation and chemical changes indifferent collectors is necessary.     

Macroinvertebrate Regionalisation for use in the Management of Aquatic Ecosystems in Victoria, Australia

The development of a broader, more holistic approach to aquaticecosystem management has been called for in recent years. Physical and chemical objectives alone are no longer consideredsufficient for the protection of aquatic ecosystems and shouldbe supplemented with biological objectives. The ubiquitousand sedentary nature of macroinvertebrates, combined with theirmeasurable response to environmental conditions, favour their use as important indicators in environmental policies. To establish biological objectives, there is a need for a regionalframework to limit the variability between ecosystems. Past studies have demonstrated that an a posteriori regionalisationapproach may be more useful than an a priori approach in explaining single component (e.g. macroinvertebrates) patternsacross ecosystems. This is particularly important as aquaticresource management agencies often focus on one or twocomponents of the ecosystem to assess environmental health. This study uses an a posteriori method to delineate and describebiological regions based on edge and riffle macroinvertebrate data. The regionalisation will provide a framework for settingbiological objectives, based on the range of reference conditionsmeasured within each separate region. The objectives will includeregional checklists for taxa and biotic indices. Predictive modelling in the style of RIVPACS or AUSRIVAS will also be usedwithin each region to develop objectives, incorporating local, regional and systematic features as predictor variables.     

Economic and Spatial Impacts of an Existing Reserve Network on Future Augmentation

An optimization model for land reservation was developed that explicitly selects parcels in the most compact or contiguous manner possible while meeting habitat requirements and a budget limitation. The model was used to compare the effects of an existing reserve network on future parcel spatial locations and total cost. Using habitat and land value data from Josephine County, Oregon, it was found that a system of existing reserves created by various policies and overseen by different agencies can decrease future reserve compactness and contiguity, and increase total cost. This work suggests that coordinated planning can result in more efficient conservation efforts for less cost.     

Mechanistic studies of N-nitrosodimethylamine (NDMA) formation in chlorinated drinking water

Studies were conducted to investigate the hypothesis that N-nitrosodimethylamine (NDMA) is a potential disinfection by-product specifically produced during chlorination or chloramination. Experiments were conducted using dimethylamine (DMA) as a model precursor. NDMA was formed by the reaction of DMA with free chlorine in the presence of ammonia and also with monochloramine. We proposed a mechanism for NDMA formation in chlorinated or chloraminated water, which does not require nitrite as in N-nitrosation. The critical NDMA formation reactions consist of (i) the formation of monochloramine by combination of free chlorine with ammonia, (ii) the formation of 1,1-dimethylhydrazine (UDMH) intermediate from the reaction of DMA with monochloramine followed by, (iii) the oxidation of UDMH by monochloramine to NDMA, and (iv) the reversible chlorine transfer reaction between free chlorine/monochloramine and DMA which is parallel with (i) and (ii). A kinetic model was also developed to validate the proposed mechanism.     

Examples of the role of analytical chemistry in environmental risk management research

Analytical chemistry is an important tier of environmental protection and has been traditionally linked to compliance and/or exposure monitoring activities for environmental contaminants. The adoption of the risk management paradigm has led to special challenges for analytical chemistry applied to environmental risk analysis. Namely, methods developed for regulated contaminants may not be appropriate and/or applicable to risk management scenarios. This paper contains examples of analytical chemistry applied to risk management challenges broken down by the analytical approach and analyte for some selected work in our laboratory. Specific techniques discussed include stable association complex electrospray mass spectrometry (cESI-MS), gas chromatography-mass spectrometry (GC-MS), split-flow thin cell (SPLITT) fractionation and matrix-assisted laser desorption time of flight mass spectrometry (MALDI-ToF-MS). Specific analytes include haloacetic acids (HAA9), perchlorate, bromate, triazine degradation products, metal-contaminated colloids and Cryptosporidium parvum oocysts.     

