Accumulation of organotin in Littorina littorea and Mya arenaria from Danish coastal waters

Organotin concentrations were determined in seawater, sediment and selected molluscs collected from the vicinity of the island of Fyn, Denmark. The extent of organotin contamination varied with the proximity of sampling sites to marinas and commercial shipping activities. Seasonal reductions in environmental TBT concentrations coincided with removal of pleasure craft from marinas during the winter season. At marina sites, concentration factors for TBT were 150-1500 for sediment and 500-10,000 for Littorina littorea (compared with seawater concentrations). Away from marina sites, Mya arenaria concentrated TBT by a factor of 57,000 to 220,000. The concentrations of TBT in M. arenaria from relatively clean sites were more than 10 times higher than found in L. littorea from heavily polluted marinas. M. arenaria were absent from marina sites and their immediate surroundings. Of the total organotin found in M. arenaria throughout the year, 80-90% was in the form of TBT. In contrast, in L. littorea approximately 60-70% of the total organotin was present as TBT in spring, but this proportion fell to 20-40% during autumn and winter. M. arenaria shows potential as a bioindicator organism of TBT pollution as it appears to have a very limited ability to metabolise and eliminate TBT, yet can tolerate quite high levels of TBT exposure. L. littorea might be used as a bioindicator of short-term fluctuations in TBT concentrations at heavily polluted sites. It is concluded that continued presence of TBT in the Danish coastal ecosystem may still pose an ecotoxicological threat.     

Concentrations of organotin compounds in sediment and clams collected from coastal areas in Vietnam

Levels of butyltin (BT) and phenyltin (PT) compounds were determined in sediments and clam Meretrix spp. collected from north and central coastal areas in Vietnam. Concentrations of TBT in sediments ranged from 0.89 to 34 ng g(-1) dry wt and those in clams ranged from 1.4 to 56 ng g(-1) wet wt. The levels of TBT in sediments and clams from Vietnam were within limits reported from other countries. Further, the TBT level in clams was lower than the tolerable average residue level (TARL) estimated based on tolerable daily intake (TDI). Trace amounts of PTs were also found in both sediment and clam samples. In sediments from north and central Vietnam, the concentrations of TBT were highest in the order of Hue (28 ng g(-1) dry wt), Cua Luc (15 ng g(-1) dry wt), Sam Son (6.3 ng g(-1) dry wt), and Tra Co (5.5 ng g(-1) dry wt). Among the clams from north and central Vietnam, the levels of TBT in clams from Cua Luc were dramatically high at 47 ng g(-1) wet wt. TBT formed the principal butyltin species in sediment at all sites studied. The ratios of TBT in sediment were higher among BT compounds at all study sites. Of total BTs, TBT was the dominant species in clams from almost all sites studied. In spatial distribution, TPT showed a pattern similar to TBT, suggesting the use of TPT as an antifouling paint. The partition coefficient between sediment and calms was calculated. The partition coefficients of TBT and TPT were 2.01 (0.56-5.5) and 9.23 (3.1-20), respectively. These results show that sediment-bound TBT is a source of contamination to clams in addition to dissolved TBT.     

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.     

Concentration of bioactive compounds in mussels Mytilus galloprovincialis as an indicator of pollution

The polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organotins were analyzed in mussels Mytilus galloprovincialis from polluted and unpolluted sites from Mokpo Bay, Korea. The total PAH's concentrations (10(-3)mgkg(-1)) measured by GC-MS were in the range from 31+/-23 to 1+/-1. Among the eight PAHs the predominant ones were fluoranthene, phenanthrene and pyrene and accounted approximately 63% of the total PAHs. Among the four detected PCBs the highest content was of PCB 153, which accounted about 47% of the total PCBs. The main organotin compounds were dibutyltindichloride (DBT) and tributyltinchloride (TBT) and their composition was approximately 33% and 24%. PAHs, PCBs and organotins were found only in the mussels from polluted site. The antioxidant activity by ABTS [2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonic acid)] test was higher in mussels from polluted than from unpolluted sites (P<0.05). It was found a correlation between the determined compounds (PAHs, PCBs and organotins) and the antioxidant activity of the mussel tissue from polluted site and the correlation coefficients were 0.96, 0.92 and 0.80, respectively. Such correlation can be explained by the properties of mussels. Since the mussel cell wall and tissues are hydrophobic, they can concentrate a number of hydrophobic pollutants like PAHs and PCBs from the marine environment by solubility rules. On the other hand, proteins are lipophilic compounds having antioxidant properties. Certain amino acid residues and thiol (-SH) groups, contained in proteins, respond to the ABTS antioxidant activity assay. Thus there may be a correlation between the total antioxidant activity of the organism and the PAH-PCB pollutants which were concentrated from its environment. The studied properties of mussels from polluted site can be used as an additional indicator of pollution.     

