Organochlorine contaminant concentrations in caddisfly adults (Trichoptera) collected from great lakes connecting channels

Pennsylvania-style light traps were used to capture adult Trichoptera from the St. Marys, St. Clair, Detroit and Niagara rivers, Canada. Adequate biomass was acquired in single, 2-h collections to permit triplicate gas chromatographic analyses of 1–4 g samples for 36 organochlorine contaminants. Contaminant levels varied unpredictably but relatively little among samples taken at monthly intervals over the summer. Samples collected simultaneously from the two sides of the Detroit R. reflected local sediment contaminant patterns, suggesting limited dispersal by adults. Genus-specific differences in contaminant concentrations within the Hydropsychidae and Leptoceridae probably reflect differences in larval habitats and manner of feeding. Contaminant concentrations and relative composition paralleled published reports of contaminants in sediments from collection locations. St. Marys R. caddisflies contained contaminant levels indistinguishable from samples collected at reference sites. St. Clair R. samples contained high levels of compounds associated with petrochemical industries located in the river's upstream reaches. High levels of polychlorinated biphenyls (PCBs) and most other contaminants in Detroit R. samples reflected industrial loadings near Detroit, Michigan. Niagara R. samples contained elevated concentrations of PCBs and pesticides. Cluster analysis grouped samples into five clusters each with unique contaminant composition. These also corresponded to geographic origin: St. Marys, St. Clair, Detroit and upper and lower Niagara rivers. The relative ease of collection and consistent results obtained render adult Trichoptera potentially valuable candidates for surveys of aquatic contamination over a broad range of geographical and ecological conditions.     

Multimedia environmental monitoring: 50 years at Hanford

Environmental monitoring has been an ongoing activity on the U.S. Department of Energy's Hanford Site in southeastern Washington for almost 50 years. Objectives are to detect and assess potential impacts of Site operations on air, surface and ground waters, foodstuffs, fish, wildlife, soil and vegetation. Data from monitoring effects are used to calculate the overall radiological dose to humans working onsite or residing in nearby communities. In 1989, measured Hanford Site perimeter concentrations of airborne radionuclides were below applicable guidelines. Concentrations of radionuclides and nonradiological water quality in the Columbia River were in compliance with applicable standards. Foodstuffs irrigated with river water taken downstream of the Site showed radionuclide levels that were similar to those found in foodstuffs from control areas. Low levels of ¹³⁷Cs and ⁹⁰Sr in most onsite wildlife samples and concentrations of radionuclides in soils and vegetation from on- and offsite locations were typical of those attributable to worldwide fallout. The calculated dose potentially received by a maximally exposed individual (i.e., based on hypothetical, worst-case assumptions for all routes of exposure) in 1989 (0.05 mrem/yr) was similar to those calculated for 1985 through 1988.In addition to monitoring radioactivity in fish and wildlife, population numbers of key species are determined. Chinook salmon (Oncorhynchus tshawytscha) spawning in the Columbia River at Hanford has increased in recent years with a concomitant increase in winter roosting activity of bald eagles (Haliaeetus leucocephalus). An elk (Cervus elaphus) herd, established by immigration in 1972, is also increasing. The Hanford Site currently serves as a refuge for Canada goose (Branta canadensis), great blue heron (Ardea herodias), and various plants and other animals, e.g., mule deer (Odocoileus hemionus), and coyotes (Canis latrans).     

Patchy distributions: Optimising sample size

A method for estimating sample size which does not require an a priori definition of desired precision, or the assumption that the population is normally distributed with constant variance, has recently been proposed. This paper discusses this method and presents five modifications which make the method easier to use and reduce the probability of estimating a larger sample size than is actually required. The method is extended and used to estimate the mean abundance of patchily distributed benthic organisms. The technique can be used to guide the design of any environmental sampling programme, be it physical, chemical or biological, where comparisons between times and/or locations are required. Trade-offs between numbers of replicates and numbers of levels/sites are discussed.     

