Spatial and Temporal Trends in Organochlorine Contamination and Bill Deformities in Double-Crested Cormorants (Phalacrocorax Auritus) from the Canadian Great Lakes

The levels of organochlorine contaminants (OCs) in the eggs of double-crested cormorants (Phalacrocorax auritus) from the Canadian Great Lakes, Lake Nipigon and Lake-of-the-Woods were monitored between 1970 and 1995. PCBs and p,p-DDE were present at the highest concentrations. Significant declines in OC concentrations on the Great Lakes were observed over this period for Lake Ontario, Lake Superior, Georgian Bay and North Channel but not Lake Erie where levels remained relatively stable. In the early 1970s, the greatest OC levels were generally observed in cormorant eggs from nesting sites in Georgian Bay and North Channel of Lake Huron. Between 1984 and 1995 mirex and PCB levels were consistently highest in samples from Lakes Ontario and Erie, respectively. Similar levels of PCDDs and PCDFs were observed from all regions of the Canadian Great Lakes in 1989. In general, OC levels in cormorant eggs between 1984-95 were ranked as follows: Lake Erie>Lake Ontario Lake Superior>Lake Huron. In 1995, eggshell thickness in Canadian Great Lakes cormorants, ranged from 0.423 to 0.440 mm and was on average only 2.3% thinner than pre-DDT era values. Between 1988 and 1996, 31 cormorant chicks with bill defects were observed at 16 different colonies (21% of all colonies surveyed) in Lakes Ontario and Superior, Georgian Bay and North Channel, and the main body of Lake Huron. No bill deformities were observed at reference sites in northwestern Ontario (Lake Nipigon and Lake-of-the-Woods). For the period 1988-96, the prevalence of bill defects in cormorant chicks (0.0 to 2.8/10,000 chicks) did not differ significantly (P > 0.05) among most regions in the Canadian Great Lakes. Georgian Bay was the only region to show a significant decrease in the prevalence of bill defects between the periods 1979-87 and 1988-95.     

PCB and p,p′-DDE in Lake Geneva brown trout (Salmo trutta L.), and their use as bioenergetic indicators

Gross growth efficiency of Lake Geneva brown trout (Salmo trutta) was estimated by monitoring age-related PCB and p,p-DDE accumulation, food contamination and annual growth.Estimation was carried out using 3-, 4-, and 5-yr old fish. Roach (Rutilus rutilus) were determined as the main component of trout diet. Estimated growth efficiency coefficients were 0.4 (3–4 yr old fish) and 0.17 (4–5 yr old fish). Nevertheless numerous parameters can affect the result; their respective influences are discussed.Related to fish age, PCB and p,p-DDE concentrations increase if expressed on a wet weight basis, but not if expressed on a lipid weight basis.At the same age, organochlorine residue concentrations keep similar values for trout and roach in spite of different trophic levels. Growth must be considered as a more dilution factor of PCB and p,p-DDE in trout compared with roach.     

Persistent organochlorine residues in fish and water birds from the Biobio river,Chile

Concentrations of polychlorinated biphenyls (PCBs), DDT and its metabolites, HCH isomers and hexachlorobenzene (HCB) were determined in fish and birds from different locations in the Biobio river basin (central Chile). Samples collected near the mouth of the river contained high concentrations of PCBs, reflecting the massive use of these xenobiotics in the urban and industrial areas of Concepcion and Talcauano. Samples collected in the central part of the basin contained very high concentrations of lindane that coincide with the widespread use of lindane-based pesticides (purified -HCH) in this area. DDT was distributed homogeneously throughout the basin, except at Laguna Icalma, the source of the river in the Andes. Most PCB residues in fish and birds consisted of congeners between penta- and hepta-chlorobiphenyls. In fish, the predominant congeners were the pentachlorobiphenyl 23445 (IUPAC number 118) and the hexachlorobiphenyl 2234455 (PCB-153); in birds 224455 (PCB-180) prevailed.     

