Escape and survival of Corophium volutator and Ilyanassa obsoleta exposed to freshwater and chlorothalonil.

The behavioural response and survival of marine mud snails and mud shrimp exposed to freshwater and the fungicide chlorothalonil (tetrachloroisophthalonitrile) was investigated. Amphipods were less tolerant of lower salinity than snails, with 50 and 76% survival associated with 5 and 0% seawater in freshwater, respectively. However, 50% of snails displayed a defence mechanism by retracting within their shell when exposed to 70% freshwater. Both species displayed an avoidance to chlorothalonil spiked at >100 ng/g and/or >100 ng/mL in sediments and seawater, respectively. The avoidance response of amphipods was observed along with a reduced swimming ability and increased lipid content. Snails displayed a higher susceptibility to physical stress, with an increased number unable to twist from being on their shell to their foot, and with longer righting time. Behaviour was affected at chlorothalonil concentrations of 0.001-0.01 ng/g and/or ng/mL, with a variability that could be due to degradation by the microbial community. Ascertaining the latter observations requires state-of-the-art chemical analyses.

Spatial variations in biomarkers of Mytilus edulis mussels at four polluted regions spanning the Northern Hemisphere.

Economic and social developments have taken place at the expense of the health of the environment, both locally and on a global scale. In an attempt to better understand the large-scale effects of pollution and other stressors like climate change on the health status of Mytilus edulis, mussels were collected during the first two weeks of June 2005 at three sites (one pristine and two affected by pollution) located in each of the regions of the Canadian West Coast, the St. Lawrence estuary, the Atlantic East Coast and the northwestern coast of France, covering a total distance of some 11000km. The mussels were analyzed for morphologic integrity (condition factor), gametogenic activity (gonado-somatic and gonad maturation index, vitellogenin(Vtg)-like proteins), energy status (temperature-dependent mitochondrial electron transport activity and gonad lipid stores), defense mechanisms (glutathione S-transferase, metallothioneins, cytochrome P4503A activity and xanthine oxidoreductase-XOR), and tissue damage (lipid peroxidation-LPO and DNA strand breaks). The results showed that data from the reference sites in each region were usually not normally distributed, with discriminant factors reaching the number of regions (i.e. four), except for the biomarkers gonadal lipids, XOR and LPO in digestive gland. The integrated responses of the biomarkers revealed that biomarkers of stress were significantly more pronounced in mussels from the Seine estuary, suggesting that the impacts of pollution are more generalized in this area. Mussels from the Seine estuary and the Atlantic East Coast (Halifax Harbor) responded more strongly for Vtg-like proteins, but was not related to gonad maturation and gonado-somatic indexes, suggesting the presence of environmental estrogens. Moreover, these mussels displayed reduced DNA repair activity and increased LPO. Factorial analyses revealed that energy status, cytochrome P4503A activity and Vtg-like proteins were the most important biomarkers. Adaptation to warmer temperatures was reflected at the energy status levels, mussels from both the polluted and warmer sites displaying increased ratios of mitochondrial activity to lipid stores. Regional observations of biomarkers of energy status, gametogenesis and pollutant-related effects were influenced by nutrition, oxygen availability (eutrophication), and thermal history.

Assessing PAH exposure in feral finfish from the Northwest Atlantic.

Polycyclic aromatic hydrocarbon (PAH) concentrations were examined in small finfish (<30 cm) represented by capelin, sand lance, American plaice, yellowtail flounder and herring collected opportunistically in various NAFO divisions. Analyses were performed on whole fish and in a portion of the samples; concentrations in internal organs were compared to the rest of the carcass. The effect of pool size, size differences within and between species, lipid content and location were examined to interpret PAH concentrations. Measurements were carried out before the development of the Hibernia oil fields and represent baseline levels for future comparison. Limits in assessing future risk that could be due to discharges of produced water or accidental oil spills are also discussed. Increasing knowledge on the bioaccumulation of PAH, on the production of bile metabolites, the formation of DNA-adducts and of the potential toxic effects associated with PAH will lead to better ecosystem management and protection for future generations.

Endocrine disruption and health effects of caged mussels, Elliptio complanata, placed downstream from a primary-treated municipal effluent plume for 1 year.