Metabolism of pyrene by two clam species,Mya arenaria and Protothaca staminea

Two species of marine clam, Mya arenaria and Protothaca staminea, were exposed to pyrene and 1-hydroxypyrene in small glass aquaria. After 10 days of exposure the clams were sacrificed, and both clam tissue and seawater were assayed for pyrene metabolites by using HPLC, fluorescence spectroscopy, HPLC-ESI-MS, GC-MS and 1H-NMR spectrometry. 1-Pyrenol-1-hydrogensulfate (pyrene-1-sulfate) was identified as the major water soluble metabolite formed from both pyrene and 1-hydroxypyrene by both species of clam. 1-Hydroxypyrene was identified as a minor metabolite of pyrene, and pyrenediol-hydrogen sulfate was identified as a minor metabolite of 1-hydroxypyrene.     

Butyltin residues in blue mussels (Mytilus edulis) and arkshells (Scapharca broughtonii) collected from Korean coastal waters

Butyltin compounds (BTs) including tributyltin (TBT) and its degradation products, di- (DBT) and mono-butyltin (MBT), were determined in bivalves such as blue mussels (Mytilus edulis) and arkshells (Scapharca broughtonii) collected from Korean coastal waters. BTs were detected in all the blue mussels and arkshells analyzed. The concentrations of total butyltin (sigmaBTs: MBT + DBT + TBT) in blue mussels and arkshells ranged from 49 to 2500 ng/g and 29 to 87 ng/g wet weight, respectively. Higher concentrations of BTs were found in blue mussels collected from Okpo and Kohyonsong Bays and Jangsengpo Harbor where large shipyards and harbors are located with dry-dock facilities. This suggested that maritime activities nearby the harbors play a major role as the source of BTs. Concentrations of TBT in mussels collected from Korea were one of the highest values reported, suggesting ongoing TBT contamination in Korea. Among BTs, TBT was the predominant compound both in blue mussels and arkshells collected from almost all the sampling locations, indicating the fresh input of TBT in Korean coastal waters. Smaller mussels tended to accumulate BTs at higher concentrations than larger ones, which may be due to higher filtration rate of small mussels and/or contact with surface microlayer in intertidal zones.     

Processing of antifouling paint particles by Mytilus edulis

Particles of spent antifouling paint collected from a marine boatyard were ground and subsequently administered to the filter-feeding bivalve, Mytilus edulis, maintained in static aquaria. Concentrations of Cu and Zn were measured in seawater throughout a 16 h feeding phase and a 24 h depuration phase, in rejected and egested particles collected during the respective phases, and in the organisms themselves at the end of the experiments. Concentrations and distributions of Cu and Zn in processed particles indicated that M. edulis was able to ingest paint particles, regardless of whether nutritionally viable silt was present, and no mechanism of particle discrimination was evident. Enrichment of Cu and Zn in the visceral mass of individuals and in the aqueous phase during depuration supported these assertions, although elevated concentrations in other compartments of the organism (e.g. shell, gill) suggested that biotic and abiotic uptake of aqueous metal was also important.     

Spatial distribution and accumulation of brominated flame retardants, polychlorinated biphenyls and organochlorine pesticides in blue mussels (Mytilus edulis) from coastal waters of Korea

Blue mussels (Mytilus edulis) from 20 locations along the coastal waters of Korea were analyzed to elucidate the characteristic distribution and contamination status of polybrominated diphenyl ethers (PBDEs), hexabromocyclododecanes (HBCDs), polychlorinated biphenyls (PCBs) and organochlorine pesticides. To our knowledge, this is the first study to report on the contamination status of HBCDs from Korea. PBDEs and HBCDs were found in mussels at levels ranging from 6.6 to 440 and from 6.0 to 500 ng/g lipid wt., respectively. Concentrations of PBDEs in mussels from Korea were higher or comparable to available data in mussels from other countries. Among the organochlorine compounds (OCs) analyzed, levels of PCBs and DDTs were the highest followed by CHLs, HCHs and hexachlorobenzene. For all the compounds, higher concentrations were found in mussels from southeastern coast of Korea. The present study shows the importance of mussels as bioindicators for monitoring contaminants in coastal waters.     