Polychlorinated biphenyls, organochlorine pesticides and chlorobenzenes content of livers from Atlantic cod (Gadus morhua) caught off Halifax Nova Scotia

The mean levels ± s.d., (ranges) of organochlorines, pesticides, chlorobenzenes and polychlorinated biphenyl were determined in the livers of 100 Atlantic cod (Gadus morhua) caught off the east coast of Canada in 1980 and were as follows: PCB 1.71±0.90 (0.24–4.33); p,p-DDE 0.28±0.15 (0.01–0.84); p,p-DDD 0.10±0.09 (trace-0.84); p,p-DDT 0.15±0.09 (ND-0.58); -HCH 0.06±0.02 (trace-0.10); -HCH (ND-trace); heptachlor 0.02±0.01 (ND-0.04); heptachlor epoxide 0.15±0.37 (ND-2.16); dieldrin 0.06±0.11 (ND-0.71); hexachlorobenzene 0.02±0.01 (trace-0.05) mg kg^–1 (wet wt.). The levels of these compounds in 1980 have not changed over the previous eight years with the exception of PCB and the DDT group where there appears to be a general decline between 1972 and 1975 with no significant change thereafter.     

Declines in organochlorines in eggs of red-breasted mergansers from Lake Michigan, 1977–1978 versus 1990

From 1977–1978 to 1990, concentrations of polychlorinated biphenyls (PCBs) and most organochlorine pesticides declined in eggs of red-breasted mergansers (Mergus serrator) nesting on islands in northwestern Lake Michigan. Total PCBs decreased 60% (from 21 ppm in 1977–1978 to 8.5 ppm in 1990) and p,p-DDE decreased 66% (from 6.5 to 2.2 ppm). Dieldrin decreased only 16% (from 0.82 to 0.69 ppm). In 1990, 79.1% of incubated eggs hatched, which was not significantly different from the 83.5% that hatched in 1977–1978.The U.S. Government right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged.     

Concentrations and profiles of polychlorinated biphenyls, -dibenzo-p-dioxins and -dibenzofurans in livers of mink from South Carolina and Louisiana,U.S.A

In South Carolina, U.S.A., mink have been reintroduced from two apparently healthy populations to areas where populations haveexisted in the past but have been extirpated. High mortality wasobserved during transport of mink from the source populations. Inorder to elucidate the potential effects of dioxin-like compoundson the survival and reproduction of mink, concentrations of totalpolychlorinated biphenyls (PCBs), p,p-DDE, dioxin-likePCBs, polychlorinated dibenzo-p-dioxins (PCDDs), anddibenzofurans (PCDFs) were measured in livers of mink collectedfrom the source populations in South Carolina and Louisiana. Concentrations of total 2,3,7,8-tetrachlorodibenzo-p-dioxinequivalents (TEQs) for the South Carolina and Louisiana mink were21 and 14 pg g^-1, wet wt., respectively. PCB and TEQ concentrations were close to the threshold values that can, under laboratory conditions, elicit toxic effects in ranchmink. Therefore, any additional exposures of these populations toTEQs might adversely affect their populations.     

Distribution of Organochlorine Pesticides in the Chao Phraya River, Thailand

Water samples from the Chao Phraya River, the main river in Thailand were collected and analyzed during 1988–1994. Organochlorine pesticides such as HCHs, DDTs, aldrin, dieldrin and chlordanes were determined. Aldrin and dieldrin had high frequencies of occurrence in water samples. The concentration median of the pesticides was approximately one order of magnitude higher than those of total HCHs and DDTs. Levels of aldrin were relatively high in the upstream while levels of DDTs were high in the urban area of Bangkok during 1989–1990. p,p-DDE levels were relatively higher in 1992. No clear trends in the levels of pesticides were observed.     

Debromination of 1,4-Dibromobenzene and 4,4′-Dibromobiphenyl: A Model for Cleansing of PCBs

The aim of this study is to develop a catalytic method which has advantages over current method to detoxify and degrade environmentally harmful polychlorinated biphenyls (PCBs). A variety of catalysts have been employed in a preliminary study on 1,4-dibromobenzene and 4,4-dibromobiphenyl which may be considered to represent simple analogues of PCBs. The most satisfactory catalysts are those involving [Pd(dppf)] [dppf = 1,1-bis(diphenylphosphino)ferrocene], generated in situ from PdCl2(dppf) or Pd(dppf)2. In the presence of the reducing reagent, namely NaBH4, debromination has been achieved at relative mild conditions with high product yields (> 70%). Thus, our results indicate the possibility of dechlorination of PCBs with such catalysts.     