Freshwater mussels, Elliptio complanata, were caged in special benthic pens and were immersed at one upstream (Ups) site and two downstream sites (8 and 11 km) of a primary-treated municipal effluent plume for 1 year. The levels of metallothionein-like proteins (MT), lipid peroxidation, protein-free DNA strands and glutathione S-transferase (GST) activity were assayed in digestive gland, gill and gonad tissues to evaluate biological effects and damage. The levels of monoamines (serotonin and dopamine) in nerve ganglia, ATP-dependent transport activity and monoamine oxidase (MAO) activity were also investigated in the homogenates, synaptosomes and mitochondria, respectively. Results showed that significant amounts of sediment accumulated in cages and 82% of mussels survived the yearlong exposure period at the downstream sites. MT-like proteins were induced in all tissues with the following response intensity: gill (3-fold), digestive gland (1.4-fold) and gonad tissues (1.3-fold). Lipid peroxidation decreased (2.5-fold) in digestive gland but increased in gill (1.6-fold) and in gonad tissues (1.5-fold). GST activity was readily increased in digestive gland (2.5-fold), suggesting the presence of organic contaminants in the plume. Levels of protein-free DNA strands did not vary significantly in digestive gland and gill tissues but were significantly reduced in gonad tissues (2.5-fold) relative to the upstream site. In visceral nerve ganglia, both serotonin and ATP-dependent serotonin transport decreased 1.7-fold with a 4-fold increase of 5-hydroxyindole acetate (5-HIAA, a serotonin metabolite) level relative to the upstream site. However, MAO activity was somewhat reduced at downstream sites (0.7- to 0.9-fold of the activity at the upstream site). Dopamine levels were found to be decreased (1.5-fold), but dopamine ATP-dependent transport activity was increased 1.8-fold, suggesting reduced dopaminergic activity. These results indicate that estrogenic chemicals are likely at play, and the increased dopamine and decreased serotonin ATP-dependent transport suggest that the municipal plume was serotonergic for mussels located at the downstream sites. Mussels exposed for 1 year display a complex but characteristic pattern of responses that could lead to harmful health effects including neuroendocrine disruption of reproduction.

Stress on stress response of wild mussels, Mytilus edulis and Mytilus trossulus, as an indicator of ecosystem health.

Mussels' health as indicated by the survival time of 50% of sampled animals (LT(50)) when maintained in air at 15 degrees C was examined at three sites in Halifax Harbour with expected differing levels of contamination. Condition and gonad indices, lipid content and the body burden of polycyclic aromatic compounds (PACs) were compared with this stress response in 60 groups of mussels covering two species. At each sampling time, the bioaccumulation of PACs, lipid content and condition indices were higher within Mytilus edulis and Mytilus trossulus displaying shorter survival than at the other sites. M. edulis was generally more tolerant than M. trossulus (for n=11, LT(50) of 9.3 and 7.9 days), with indications of shorter and later gonad development in M. trossulus. Minimum and maximum tolerance was apparent in June and October (LT(50) spanning 3-14 days), respectively. Our results indicate that the stress on stress response provides a simple and sensitive indicator of environmental health, which could be integrated with mussel watch studies.

Polycyclic aromatic musk compounds in sewage treatment plant effluents of Canada and Sweden--first results.

Polycyclic musk fragrances (PMF) are widely used fragrances for cosmetics and other personal and household care products. Quantitative data on PMF (HHCB-Galaxolide, AHTN-Tonalide, ATTI-Traseolide, AHMI-Phantolide, ADBI-Celestolide, and DPMI-Cashmeran) and the most prominent nitro musks (Musk Xylene-MX, and Musk Ketone-MK) in different wastewater treatment effluents in Canada and Sweden are presented to provide preliminary information on the variations within the emission pattern of these compounds. In all samples HHCB and AHTN were detected at concentrations of up to 1300 and 520 ngl(-1), respectively. ADBI, AHMI were also present, but close to the detection limit. The other PMF DPMI, ATTI, and more surprisingly musk ketone and musk xylene were not detected in any sample analysed. In comparison the samples from Canada were contaminated at a higher level than the Swedish samples, by a maximum factor of ca 10 for HHCB and AHTN.

