A ten year summary of concurrent ambient water column and sediment toxicity tests in the Chesapeake Bay watershed: 1990-1999

The goal of this study was to identify the relative toxicity ofambient areas in the Chesapeake Bay watershed by using a suiteof concurrent water column and sediment toxicity tests at seventy-five ambient stations in 20 Chesapeake Bay rivers from1990 through 1999. Spatial and temporal variability was examinedat selected locations throughout the 10 yr study. Inorganicand organic contaminants were evaluated in ambient water andsediment concurrently with water column and sediment tests toassess possible causes of toxicity although absolute causalitycan not be established. Multivariate statistical analysis wasused to develop a multiple endpoint toxicity index (TOX-INDEX) at each station for both water column and sediment toxicity data. Water column tests from the 10 yr testing period showed that49% of the time, some degree of toxicity was reported. The mosttoxic sites based on water column results were located inurbanized areas such as the Anacostia River, Elizabeth River andthe Middle River. Water quality criteria for copper, lead,mercury, nickel and zinc were exceeded at one or more of thesesites. Water column toxicity was also reported in localizedareas of the South and Chester Rivers. Both spatial and temporalvariability was reported from the suite of water column toxicitytests. Some degree of sediment toxicity was reported from 62% of the tests conducted during the ten year period. The ElizabethRiver and Baltimore Harbor stations were reported as the most toxic areas based on sediment results.Sediment toxicity guidelines were exceeded for one or more of thefollowing metals at these two locations: arsenic, cadmium,chromium, copper, lead, nickel and zinc. At the Elizabeth Riverstations nine of sixteen semi-volatile organics and two of sevenpesticides measured exceeded the ER-M values in 1990. Ambientsediment toxicity tests in the Elizabeth River in 1996 showedreduced toxicity. Various semi-volatile organics exceeded the ER-M values at a number of Baltimore Harbor sites; pyrene anddibenzo(a,h)anthracene were particularly high at one of thestations (Northwest Harbor). Localized sediment toxicity was alsoreported in the Chester, James, Magothy, Rappahannock, andPotomac Rivers but the link with contaminants was not determined.Both spatial and temporal variability was less for sedimenttoxicity data when compared with water column toxicity data. Acomparison of water column and sediment toxicity data for thevarious stations over the 10 yr study showed that approximatelyhalf the time agreement occurred (either both suite of testsshowed toxicity or neither suite of tests showed toxicity).     

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.     

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.     

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.     

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.     

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.     

Seasonal characteristics of haze observed by continuous visibility monitoring in the urban atmosphere of Kwangju, Korea

Continuous visibility monitoring has been carried out inKwangju, Korea since May 1999. The total light extinctioncoefficient b _ext measured by a transmissometer andreveals seasonal trends in urban visual air quality,especially under hazy conditions with a visual range of lessthan 15 km. Seasonal atmospheric visibility under lowrelative humidity during the winter was observed to be betterthan during any other seasons. Summertime visibility wasseverely degraded due to highly increased light scattering byhygroscopic particles under high humidity atmosphericconditions. Visibility during spring and fall was alsomoderate. However, yellow sand in spring caused the lowestvisibility conditions over the measurement area for a fewdays. With continuous monitoring using the transmissometer,the daily average seasonal visual range was measured to be13.1, 9.2, 11.0, and 13.9 km in spring, summer, falland winter, respectively. Under the atmospheric humiditycondition less than 60%, visual range was observed tobe 16.1, 13.9, 15.1, and 16.6 km in spring, summer,fall, and winter, respectively. The mean light extinctionbudget by sulfate and nitrate aerosols was determined to bethe highest value of 63.71% during the summer and thelowest value of 27.08% during spring. During the `yellow sand dust' period, a mean light extinction budget by soil particles was estimated to be at an unusually high value of 44.22%.     

An Evaluation of Selenium Concentrations in Water, Sediment, Invertebrates, and Fish from the Republican River Basin: 1997–1999

The Republican River Basin of Colorado,Nebraska, and Kansas lies in a valley which contains PierreShale as part of its geological substrata. Selenium is anindigenous constituent in the shale and is readily leached intosurrounding groundwater. The Basin is heavily irrigated throughthe pumping of groundwater, some of which is selenium-contaminated, onto fields in agricultural production. Water,sediment, benthic invertebrates, and/or fish were collected from46 sites in the Basin and were analyzed for selenium to determinethe potential for food-chain bioaccumulation, dietary toxicity,and reproductive effects of selenium in biota. Resultingselenium concentrations were compared to published guidelines orbiological effects thresholds. Water from 38% of the sites (n = 18) contained selenium concentrations exceeding 5 g L^-1, which is reported to be a high hazard for selenium accumulation into the planktonic food chain. An additional 12 sites (26% of the sites) contained selenium in water between 3–5 g L^-1, constituting a moderate hazard. Selenium concentrations in sedimentindicated little to no hazard for selenium accumulation fromsediments into the benthic food chain. Ninety-five percent ofbenthic invertebrates collected exhibited selenium concentrationsexceeding 3 g g^-1, a level reported as potentially lethal to fish and birds that consume them. Seventy-five percent of fish collected in 1997, 90% in 1998, and 64% in 1999 exceeded 4 g g^-1selenium, indicating a high potential for toxicity andreproductive effects. However, examination of weight profilesof various species of collected individual fish suggestedsuccessful recruitment in spite of selenium concentrations thatexceeded published biological effects thresholds for health andreproductive success. This finding suggested that universalapplication of published guidelines for selenium may beinappropriate or at least may need refinement for systems similarto the Republican River Basin. Additional research is needed todetermine the true impact of selenium on fish and wildliferesources in the Basin.