Preliminary air pollution monitoring in San Miguel, Buenos Aires

Passive diffusion samplers were employed in San Miguel(Buenos Aires Metropolitan Area) for a preliminary airpollution monitoring. The highest loads were observedin downtown, compared with an urban background site.Total suspended particulate matter (TSPM) varied from0.257 to 0.033 mg cm^-2 month^-1; dust was examinedfor particle nature and size distribution. A similartrend was observed for nitrogen dioxide (NO₂) andTSPM spatial distribution, suggesting that traffic isthe major pollution source. Sulphur dioxide (SO₂)values were low and rather homogeneous. Levels for theinvestigated pollutants are below EPA's guide linevalues. Geographic (flat area, near to Rio de LaPlata) and climatologic factors (rainfalls andvariable wind directions) contribute to disperse pollutants.     

A Watershed-based Cumulative Risk Impact Analysis: Environmental Vulnerability and Impact Criteria

Swine Concentrated Animal Feeding Operations (CAFOs) have received much attention in recent years. As a result, a watershed-based screening tool, the Cumulative Risk Index Analysis (CRIA), was developed to assess the cumulative impacts of multiple CAFO facilities in a watershedsubunit. The CRIA formula calculates an index number based on: 1) the area of one or more facilities compared to the area of the watershed subunit, 2) the average of the environmental vulnerability criteria, and 3) the average of the industry-specific impact criteria. Each vulnerability or impact criterion is ranked on a 1 to 5 scale, with a low rank indicating low environmental vulnerability or impact and a high rank indicating high environmental vulnerability or impact. The individual criterion ranks, as well as the total CRIA score, can be used to focus the environmental analysis and facilitate discussions with industry, public, and other stakeholders in the Agency decision-making process.     

Luminescence spectroscopy as a screening tool for the potential carcinogenicity of asphalt fumes

A subset of polycyclic aromatic compounds (PACs), which contain 4-6 annulated rings, has been documented as the source of carcinogenicity in animal skin painting studies of petroleum products and asphalt fumes (M. L. Machado, P. W. Beatty, J. C. Fetzer, A. H. Glickman and E. L. McGinnis, Fundam. Appl. Toxicol., 1993, 21, 492; T. A. Roy, S. W. Johnson, G. R. Blackburn and C. R. Mackerer, Fundam. Appl. Toxicol., 1988, 10, 466). Because of the chemical complexity of these materials, it has been difficult to identify the specific compounds within this broad range of PACs responsible for their carcinogenicity. An alternative approach using luminescence spectroscopy was taken in this study to quantify, without identification, a subset of these compounds that appears to cause cancer. The fluorescence response at a specific wavelength pair was obtained for 39 laboratory asphalt fume condensates from animal skin painting studies, yielding a linear correlation coefficient of R2 = 0.96 between the fluorescence response in these materials and the carcinogenicity found in animal studies. In the absence of other asphalt fume condensates from animal studies, 17 petroleum oils were also evaluated using this method and compared with the available animal skin painting data. The details of the method include a clean-up step that removes the highly polar compounds and spectral subtraction of two- and three-ring PAC interference, both of which add to the fluorescence response, yet were not found to contribute to a carcinogenic response from skin painting studies. Full scan fluorescence plots also produce a fingerprint which can be used to assess contamination, such as coal tar products or mixtures of materials, that are not defined as asphalt, yet may be present in the working environment.     

Partitioning of mercury onto suspended sediments in estuaries

Radiochemical partitioning experiments using 203Hg have been undertaken with mixtures of river, seawater and sediment samples taken from three geochemically contrasting UK estuaries: the Plym, Beaulieu and Mersey. Species of dissolved Hg were determined using reversed-phase C18 chelating columns and particulate species were determined by sequential leaching with 1 M NH4OAc and 1 M HCl. Mercury had a high particle reactivity with partition coefficients, KDs, ranging from 10(4) to 5 x 10(5) ml g(-1), depending on salinity, the chemical composition of the end-member waters, and on the physico-chemical characteristics of the sediment. Dissolved organic matter present in the waters (humic substances and/or anthropogenic compounds) was found to be the main factor governing the forms of dissolved Hg and their reactivity. From the spiked 203Hg, up to 95% of the dissolved metal was retained on the C18 columns for the Mersey waters, whereas this fraction was < 60% in the Plym and Beaulieu waters. Quasi-irreversible adsorption of Hg onto particles from each estuary was observed over a time-scale of a few hours and < 20% of total particulate Hg was released by the sequential leach. In this paper, physico-chemical processes are proposed to explain the estuarine behaviour of Hg and the results are discussed in terms of Hg availability in estuarine systems.