Tracing the source of 3,3'-dichlorobiphenyl found in samples collected in and around Halifax Harbour.

3,3'-dichlorobiphenyl (IUPAC No. 11), a chlorobiphenyl (CB) that is not generally analysed in environmental studies of CBs, is found, sometimes at high concentrations, in water, suspended particulate material, biota and sediments from Halifax Harbour, NS, Canada. The results presented demonstrate the need for investigations of non-Aroclor CBs like CB 11. Not only can they have rather elevated environmental concentrations like those reported here for CB 11, but they also can be members of the more toxic non-ortho class of CBs and thus important from a toxicity standpoint. The focus of this paper was to investigate the possible sources of CB 11, a trace constituent of commercial mixtures, but dominant in various environmental compartments of Halifax Harbour.

Distribution of PACs in surficial sediments and bioavailability to mussels, Mytilus edulis of Halifax Harbour.

Surficial sediments and blue mussels were collected around the perimeter of Halifax Harbour. Samples were analysed for the levels and fingerprint of polycyclic aromatic compounds (PACs). The objective was to explore the relationship between contaminant profiles in sediments and in mussels and to explore the possibility of deducing their sources, pattern of deposition and circulation in the harbour. Combustion derived compounds predominated in both sets of samples, with more variability observed in the level of petroleum derived hydrocarbons in mussel samples. Biota-sediment accumulation factors (BSAF, dry/dry wt.) varied throughout the harbour, ranging from means of 0.006 to 1.26, where generally fluoranthene displayed the highest BSAF. Sediments and mussels give complementary views of the geographical distribution of contaminants, they reflect the state of benthic and pelagic habitats. Results observed for Halifax Harbour are discussed from the perspective of published data.

Dietary exposure of finfish to aromatic contaminants and tissue distribution.

Large rainbow trout (400 g) were exposed to food pellets spiked with four polycyclic aromatic compounds (PACs). Muscle, liver, internal organs, fatty tissue, and blood were analyzed after 5, 10, 15, and 19 weeks for PAC, lipid, and moisture content. At all collection times, concentrations expressed on a per gram basis were higher in fatty tissue and internal organs, followed by liver and muscle, and lowest levels were observed in blood. When examining the tissue burden, the highest bioaccumulations of carbazole, dibenzofuran, dibenzothiophene, and fluorene were in muscle and internal organs, intermediate in fatty tissue, and lowest in blood and liver. Carbazole with the lowest log K(OW) showed the lowest concentration within any tissue. Levels in tissues were significantly correlated to log K(OW) (> 5% level of significance), especially with longer exposure, and were more highly correlated when examining muscle, fatty tissue, and internal organs (> 0.05%). Different tissues displayed different time trends, and ratios between organs help determine the length of exposure. The most striking change in levels observed with time was in internal organs relative to other tissues, particularly when compared to daily exposure. The elimination of contaminants in feces and gallbladder bile was also compared, because they represent additional tools to assess recent exposure.

Separation and characterization of gall bladder bile metabolites from speckled trout, Salvelinus fontinalis, exposed to individual polycyclic aromatic compounds.

Speckled trout, Salvelinus fontinalis, were orally exposed to individual polycyclic aromatic compounds (PACs) represented by benzo[a]pyrene, carbazole, chrysene, dibenzofuran, dibenzothiophene, fluorene, phenanthrene, and pyrene. Fish were sacrificed 7 d after exposure and the gall bladder removed for bile analysis. High pressure liquid chromatography (HPLC) with fluorescence (F) and ultraviolet (UV) detection was used to determine the presence of PAC derivatives in the bile without pretreatment. Glucuronide conjugates were predominant in all exposures with variable amounts (0-53%) of phenols and starting material. Identification of compounds was confirmed by selective extraction of less polar nonconjugated PACs and enzymatic hydrolysis of water-soluble material. This was followed by HPLC and/or gas chromatography-mass spectrometry (GCMS) characterization of the produced phenols. Total metabolite levels varied widely among compounds.

Essential elements and priority contaminants in liver, kidney, muscle and blubber of harp seal beaters.

