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1.
Since the restriction imposed by European Union regulations on the use of TBT-based antifouling paints on boats below 25 m in length, new terms have been introduced in the 'small boat' market. Replacement products are generally based on copper metal oxides and organic biocides. Several studies have demonstrated the presence of these biocides in European ports and marinas of Spain, France, Germany and the United Kingdom. An extended survey of the antifouling biocides chlorothalonil, dichlofluanid, irgarol 1051 and sea-nine 211 was carried out in Greek ports and marinas of high boating activities from October 1999 to September 2000. The sampling sites were: Piraeus, Elefsina, Thessaloniki, Patras, Chalkida, Igoumenitsa, and Preveza (Aktio). The extraction of these compounds from the seawater samples was performed off-line with C18 solid phase extraction (SPE) disks while the determination was carried out with gas chromatography coupled to electron capture (ECD), thermionic (FTD) and mass spectroscopy (MS) detectors. The concentration levels of biocides were higher during the period from April to October. This seasonal impact depends on the application time of antifouling paints and mimic trends in the seasonal distribution of biocides in other European sites.  相似文献   

2.
Current regulatory risk assessment procedures only assess the impact of antifouling paint biocides that are released through leaching from a painted surface. Hull cleaning activities can lead to particles of antifouling paint containing biocides to enter the environment. Comparative pseudo-first order anaerobic degradation rate constants and half-lives were determined for a selection of common antifouling paint booster biocides, their degradation products, and associated with paint particles. Anaerobic half-lives of <0.5 days were calculated for chlorothalonil, dichlofluanid, and SeaNine 211, between 1 and 3 days for DCPMU and DCPU, between 14 and 35 days for diuron and CPDU, and over 226 days for GS26575 and Irgarol 1051. Increased persistence was observed when the compounds were introduced to sediments associated with antifouling paint particles. When present as antifouling paint particles, an increased half-life of 9.9 days for SeaNine 211 and 1.4 days was calculated for dichlofluanid, no significant degradation was observed for diuron. It is suspected that this is due to much of the biocide being initially bound within the matrix of the paint particle that is slowly released through dissolution processes into the sediment pore water prior to degradation. The release of booster biocides associated with paint particles into marinas has the potential to lead to their accumulation unless activities such as hull cleaning are strictly regulated.  相似文献   

3.
Sargent CJ  Bowman JC  Zhou JL 《Chemosphere》2000,41(11):1755-1760
Irgarol 1051 (2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine) is an antifouling agent used in paint formulations that are applied to the hulls of ships. A survey was carried out at Conwy Marina in North Wales to determine the levels of the herbicide over a period of three months. Liquid/liquid extraction was used to concentrate the analyte for quantitative analysis using gas chromatography/mass spectrometry (GC/MS) in the selected ion monitoring (SIM) mode. The concentrations of Irgarol 1051 in Conwy marina ranged from 7 to 543 ng/l, similar to the levels found in many other marinas, estuaries and ports in England, although much lower than those in C?te d'Azur, France. The concentrations of Irgarol 1051 were not found to be influenced by salinity, pH or temperature, although there is a strong correlation between the average concentrations of Irgarol 1051 and the density of boating activity. At the levels found in the marina, it is possible that non-target photosynthetic inhibition could occur.  相似文献   

4.
Analytical procedures for the determination of nine organic booster biocides which are currently licensed for use in marine antifouling paints, and are thought likely to occur at concentrations in the ng 1−1 range in estuarine water samples, are reviewed. A robust multiresidue method for the determination of four compounds (chlorothalonil, dichlofluanid, diuron and Irgarol 1051) is suggested. A route for the development of a method for the analysis of zinc pyrithione is outlined, based on an extraction method and subsequent derivatisation prior to determination by HPLC with fluorescence detection. Methodology for Zineb, Kathon 5287, TCMS pyridine and TCMTB is less clearly defined.  相似文献   

5.
Escherichia coli and total coliforms in water and sediments at lake marinas   总被引:2,自引:0,他引:2  
Escherichia coli, a fecal coliform, and total coliforms were monitored between September 1999 and October 2001 in five marinas at Lake Texoma, located on the Oklahoma and Texas border. The general trend was that densities of E. coli were lower in the summer season due to the lower loading of fecal material into Lake Texoma and the ecological conditions of the lake, such as more vigorous grazing by protozoa and less viability of E. coli at an elevated temperature. The densities of total coliforms greatly increased in the summer. E. coli levels increased with depth, and the bottom water samples had higher densities of E. coli mainly due to their association with particles. There was a direct relationship between amount of gasoline sold, which was related to recreational boating activity, and the resuspension of E. coli. This indicated that recreational boating activity in lake marinas may have resuspended bottom sediments with bound E. coli, and the presence of E. coli in marinas was not an indication of recent fecal contamination. E. coli were detected in the largest densities at the boat dock points, followed by the gasoline filling station, and marina entrance. In addition, enumeration of bacteria in bottom sediment showed that the densities of E. coli and total coliforms in sediment were much higher compared to those in lake water.  相似文献   