Differences in Cd elimination from Mytilus californianus and Mytilus trossulus soft tissues

Field results have shown that Mytilus californianus is able to release its Cd concentrations significantly in just a few days. The existing paradigm states that Cd elimination from Mytilus soft tissues is a very slow process. This discrepancy was investigated in the laboratory, testing the effect of two Cd levels (10 and 1 microgram l-1) on its release from Mytilus trossulus and M. californianus soft tissues. After exposure to 10 micrograms l-1, both species showed a significant uptake with no elimination after several days of depuration. After exposure to 1 microgram l-1, the responses were different. No significant Cd uptake was seen in M. trossulus while in M. californianus uptake was significant but returned to the background level after just 1 day of depuration. This response of M. californianus is consistent with that reported from field studies. These results are important for environmental monitoring programs since M. californianus has been used as equivalent to other Mytilus species in the assessment of Cd pollution.     

Biological effects of palytoxin-like compounds from Ostreopsis cf. ovata: A multibiomarkers approach with mussels Mytilus galloprovincialis

Massive blooms of the harmful benthic dinoflagellate Ostreopsis cf. ovata are of growing environmental concern in the Mediterranean, having recently caused adverse effects on benthic invertebrates and also some intoxication episodes to humans.The toxicological potential of produced palytoxin-like compounds was investigated in the present study on a typical marine sentinel species, the mussel Mytilus galloprovincialis. Organisms were sampled during various phases of a O. cf. ovata bloom, in two differently impacted sites. The presence of the algal toxins was indirectly assessed in mussels tissues (mouse test and hemolysis neutralization assay), while biological and toxicological effects were evaluated through the measurement of osmoregulatory and neurotoxic alterations (Na⁺/K⁺-ATPase and acetylcholinesterase activities), oxidative stress responses (antioxidant defences and total oxyradical scavenging capacity), lipid peroxidation processes (level of malondialdehyde), peroxisomal proliferation, organelle dysfunctions (lysosomal membrane stability, accumulation of lipofuscin and neutral lipids), immunological impairment (granulocytes percentage).Obtained results demonstrated a significant accumulation of algal toxins in mussels exposed to O. cf. ovata. These organisms exhibited a marked inhibition of the Na⁺/K⁺-ATPase activity and alterations of immunological, lysosomal and neurotoxic responses. Markers of oxidative stress showed more limited variations suggesting that toxicity of the O. cf. ovata toxins is not primarily mediated by an over production of reactive oxygen species. This study provided preliminary results on the usefulness of a multi-biomarker approach to assess biological alterations and toxicological events associated to blooms of O. cf. ovata in marine organisms.     

Butyltin accumulation in the marine clam Mya arenaria: an evaluation of its suitability for monitoring butyltin pollution

The use of Mya arenaria as a new sensitive biomonitor of butyltins pollution in the oceanic system was investigated. Field survey indicated that much higher levels of butyltin compounds were found in M. arenaria compared with the other species investigated. Using Mytilus edulis as a control organism, a 28 days exposure of tributyltin chloride (TBT) to M. arenaria for accumulation and subsequent 28 days breeding in clean seawater for elimination were conducted under laboratory conditions in order to confirm its high accumulation ability and characterize its kinetic behavior to TBT. Bioconcentration factor (BCF) of M. arenaria ranged from 15,538 to 91,800 after 28 days exposure. The rapid uptake and low rate to eliminate TBT of M. arenaria displayed first-order kinetics. M. arenaria shows potential as a new bioindicator to monitor TBT pollution in marine environment.     

Distribution and relationships of trace metals in soft tissue,byssus and shells of Mytilus edulis trossulus from the southern Baltic

Concentrations of Hg, Cd, Pb, Ag, Cu, Zn, Cr, Ni, Co, Mn, and Fe in soft tissues, shells and byssus of blue mussel (Mytilus edulis trossulus) from 23 sites along the Polish coast of the Baltic Sea were determined by AAS method. Byssus, as compared with the soft tissue, concentrated more effectively Pb, Cu, Cr, and especially Ag, Ni, Mn and Fe, moderately Hg and Zn and less effectively Cd. Significant inter-regional and inter-size differences in metal concentrations in both soft tissues and byssus were recorded. Highly significant correlations (P<0.01, P<0.05) were observed between tissue and byssal concentrations of Cd, Pb, Ni and Ag. Factor analysis showed clear separation of both the tissue and byssi samples based on their geographic distribution, possibly reflecting a different rate of deposition of clay minerals at the head of the Pomeranian Bay and the Gulf of Gdańsk. The Pomeranian Bay differs from the Gulf of Gdańsk in respect to geological structure of bottom sediments as a substrata for the M. edulis trossulus as well as in relation to various sources of metallic pollutants. From the data obtained in the present study and those reported previously the soft tissue and especially byssus of M. edulis, in contrast to shells, appear to be a significantly better bioindicator for identification of coastal areas exposed to metallic contaminants.     