Concentrations of 22 elements were determined in blubber, liver, kidney and muscle of five male and five female, 8-month-old harp seals (Phoca groenlandica) by ICP-MS. Young harp seals are hunted during the spring and fall and represent an important traditional dietary item for some northern fishing communities. Interest in the commercial use of seal meat products and the limited data on the level of contaminants in tissues of harp seal beaters motivated our investigation. For most elements, concentrations in liver or kidney were greater than those in muscle. Blubber concentrations were generally lowest, but concentrations of Li, As, Sr, Ba and Pb were highest in blubber. Largest concentration factors [(tissue)/(water) > 10,000] were seen for P, Fe, Zn, Cu, Cd, Se, Mn, Ag, Pb and Co, a list that includes essential elements such as Fe and Zn, as well as several important contaminants such as Cd and Pb. Differences in concentration between male and female seals were only seen in eight of 88 element/tissue comparisons. Any effects of environmental exposure due to location or dietary intake are difficult to detect. Principle component analysis shows an association of Ca with Sr and P with S; and also a distinct grouping of the elements V, Mo, Cu and Ag.

Levels, persistence and bioavailability of organic contaminants present in marine harbor sediments impacted by raw sewage.

As part of a program to investigate the levels, fate and bioaccumulation of organic contaminants in a polluted marine harbor, organochlorine compounds including the polychlorinated biphenyls (PCBs), dichloro diphenyltrichloroethane and metabolites (DDTs), chlordanes, dibenzo-p-dioxins (Ds) and dibenzofurans (Fs), polycyclic aromatic hydrocarbons (PAHs) and sulphur hetero cycles were analysed in sediments spiked with St. John's Harbor sludge. Winter flounder (Pseudopleuronectes americanus) were exposed to these sediments containing six levels of harbor sludge during four winter months. Following exposure, sediments were reanalysed to investigate the persistence of the contaminants. The primary contaminants detected were PAHs (approximately 5000 ng/g), predominantly alkylated phenanthrenes, fluoranthene and pyrene; PCBs with a predominance of Aroclor 1260 signature (approximately 64 ng/g), DDTs (approximately 5 ng/g), hepta and octachloro dioxins and furans (approximately 0.5 ng/g) with very low levels of less chlorinated congeners. The PAHs degraded with an estimated half life of 2 to 3 months, while no significant degradation could be attributed to the other compounds. Bioaccumulation to muscle showed the potential uptake of contaminants in biota inhabiting the harbor. A dose-response relationship was observed between spiked sediments and the concentrations of PCB congener 153 and unresolved congeners 138/163/164 in muscle. Of the dioxins and furans, only 2, 3, 7, 8-tetrachlorofuran was detectable in muscle and at a similar concentration in all exposures indicating a similar bioavailability independent of the fraction of sludge in sediments. Of the PAHs, only naphthalene and methyl naphthalenes were detected in muscle, but did not display a dose-response. One bile metabolite of pyrene was quantified and demonstrates metabolism. Biota-sediment accumulation factors were of 0.2 to 7 indicating that equilibrium was approached, with the exception of the hepta and octachloro dioxins and furans which were not significantly bioaccumulated.

Levels of organochlorine and polycyclic aromatic compounds in harp seal beaters (Phoca groenlandica).

Chlorinated dibenzo-p-dioxins, dibenzofurans, chlorobiphenyls, organochlorine pesticides and polycyclic aromatic hydrocarbons were measured in blubber, liver, kidney and muscle of five male and five female, 8-month-old harp seals (Phoca groenlandica). Levels of organochlorine contaminants were lowest in muscle, nearly 100 times higher in blubber and intermediate in kidney and liver. Only 2,3,7,8-tetrachlorodibenzofuran was detected in all liver and blubber samples (0.45 and 3.15 pg/g wet wt., respectively). Concentrations of chlorobiphenyls expressed as Aroclor 1254 were 3.8 and 8.2, 8.6 and 21.5, 23 and 73, and 945 and 890 ng/g wet wt. in the muscle, kidney, liver and blubber of female and male seals, respectively. p,p'-DDE, trans-nonachlor, oxychlordane and alpha-HCH were the additional predominant organochlorine compounds at 460 and 460, 415 and 530, 300 and 390, and 190 and 230 ng/g wet in the blubber of female and male seals, respectively. Concentrations of chlorobiphenyls and pesticides in muscle, liver and kidney were two-three times higher in males compared to females, whether expressed on a wet weight or a lipid weight basis, and approximately equal in blubber, even though the blubber layer of females was 30% thicker than that of males. Naphthalene and its C1-C3 homologues were detected in all tissues, generally at concentrations below 10 ng/g wet wt. The concentrations of PCBs and DDTs in blubber are considerably lower than those reported for juvenile seals from the same area 20 years ago. PCB and organochlorine pesticide concentrations and profiles are discussed in relation to those reported from other areas, as well as to sex and age of the seals.