6.
Tolhurst LE  Barry J  Dyer RA  Thomas KV 《Chemosphere》2007,68(8):1519-1524
The effect of resuspending sediment contaminated with Irgarol 1051 based antifouling paint particles on the green macroalga Ulva intestinalis was examined. U. intestinalis was also exposed to sediment spiked with Irgarol 1051. The macroalga were exposed over 21 days to the resuspension of sediments containing 61.2 mg kg(-1) of antifouling paint particles containing Irgarol 1051 that provided aqueous Irgarol 1051 concentrations of approximately 0.3 microg l(-1), Irgarol 1051 and appropriate controls. The growth response was compared with that for 'clean' sediment. Resuspension of sediment was associated with reduced growth when compared to seawater alone. Resuspension of sediment spiked with Irgarol 1051 was associated with a greater reduction in growth, with growth being significantly reduced when sediment containing antifouling paint particles was resuspended. The data suggest that the prolonged disturbance of sediments containing antifouling paint particles in marinas represents a potential and as yet unquantified hazard to photosynthetic organisms.  相似文献   

7.
Dichlofluanid (N-dichlorofluoromethylthio-N'-dimethyl-N-phenylsulphamide) is used as booster biocide in antifouling paints. The occurrence of dichlofluanid and its metabolite DMSA (N'-dimethyl-N-phenyl-sulphamide) was monitored in seawater and marine sediment from three Greek marinas. Seawater and sediment samples were collected at three representative positions and one suspected hotspot in each marina and shipped to the laboratory for chemical analysis. As part of the project, an analytical method had been developed and validated. Furthermore, some additional experiments were carried out to investigate the potential contribution of paint particle bound dichlofluanid on the total concentration in the sediment. As expected, given its known high hydrolytic degradation rate, no detectable concentrations of dichlofluanid were measured in any of the seawater samples. DMSA was detected in seawater samples at very low concentrations varying from <3 ng l(-1) (LOD) to 36 ng l(-1). During method validation, it had already been demonstrated that dichlofluanid is unstable in sediment and can therefore only be determined as its metabolite DMSA. In a separate experiment, in which marine sediment was spiked with artificial paint particles containing dichlofluanid and then analysed according to the validated method, it was demonstrated that if there is any dichlofluanid originating from paint particles, this would be determined as DMSA. No DMSA was detected in any of the sediment samples. It could therefore be concluded that there were no significant concentrations of dichlofluanid in the sediment samples.  相似文献   

8.
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.  相似文献   

9.
Water quality in five marinas on Lake Texoma, located on the Oklahoma and Texas border, was monitored between June 1999 and November 2000. Focus was to evaluate lake water associated with marinas for methyl tert-butyl ether (MTBE). Lake water was collected at locations identified as marina entrance, gasoline filling station, and boat dock. Occurrence of MTBE showed a direct seasonal trend with recreational boating activity at marina areas. There was a positive correlation with powerboat usage ratio, which was directly related to the gallons of gasoline sold. Sampling before and after the high boat use holiday weekends determined the apparent influence of powerboat activity on MTBE contamination. Boat dock locations were the most sensitive sites to MTBE contamination, possibly due to gasoline spillage during engine startup. The most common compound of the BTEX series found with MTBE was toluene and co-occurrence was most frequent at gasoline filling stations.  相似文献   

10.
Antifoulant concentrations were determined in marine sediments collected from commercial harbours, marinas, mooring locations on mid-shelf continental islands, and outer reef sites in four regions within the Great Barrier Reef World Heritage Area in 1999. Highest copper concentrations were present in sediments collected from commercial harbour sampling sites (28-233 microg Cu g(-1) dry wt.). In contrast, copper concentrations in sediments collected from boat mooring sites on mid-shelf continental islands and outer reef sites were at background concentrations (i.e. <20 pg Cu g(-1) dry wt.). Butyltin was only detectable in four of the 42 sediments sampled for analysis, and was only present in sediments collected from commercial harbours (18-1275 ng Sn g(-1) dry wt.) and from marinas (4-5 ng Sn g(-1) dry wt.). The detection of tributyltin at marina sites implies that this antifoulant may continue to be used illegally on the hulls of smaller recreational vessels. Sediment samples were also collected opportunistically from the site of a 22,000 t cargo ship grounding in May 1999 at Heath Reef, in the far northern Great Barrier Reef. Butyltin concentrations were grossly elevated (660-340,000 ng Sn g(-1) dry wt.) at the grounding site. The impact of residual antifoulants at large ship grounding sites should be recognised as a significant, long-term environmental problem unless antfoulant clean-up strategies are undertaken.  相似文献   

11.
Total,dissolved, and bioavailable metals at Lake Texoma marinas   总被引:2,自引:0,他引:2  
Dissolved metals in water and total metals in sediments were measured at marina areas in Lake Texoma during June 1999 to October 2001, and October 2001, respectively. The metals most often found in the highest concentrations in marina water were Na and Ca, followed by Mg and K. Elevated Cu levels detected in lake water appeared to be associated with Cu based anti-fouling paint used on boats. Metal concentrations in sediment were much higher than in water. The relative order of the concentration in sediment was Ca > Al > Fe > K > Mg > Na. Elevated Cu level at specific locations appeared to be associated with local anthropogenic sources of boat repair activities. There were positive relationships between several metal elements in water and sediment. Metals in 16 sediments from lake marinas were extracted with a weak electrolyte solution [0.1 M Ca(NO3)2] to predict the bioavailability of metals. Among the five heavy metals studied (As, Cd, Cr, Cu and Zn), Cu was the most bioavailable in Lake Texoma marinas.  相似文献   