Occurrence of organotin compounds in water and sediment in Canada

Water and sediment samples from 265 locations across Canada were analyzed for butyltin and methyltin species, and inorganic tin. In 10% of the water samples the highly toxic tributyltin species was found at concentrations which could cause growth retardation upon chronic exposure to a sensitive organism, rainbow trout yolk sac fry. High concentrations of tributyltin were found in some sediments (up to 10 mg Sn/kg dry weight), but the biological availability of sediment-associated tributyltin is unknown. Tributyltin was mainly found in areas of heavy boating and shipping traffic, which is consistent with its use as an antifouling agent in some paints for boats, ships and docks. The methyltin species were found much less frequently in water and sediment than tributyltin and its degradation products.     

Levels of some polybrominated diphenyl ether (PBDE) flame retardants along the Dutch coast as derived from their accumulation in SPMDs and blue mussels (Mytilus edulis)

Aqueous concentrations of individual brominated diphenyl ethers (BDEs) were determined for five stations in the Scheldt estuary and the North Sea along the Dutch coast using passive sampling by semipermeable membrane devices (SPMDs). Values of 0.1-5 pg l(-1) were observed. The highest levels were found in the Scheldt estuary. Concentration differences between February and October were a factor of 4-8 for BDE209, and were smaller than a factor of 2 for the other BDEs. Bioaccumulation was studied for native mussels and for mussels that were transplanted from an uncontaminated area into the Scheldt estuary for 6 weeks. Concentrations in native mussels were higher by a factor of 10 and 2 for BDEs and PCBs, respectively. Field based bioaccumulation factors (BAFs) were higher for BDEs than for PCBs by a factor of 10. Depuration experiments showed that the larger part of the BDE209 content in mussels was associated with ingested particles, whereas no such effect was observed for the other BDEs or PCBs.     

Distribution of feminizing compounds in the aquatic environment and bioaccumulation in wild tilapia tissues

This study sampled six times of river water, sediment, and tilapia (Oreochromis niloticus) in the Dan-Shui River, Taipei, Taiwan; 10 feminizing compounds were analyzed using ultra-performance liquid chromatography-tandem mass spectrometry. Bisphenol A (508?±?634 ng/L, geometric mean (GM) 303 ng/L) and nonylphenol (491?±?570 ng/L, GM 328 ng/L) were the most abundant among analytes in the river water. Nonylphenol (770?±?602 ng/g wet weight, GM 617 ng/g wet weight) was also the highest in sediment. Fish may uptake nonylphenol and nonylphenol ethoxylates from river water and sediment because there were significant correlations between the concentrations in these matrixes and those in fish tissues (r _s ranged from 0.21 to 0.49, p?相似文献   

Accumulation and depuration of cyanobacterial toxin nodularin and biomarker responses in the mussel Mytilus edulis

Blue mussels (Mytilus edulis) were exposed to an extract made of natural cyanobacterial mixture containing toxic cyanobacterium Nodularia spumigena (70-110 microg nodularin l(-1), 24-h exposure followed by 144-h depuration period in clean water). Toxin concentration increased from initial 400 to 1100 mg kg(-1) after 24-h exposure, measured by liquid chromatography/mass spectrometry (LC/MS). Acetylcholinesterase activity (AChE), a biomarker of direct neurotoxic effects, showed inhibition after 12 and 24h exposure but returned to control level during the depuration period. Catalase (CAT) activity, an indicator of oxidative stress, showed significantly elevated levels in exposed mussels but only 72 h after the end of the exposure. No change in the activity of glutathione-S-transferase (GST) involved in conjugation reactions could be observed. A gradual yet incomplete elimination of nodularin (from 1100 to 600 mg kg(-1)) was observed during the depuration period, and the tissue levels were 30% lower in clean water after 24 h. The observed increase in oxidative stress indicated by elevated CAT activity is likely connected to detoxification reactions leading to the production of reactive oxygen species, including an apparent time lag in this specific enzymatic defence response. That no change in GST activity was observed suggests that this enzyme is not significantly involved in the detoxification process of nodularin-containing cyanobacterial extract in M. edulis.     