Dietary and aqueous exposure of finfish to organochlorine compounds: A case study

The level of organochlorine compounds was determined in whole capelin, Mallotus villosus, and compared to concentrations determined in tissues of yellowtail flounder, Pseudopleuronectes ferruginea, that fed on capelin for 2 years while maintained in tanks. Capelin represent part of the diet of offshore yellowtail flounder, however, they come to the beaches to spawn and were collected inshore for the feeding experiment. Therefore, inshore-offshore capelin concentrations were compared to investigate differences, while variables such as fish weight and lipid content were examined to give a better view of the range of contaminants concentrations in capelin. During two years, weekly exposure of flounder was to 148 L of water, as opposed to a dietary intake of 1 g of capelin. Although the level of contaminants was only measured in capelin, it can be estimated for the water, using results obtained on the level of contaminants in sediments obtained in a different study. According to our calculations, levels of contaminants were three to 20 times higher from the aqueous compared to the dietary uptake of inshore flounder, increasing with lower hydrophobicity. Exposure was from less than 10 to up to 100 times lower in expected and/or published results for offshore food and water, respectively. This comparison suggests a major influence of inshore waters on the bioaccumulation of contaminants in some inshore marine species, although the effect of altering the diet of captive finfish can not be disregarded.

Organochlorines in Pleuronectidae: comparison between three tissues of three species inhabiting the Northwest Atlantic.

Muscle, liver, and gonad from three species of flatfish, turbot, American plaice, and yellowtail flounder collected in the Northwest Atlantic were analyzed for a variety of organochlorine contaminants. Female flounder and plaice had lower concentrations of organochlorines than males, in all tissues. Comparing values to those previously obtained for Atlantic cod showed that concentrations in liver, the organ most often used in biomarker studies, followed the order: cod > turbot > plaice > flounder and correlated with lipid content. Muscle concentrations, which are important from a consumers perspective, followed the order: turbot > plaice > flounder > cod and were also correlated with lipids. The concentration of contaminants in gonads, the organ that informs on the future of a species were nearly undetectable. Cluster analyses demonstrated that the environmental behaviour of these contaminants can be subdivided into groups, consistent with their known chemical origin. Of the series of total and specific polychlorinated dibenzo-p-dioxins and furans studied, only tetrachlorodibenzofuran was present in most tissues.

Bioaccumulation of aromatic hydrocarbons from sediments: a dose-response study with flounder (Pseudopleuronectes americanus).

Pseudopleuronectes americanus were chronically exposed to Hibernia crude oil in sediments, for 4 months. Oil was added to sediments at five concentrations between 0.09 and 4.5 mg/g (dry weight) and was 0.10-0.90 mg/g, at the termination of the exposure. Bioaccumulation measured in terms of fluorescence or in terms of the concentration of specific aromatic targets, increased with dosage. Accumulation of hydrocarbons was observed in muscle tissue (0.22 microgram/g, dry weight), when concentration of the sum of 27 polycyclic aromatic compounds (PAC) in sediments was of 0.65 microgram/g (E-50), at the end of the 4-month period. Of the 27 parental and alkylated polycyclic aromatic compounds analyzed, alkylated naphthalenes predominated in muscle (90-100%) and in sediments (30-60%). Bioaccumulation factors were derived for 13 compounds detected in muscle, at the three higher exposures. Liver concentrations (fluorescence) were higher than in muscle, but did not display a noticeable dose-response. Several alkylbenzenes, a C-2 biphenyl and C-4 acenaphthene were also detected in muscle extracts. The development of dose-response relationships for polycyclic aromatic hydrocarbons (PAH) present in sediment, in relation to bioaccumulation in flatfish, is of major interest for evaluating the environmental effects of oil contamination.