Trend evaluation of water quality parameters in the Niagara and St. Lawrence Rivers

Physical and chemical (nutrients and major ions) indicators of water quality monitored by Environment Canada between 1977 and 1987 in the Niagara River at Niagara-on-the-Lake and in the St. Lawrence River at Wolfe Island are analyzed for seasonal and annual variations. Parametric methods such as moving averages and linear regression and nonparametric methods (Spearman's rank coefficient) are used to test for the existence of trends in these data. The results indicate that specific conductivity, sodium and chloride have decreased significantly over the period of study. During the same period there is no significant trend for either discharge and nutrients.     

Emissions of gaseous and particulate pollutants in a port and harbour region in India

Ports can generate large quantity of pollutants in the atmosphere due to various activities like loading and unloading,transportation, and construction operations. Determination of the character and quantity of emissions from individual sources is an essential step in any project to control and minimize the emissions.In this study a detailed emission inventory of total suspendedparticulate matter (TSP), particulate matter less than 10 m(PM₁₀), sulfur dioxide (SO₂) and nitrogen oxides (NO_x) for a port and harbour project near Mumbai is compiled. Results show that the total annual average contributions of TSP and PM₁₀ from all the port activitieswere 872 and 221 t yr^-1, respectively. Annual average emissions of gaseous pollutants SO₂ and NO_xwere 56 and 397 t yr^-1, respectively, calculatedby using emission factors for different port activities. The maximum TSP emission (419 t yr ^-1) was from paved roads, while the least (0.4 t yr^-1) was from bulk handling activity. The maximum PM₁₀ emission (123 t yr^-1) was from unpaved roads and minimum (0.2 t yr^-1) from bulk handling operations. Similarly the ratio of TSP and PM₁₀ emission was highest (5.18) from paved roads and least (2.17) from bulk handling operations. Regression relation was derivedfrom existing emission data of TSP and PM₁₀ from variousport activities. Good correlation was observed between TSP andPM₁₀ having regression coefficient >0.8.     

Persistent chlorinated pesticides in fish and cattle fat and their implications for human serum concentrations from the Sene-Gambian region

The concentrations of organochlorine pesticides (OCPs) in fish, shrimps, cattle fat and human serum samples from the Sene-Gambian region were measured using validated analytical methodologies. The results obtained were compared with those of other existing African studies and with data from other developing countries. In fish samples, p,p'-dichlorodiphenyldichloroethylene (p,p'-DDE) and HCB were detected with a frequency of 100%, whereas p,p'-dichlorodiphenyltrichloroethane (p,p'-DDT) was detected in eight, heptachlorepoxide in six and endosulfansulfate in five of the nine fish samples. Relatively low concentrations of OCPs were found in cattle and shrimp fat samples. p,p'-DDE and alpha-hexachlorocyclohexane (alpha-HCH) were the most frequently identified. The sum of HCHs ranged from undetected to 13.3 ng g-1 fat, the sum of DDTs from 11.1 to 199.2 ng g-1 fat and the sum of endosulfans from not detected to 49.7 ng g-1 fat in fish and shrimps. In serum samples, alpha-HCH, p,p'-DDE, o,p'-DDT and p,p'-DDT were detected in all 16 pooled serum samples, whereas endosulfansulfate, methoxychlor, mirex, heptachlorepoxide and endrin were detected in 15 samples with most of the concentrations below 10 ng mL-1. The concentrations of OCPs in human serum were given on a serum lipid and whole serum volume basis. The implications for the human diet of these OCP concentrations in serum were investigated by means of biomagnification factors related to the log Kow values of the targeted compounds. The current use of HCH mixtures was suggested to explain the unusually high alpha-HCH concentration. The distribution pattern of these OCPs in humans was also discussed and compared with that in other studies.     

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.     