Immunotoxic effects of organotin compounds in Tapes philippinarum

One of the most harmful groups of coastal pollutants is the organotin compounds (OTCs) which have severe effects on both aquatic organisms and mammals including humans. The immunotoxic effects of OTCs were studied in the cultivated clam Tapes philippinarum by determining the immunosuppressant role on in vitro yeast phagocytosis at low doses (0.01, 0.05, 0.1 μM). The phagocytic index was significantly reduced in an irreversible non-lethal manner depending on concentration and lipophilic affinity. The order of inhibition was TBT≥DBT>MBT for butyltins and TPTC>TPTA≥TPTH for triphenyltins.     

Aerobic biodegradation of organotin compounds in activated sludge batch reactors

The biodegradation behavior of four organotin (OT) compounds, namely tributyltin (TBT), dibutyltin (DBT), monobutyltin (MBT) and triphenyltin (TPhT), was studied in lab-scale activated sludge batch reactors. The activated sludge was spiked with the OT compounds at a level of 100 microg l(-1) as Sn. Determination of the OT compounds by GC-FPD after ethylation in the dissolved and particulate phase revealed that 24 h after the start of the experiments, almost the total of OT compounds has been removed from the dissolved phase and is associated with the suspended solids. Calculation of mass balance in batch reactors showed that OT compounds biodegradation was performed via a sequential dealkylation process. Removals due to biodegradation were differentiated according to the parent compound. In experiments with non-acclimatized biomass, a percentage of 27.1, 8.3, 73.8 and 51.3 was still present as TBT, DBT, MBT and TPhT, respectively, at the end of the experiment (18th day). Half-lives (t1/2) of 10.2 and 5.1 days were calculated for TBT and DBT, respectively, whereas apparent t1/2 values could not be determined for MBT and TPhT (t1/2>18 days). The capacity of activated sludge to biodegrade OT compounds in the absence of supplemental substrate indicated that these compounds can be metabolized as single sources of carbon and energy in activated sludge systems. Excluding TBT, the presence of low concentrations of supplemental substrate did not affect the biodegradation potential of activated sludge. The acclimatization of biomass on OT compounds enhanced significantly biodegradation, resulting in significant decreases of half-lives of OT compounds. As a result in the presence of acclimatized biomass, half-lives of 1.4, 3.6, 9.8 and 5.0 days were calculated for TBT, DBT, MBT and TPhT, respectively.     

Inhibition of trout gill and soybean lipoxygenases by organotin compounds

Activity of trout gill and soybean lipoxygenase was inhibited by various low concentrations of tri-n-butyltin, di-n-butyltin and n-butyltin chlorides at pH 7.8. Tri-n-butyltin (0.044-0.19 mM; 8-100% inhibition) was significantly more inhibitory against trout gill lipoxygenase than di-n-butyltin (0.1-0.27 mM; 17-39% inhibition) or n-butyltin (1.2-3.6 mM; 26-43% inhibition). Soybean lipoxygenase displayed a similar sensitivity to the inhibitory effects of organotin compounds at pH 7.8. Although tri-n-butyltin (0.067-0.2 mM; 13-68% inhibition) was less inhibitory to soybean lipoxygenase, di-n-butyltin (0.134-0.537 mM; 51-75% inhibition) and n-butyltin (0.41-1.23 mM; 33-75% inhibition) were more inhibitory towards soybean lipoxygenase compared with trout gill lipoxygenase. Concentrations of butyltins required to provide substantial inhibition of trout gill lipoxygenase were of the order of magnitude of those reported for lethal water exposure concentrations of these compounds for trout and other fishes when bioaccumulation factors are considered. Thus, it is proposed that inhibition of lipoxygenase likely contributes to the biocidal activity of organotin compounds.     

Phthalates and the aquatic environment: Part II The bioconcentration and depuration of di-2-ethylhexyl phthalate (DEHP) and di-isodecyl phthalate (DIDP) in mussels (Mytilus edulis)

Mussels ($\text{Mytilus edulis}$) were exposed to di-2-ethylhexyl phthalate (DEHP) and to di-isodecyl phthalate (DIDP) over a period of 28 days. The bioconcentration factor (BCF) as measured by ¹⁴C analysis, reached estimated plateau levels corresponding to mean BCF values of approximately 2500 and 3500 for the DEHP and DIDP respectively. The mussels were then held in clean seawater for a further 14 days and ¹⁴C analysis showed a depuration half-life of approximately 3.5 days for both phthalates. During the whole 42 days of the experiment general observations on the health of the animals showed no evidence of any adverse effects.