Polycyclic aromatic compounds in cod (Gadus morhua) from the Northwest Atlantic and St. Lawrence Estuary.

There is limited information available on levels of polycyclic aromatic hydrocarbons (PAH) in major fish populations including populations from the Northwest Atlantic. The cod (Gadus morhua) stocks off eastern Canada form the basis of one of the world's most important fisheries. Muscle tissues of cod collected from Northwest Atlantic Fisheries Organisation (NAFO) management Divisions 2J, 3K and 3Ps off Newfoundland and Labrador, as well as three contaminated sites in the Gulf of St. Lawrence were analyzed for total polycyclic aromatic (PAC) by fluorimetry. Concentrations were determined in terms of crude oil and chrysene equivalents in line with recommendations of the International Oceanographic Commission. Overall, relatively low concentrations of PAC were found, the highest values generally being below 0.1 microgram/g (dry weight) in terms of chrysene equivalents. Similarly, only trace levels of a few PAH were detected in composite samples analyzed by gas chromatography-mass spectrometry (GC-MS). It is of interest that the highest levels of PAC were found in fish from NAFO Division 3K, while concentrations in fish from the two contiguous zones, 2J and 3Ps, as well as the Gulf of St. Lawrence, were similar. Division 3K is a major fishing zone and it is important to determine if trawler fleets are important sources of hydrocarbons derived from fossil fuels, in this and similar fishing areas of the world's oceans.

Polycyclic aromatic compounds in Northwest Atlantic COD (Gadus morhua).

Twenty-seven polycyclic aromatic compounds (PAC) including polycyclic aromatic hydrocarbons (PAH) and polycyclic aromatic sulphur heterocycles were analysed in muscle, liver and ovaries of cod (Gadus morhua) from the Northwest Atlantic. These PAC include the 16 PAH priority pollutants (EPA recommendation), alkylated naphthalenes, phenanthrene-anthracenes as well as dibenzothiophenes (DBT). Aromatics were undetectable in muscle. One of the analysed PAC was detected in one ovary and six in another ovary sample. Liver samples contained between 1 and 9 PAC. Of the parental PAH, only acenapthene (18 ng/g, dry weight), fluorene (28 ng/g) and chrysene (22 ng/g) were detected once each in two liver samples, while fluorene (72 ng/g) was detected once in one of the ovaries. C-2 DBT was the major component in ovaries and liver (8-86 ng/g), while C-3 and C-4 alkylated phenanthrene-anthracene (12-78 ng/g) were the next major components detected in the liver samples. This is the first detailed study of PAH and PAC in finfish from the Northwest Atlantic.

Organochlorines including polychlorinated biphenyls in muscle, liver, and ovaries of cod, Gadus morhua.

Twenty-three specific organochlorine contaminants and polychlorinated biphenyls (PCBs), measured as three Aroclor standards were analyzed in muscle, liver, and ovaries of cod, Gadus morhua, collected in the Northwest Atlantic. In general, contaminants were undetectable in muscle tissue, while concentrations were 10 times lower in ovaries than liver (wet weight). Comparison of results to other locations indicated a similarity between the ratio of the concentrations of p,p'-DDE, p,p'-DDD and p,p'-DDT, in liver of cod from the northern North Sea and from the Northwest Atlantic, although with lower levels in the present study. The ratio of alpha-HCH and gamma-HCH was between that of the central and northern North Sea. Similar ratios tend to indicate similar residence times in the atmosphere, from source to sampling area. Comparison of sigma PCB and sigma DDT in the liver of cod from various geographical locations showed the following general trend in concentrations: Arctic, Northwest Atlantic, West Atlantic, Norway < North Baltic, Nova Scotia, North Sea < South Baltic. It was observed that if the liver concentration of one compound was low (high), there was a tendency for all compounds to be low (high). Cluster analysis of organochlorines in liver pointed to the presence of four basic clusters, which could reflect similar physical chemical properties within a group. Concentrations of organochlorines in ovaries were below levels expected to affect egg and larval viability.