Comparative Studies on the Usefulness of Seven Ecological Indices for the Marine Coastal Monitoring Close to the Shore on the Swedish East Coast

The simultaneous behaviour of seven ecological indices(Hurlberts, Margalefs, Menhinicks, Shannons,species number, Jaccards and saprobic index) wasstudied based on phytoplankton data close to the shoreon the East coast of Sweden during the summer 1998.The sampling stations had a similar eutrophicationlevel and were located in bays. Standard phytoplanktondatabases were used in calculating the indices, whichwere later compared using cluster analysis.Hurlberts, Margalefs, Menhinicks, Shannons andspecies number indices, as measure of communitydiversity, produced similar trends which oftendiffered from those based on Jaccards index ofsimilarity. However, the simultaneous use of theseindices was found meaningful as a possible part of themonitoring close to the shore. The application of asaprobic index lead to erroneous conclusions in thestudied case.     

Soil-Water Partitioning and Desorption Hysteresis of Volatile Organic Compounds from a Louisiana Superfund Site Soil

The adsorption and desorption of three volatile organic compounds (1,2- dichloroethane, 1,1,2- trichloroethane and 1,1,2,2-tetrachloroethane) from a previously uncontaminated clayey soil sample from a Superfund site in North Baton Rouge,Louisiana was studied. In the linear range of the adsorption isotherm, the partition constants were not affected by the presence of the co-solutes. The adsorption isotherms over a wide concentration range on the soil followed the nonlinearFreundlich isotherm. The desorption of the compounds showedsignificant hysteresis at all concentrations studied. Approximately 20 to 70% of the adsorbed mass of organic compounds resisted the desorption even after five months ofsuccessive desorption steps. The desorption of four compounds(1,2-dichloroethane, 1,1,2-trichloroethane, 1,4-dichlorobenzeneand hexachlorobutadiene) from a contaminated soil sample fromthe same site was also studied. The aqueous concentration declined as the successive desorption steps progressed. For hexachlorobutediene the desorption can be visualized as occurring in two stages. The first stage involved a loosely bound or reversible fraction and the second stage involveda tightly bound or resistant fraction.     

The contamination of fish with chlorinated hydrocarbons in Portugal: continental coast and Azores islands

In a baseline study, muscle and liver from important commercial fish belonging to different trophic levels were analysed for organochlorines. Samples of sole, sardine and hake were collected from seven locations off the Continental coast and greater forkbeard and horse mackerel off two Azores islands. Residues of ppDDT, ppDDE and PCBs were present in all muscle and liver samples. ppDDD occurred in all liver samples and in most muscle samples, except in sole where it occurred in 29% of the samples. Dieldrin was detected less frequently and did not occur in samples from the Azores. The residue levels were generally similar to those detected in related species from the North Sea, except for samples of sole collected between the Tagus and Sado estuaries where much higher residues were obtained. In view of the low consumption of insecticides in the Azores, it is proposed that long-range transport of organochlorines by winds and/or marine currents is responsible for their presence in this area. The organochlorine residues found in these fish showed no relationship with their position in the food chain but the values did increase with the quantity of lipids present. An unknown compound analysed by GC-MS interfered with DDE quantification in one sample of greater forkbeard.     

Estimation of Emissions of γ-Hexachlorcyclohexane from the Great Lakes–St. Lawrence Ecosystem Using a Coupled Efficient Kalman Filter–Atmospheric Transport–Soil Model

An efficient linear Kalman filter has been combined with a coupled atmospheric transport and soil–air exchange model to determine organochlorine pesticides emissions on the regional scale. In this study, results of -HCH emissions from the Great Lakes–St. Lawrence ecosystem, estimated from the coupled model, are presented and discussed. A source receptor technique is used to identify a priori the locations of emission sources of -HCH, the emissions are then updated through a Kalman filtering procedure which minimizes the weighted difference between the predicted mixing ratios from the coupled model and the measured concentrations over the Great Lakes–St. Lawrence river region. Two experiments using the inverse algorithm are carried out. In the first experiment, the coupled atmospheric transport and soil–air exchange model is implemented to predict -HCH air and soil concentrations. Emissions are then updated every 12 days using the updated soil concentrations and emission factors. However, the updated emissions are not input into the coupled atmospheric transport and soil–air exchange model. On the other hand, in the second experiment the updated emissions are fed back to the coupled model, so that the model is reinitialized in each 12 days. The results from the inverse technique for the year 1995 have been compared with grided -HCH emission inventory in Canada, generated by emission factors. It is shown that the estimated emissions of -HCH are consistent with the measured emissions. It is found that the St. Lawrence valley has larger emissions of -HCH than the Great Lakes region, indicating an opposite distribution to the emission usage inventory, but in agreement with the measured -HCH concentration.     