Chemical monitoring and evaluation of the water quality of the Douro River at the Crestuma-Lever dam

Water taken from the Crestuma-Lever dam on the Douro River was evaluated considering the Portuguese Decree-law no. 236/98 of 1st August, 1998. This paper presents the metrological characteristics, validation of analytical methodologies and the data obtained from seasonal samplings. The test parameters selected are: temperature, pH, chloride, conductivity, carbon dioxide, alkalinity, hardness, oxidability, dissolved oxygen, BOD5, total suspended solids, sulfide, phosphate, silica, ammonium, nitrite, nitrate, sulfate, sodium, potassium, calcium, magnesium, iron, manganese, copper and zinc. From data analysis we can conclude that the water presented the following characteristics: a pH situated in the neutral zone; a median mineralization; a medium hardness; well oxygenated water; and a carbonate hardness exclusively due to bicarbonates. The temperature, pH, dissolved oxygen, ammonia, chlorides, sulfates, copper, zinc and BOD5 were compared with the legal limits presented in annexes XXI and I of Decree-law 236/98. The results relating to total hardness, nitrites, calcium, magnesium, sodium, potassium, aluminium, sulfides and oxidability were compared with the legal values in annex VI as there are no limits relating to these parameters in annexes XXI and I.     

SI-traceable certification of Cu, Cr, Cd and Pb in sediment and fly ash candidate reference materials

Many fields in environmental analytical chemistry deal with very low limits and thresholds as set by governmental legislations or transnational regulations. The need for the accuracy, comparability and traceability of analytical measurements in environmental analytical chemistry has significantly increased and total uncertainties are even asked for by accreditation bodies of environmental laboratories. This paper addresses achieving these goals to guarantee accuracy, quality control, quality assurance or validation of a method by means of certified reference materials. The assessment of analytical results in certified reference materials must be as accurate as possible and every single step has to be fully evaluated. This paper presents the SI-traceable certification of Cu, Cr, Cd and Pb contents in geological and environmentally relevant matrices (three sediments and one fly ash sample). Certification was achieved using isotope dilution (ID) ICPMS as a primary method of measurement. In order to reduce significantly the number of analytical steps and intermediate samples a multiple spiking approach was developed. The full methodology is documented and total uncertainty budgets are calculated for all certified values. A non-element specific sample digestion process was optimised. All wet chemical digestion methods examined resulted in a more or less pronounced amount of precipitate. It is demonstrated that these precipitates originate mainly from secondary formation of fluorides (essentially CaF2) and that their formation takes place after isotopic equilibration. The contribution to the total uncertainty of the final values resulting from the formation of such precipitates was in general < 0.1% for all investigated elements. Other sources of uncertainty scrutinised included the moisture content determination, procedural blank determination, cross-contamination from the different spike materials, correction for spectral interferences, instrumental background and deadtime effects, as well as the use of either certified values or IUPAC data in the IDMS equation. The average elemental content in the sediment samples was 30-130 micrograms g-1 for Pb, 0.5-3 micrograms g-1 for Cd and 50-70 micrograms g-1 for Cu. Cr was measured in one sample and was about 60 micrograms g-1. The concentrations in the fly ash sample were up to 2 orders of magnitude higher. Expanded uncertainty for the investigated elements was about 3% (coverae factor k = 2) except for Cr, (measured by high resolution ICPMS), for which the expanded uncertainty was about 7% (k = 2).     

A study of the distribution of lead, cadmium and copper between water and kaolin, bentonite and a river sediment

Experiments were carried out to monitor the equilibrium distribution of lead, cadmium and copper between an aqueous phase modelling natural water and a solid phase modelling natural sediment, under varying conditions. The aqueous phase was analysed using ETAAS and differential pulse anodic stripping voltammetry (DPASV), whereas XRD and FTIR were used to study the solid phase. Sorption isotherms at constant pH were measured. Conditional distribution constants were calculated as functions of the pH, the time of equilibration and the amount of solid material. The results obtained stress the need for standardization of the approaches to the study of water-sediment interactions in order to be able to evaluate and compare the extensive data from field measurements and to predict these interactions.