Exposure estimates in assessing helath effects of air pollution

Air pollution has been associated with adverse health effects. Difficulties in interpreting studies of health effects of exposure to air pollution arise in estimating exposure. Until recently, studies of effects of air pollution have relied on pollution exposure measurements obtained from fixed location air pollution stations monitoring outside air (to evaluate compliance with air quality standards, rather than to examine population exposure). However, recent evidence suggests that there are substantial differences between air pollution levels measured at such sites and levels to which people are actually exposed, i.e. personal exposure. The present study examines effects of ambient urban air pollution on persons suffering from asthma, healthy non-asthmatic subjects and school children (in 2 Canadian cities, Toronto and Hamilton). Air pollution exposure is being assessed by data obtained from: (1) conventional abatement oriented fixed location air pollution monitoring stations, (2) an extensive population oriented network, (3) inside and (4) outside structures (homes and schools) as well as (5) personal air pollution samplers. The data indicate variability in these different estimates of exposure which have implications on health effects assessment.     

Reproductive and Physiological Effects of Environmental Contaminants in Fish-Eating Birds of the Great Lakes: A Review of Historical Trends

During the 1950s and 1960s, reproductive failures and population declines were observed in fish-eating birds such as gulls, terns, cormorants, herons, and eagles in the Great Lakes. DDE-induced eggshell thinning contributed to these declines, but other factors such as embryo toxicity also were implicated. With reduced releases of many pollutants, reproduction recovered in some species. However, biomonitoring during the 1980s and 1990s indicates continuing effects at highly contaminated sites. Improved analytical techniques and bioassays have allowed the assessment of the total dioxin-like toxicity of complex mixtures of organochlorines (TCDD-equivalents). Developmental defects such as embryo mortality, deformities, and edema have been associated with dioxin-like PCBs in several avian species. Improved biochemical techniques have allowed the measurement of biomarkers that detect physiological alterations associated with contaminants. Specific biomarkers studied in Great Lakes birds include cytochrome P-450 monooxygenases, highly carboxylated porphyrins, thyroxine, vitamin A, and immune function. Reproductive and physiological alterations are associated with population-level effects in Caspian terns and bald eagles that feed on highly contaminated fish. Biomonitoring using biomarkers and population-level measures in fish-eating birds will continue to be important for assessing the effects of contaminants on the Great Lakes ecosystem.     

Sequential Determination of Trace Metals in Sea Water by Inductively Coupled Plasma Mass Spectrometry After Electrothermal Vaporization of their Dithiocarmabamate Complexes in Methyl Isobutyl Ketone

A sensitive method for sequential determination of V, Mn, Fe, Co, Ni, Cu, Zn, Mo and Sb in sea water using an inductively coupled plasma mass spectrometry (ICP-MS) after electrothermal vaporization of their dithiocarbamate complexes in methyl isobutyl ketone (MIBK) has been investigated. All analyte elements were simultaneously concentrated 20 fold in a single extract and introduced into the plasma using a graphite rod electrothermal vaporizer (ETV). A sensitivity enhancement due to a chemical modification using a mixed modifier of palladium nitrate and magnesium nitrate was observed for all analyte elements. The limits of detection of the method ranged from 2 ng l-1 for Co to 329 ng l-1 for V. For the replicate determinations of the analyte elements in a sea water sample, the repeatability was within 10% (as a coefficient variation), except for V (12.8%). The recovery test performed on a sea water sample resulted in values ranging from 87% for Sb to 119% for V. With the exception of Mo, the application of this method for the determination of the analyte elements in sea water samples collected from the surface to the depth of 5000 m at the sampling station of 34°12.08N, 141°57.50E (Oct. 12, 1994) in the northwest Pacific Ocean resulted in vertical distributions and concentration ranges which were in a good agreement with those reported in literatures.     

Routine Measurement of Dissolved Inorganic 15N in Precipitation and Streamwater

The difficulty of measuring 15N in dilute solutions has limited the potential of ecosystem labeling experiments and model comparisons. By concentrating the N from large (up to 20 L) water samples on ion-exchange resin columns, we obtained enough N for accurate and reproducible 15N measurement using the Teflon tape diffusion method. Analysis of standards demonstrated >95% recovery of inorganic N from samples, and 15N values comparable to those obtained using standard distillation methods. The value of the blank at our laboratory was 0.16 moles N. Analytical precision was within 2 15N when samples of streamwater from the Bear Brook Watersheds (1800 eq · ha-1 · yr-1 N addition at 192 15N) were kept frozen until analysis. The analytical process is lengthy, but once set up can easily be performed for large numbers of samples.     

Heavy metal concentration in the moss Pleurozium schreberi in the Niepołomice Forest,Poland: changes during 20 years

The Niepoomice Forest is a large forestcomplex (110 km²) situated in southern Poland 10 to 30 kmto the east of the urban industrial Kraków agglomeration andsteelworks, which was built up on the outskirts of the city in1950. Due to prevailing westerly winds, the forest is affectedby pollutants emitted by both the steelworks and the city. Thelevel of heavy metal contamination in the Niepoomice Forestwas described using a sensitive bioindicator – the moss Pleurozium schreberi. Mean concentrations of metals in mosscollected in the Niepoomice Forest were Cd – 0.71, Cr – 2.4,Cu – 8.6, Fe – 673, Pb – 12.7, and Zn – 61 mg/kg.Concentrations of heavy metals in moss in the NiepoomiceForest decreased in time. As compared with the relatively cleanarea in north-eastern Poland (Puszcza Biaowieska), the concentration of Fe was 2–9 fold and Pb 4–6 fold higher in theNiepoomice Forest in 1975, while in 1998 4 fold and 2 fold,respectively. In both 1975 and 1998 the most polluted by heavymetals was the western part of the Niepoomice Forest (closestto the pollution sources) and the area along the roads insidethe forest complex.     

Biological effect-test systems for the early recognition of unexpected environmental changes

Pre-marketing assessments of chemicals regarding their potential environmental impacts contain numerous sources of error and uncertainties. Practices and methods for the evaluation of environmental risks posed by individual pre-selected agents seem unsuitable for detecting unexpected trends in the environment. This is particularly so in view of the multitude of anthropogenic assaults on the environment and their complex interactions. Therefore, requirements for symptom-oriented biological effect-test systems, bioprobes, capable of reacting sensitively to environmental changes of unknown origin were conceived. Bioprobes designed to detect biological effects should respond to a broad spectrum of anthropogenic chemicals. They are environmental quality measuring devices consisting of cultivated organisms, cells, organelles or biomolecules in combination with recording units. In contrast to traditional biotests for chemical testing, bioprobes are deliberately exposed to selected segments of the environment for certain periods of time. During and after such exposures, changes of defined biological states or process rates—observation elements—are registered.     

Methane in ocean waters: Concentration and carbon isotope variability at East Pacific Rise and in the Arabian Sea

Methane concentrations and stable carbon isotope ratios of water samples from the East Pacific Rise (EPR) at 21°S and the Arabian Sea (24°N, 65°E) have been determined. EPR surface water is in equilibrium (ca. 50 nl/L and –50<¹³CH₄<–46) with atmospheric methane. Deep background water has the signature of the remaining fraction of atmospheric methane partially oxidized in the water column by bacteria. Bottom near, hydrothermally influenced vent methane (>100nl/L and –30<¹³CH₄<–22) is detectable only close to the seep site. There is no input of hydrothermal methane into the atmosphere. EPR water is considered to be rather a sink than a source of atmospheric methane. Surface waters of the Arabian Sea are enriched in methane relative to the atmosphere (source for atmospheric methane). Carbon isotope ratios point to a bacterial origin of methane (¹³CH₄<–55) that is generated in the surface waters. Concentration changes and variations of carbon isotope ratios also suggest that methane seeping from the sea floor sediments of the Arabian Sea is oxidized by bacterial activity and does not reach the atmosphere.     

Thresholds in eutrophication of natural waters

The population density of bacterioplankton and the concentration of dissolved organic carbon combined is a useful indicator to monitor subtle variations in the amount of eutrophication. Both parameters can be measured precisely and readily by widely accepted routine techniques that require little skill. Thresholds of eutrophication can be established to maintain the Health of Natural Waters using this indicator.