12.
A 2-year study was implemented to characterize the contamination of estuarine continuums in the Bay of Vilaine area (NW Atlantic Coast, Southern Brittany, France) by 30 pesticide and biocide active substances and metabolites. Among these, 11 triazines (ametryn, atrazine, desethylatrazine, desethylterbuthylazine, desisopropyl atrazine, Irgarol 1051, prometryn, propazine, simazine, terbuthylazine, and terbutryn), 10 phenylureas (chlortoluron, diuron, 1-(3,4-dichlorophenyl)-3-methylurea, fenuron, isoproturon, 1-(4-isopropylphenyl)-3-methylurea, 1-(4-isopropylphenyl)-urea, linuron, metoxuron, and monuron), and 4 chloroacetanilides (acetochlor, alachlor, metolachlor, and metazachlor) were detected at least once. The objectives were to assess the corresponding risk for aquatic primary producers and to provide exposure information for connected studies on the responses of biological parameters in invertebrate sentinel species. The risk associated with contaminants was assessed using risk quotients based on the comparison of measured concentrations with original species sensitivity distribution-derived hazardous concentration values. For EU Water Framework Directive priority substances, results of monitoring were also compared with regulatory Environmental Quality Standards. The highest residue concentrations and risks for primary producers were recorded for diuron and Irgarol 1051 in Arzal reservoir, close to a marina. Diuron was present during almost the all survey periods, whereas Irgarol 1051 exhibited a clear seasonal pattern, with highest concentrations recorded in June and July. These results suggest that the use of antifouling biocides is responsible for a major part of the contamination of the lower part of the Vilaine River course for Irgarol 1051. For diuron, agricultural sources may also be involved. The presence of isoproturon and chloroacetanilide herbicides on some dates indicated a significant contribution of the use of plant protection products in agriculture to the contamination of Vilaine River. Concentration levels and associated risk were always lower in estuarine sites than in the reservoir, suggesting that Arzal dam reduces downstream transfer of contaminants and favors their degradation in the freshwater part of the estuary. Results of the additional monitoring of two tidal streams located downstream of Arzal dam suggested that, although some compounds may be transferred to the estuary, their impact was probably very low. Dilution by marine water associated with tidal current was also a major factor of concentration reduction. It is concluded that the highest risks associated to herbicides and booster biocides concerned the freshwater part of the estuary and that its brackish/saltwater part was exposed to a moderate risk, although some substances may sometimes exhibit high concentration but mainly at low tide and on an irregular basis.  相似文献   

13.
Sediment and water samples have been collected between 1992 and 1995 for evaluating butyltin contamination in two marinas from the coastal area in The Netherlands, two years after the ban of TBT. Sediments extracts were analysed by capillary gas chromatography-inductively coupled plasma-mass spectrometry. Sediment concentrations for TBT showed no trend of decrease between 1992 and 1995 and were extremely high in the marina secluded from tidal action; 17.5 +/- 8.0 microg g(-1) and much lower for the marina with tidal action; 0.117 +/- 0.073 microg g(-1). High ratios between TBT and DBT in the sediments indicate that degradation mechanisms in the sediments are of minor importance. Dissolved butyltin compounds were analysed in water by means of gas chromatography-atomic absorption spectrometry. Water concentrations of TBT showed no clear trend of decrease between 1992 and 1995 and were high in the marina secluded from tidal action; 139 +/- 166 ng litre(-1) but much lower for the marina with tidal action; 48 +/- 98 ng litre(-1). An active degradation mechanism during summer periods was indicated by low (<1) TBT/DBT ratios in the water phase of the marina secluded from tidal action.  相似文献   

14.
This study examined the toxicity of irgarol, individually and in binary mixtures with three other pesticides (the fungicide chlorothalonil, and the herbicides atrazine and 2,4-D), to the marine phytoplankton species Dunaliella tertiolecta. Standard 96-h static algal bioassays were used to determine pesticide effects on population growth rate. Irgarol significantly inhibited D. tertiolecta growth rate at concentrations > or = 0.27 micro g/L. Irgarol was significantly more toxic to D. tertiolecta than the other pesticides tested (irgarol 96 h EC50 = 0.7 micro g/L; chlorothalonil 96 h EC50 = 64 micro g/L; atrazine 96 h EC50 = 69 micro g/L; 2,4-D 96 h EC50 = 45,000 micro g/L). Irgarol in mixture with chlorothalonil exhibited synergistic toxicity to D. tertiolecta, with the mixture being approximately 1.5 times more toxic than the individual compounds. Irgarol and atrazine, both triazine herbicides, were additive in mixture. The toxicity threshold of 2,4-D was much greater than typical environmental levels and would not be expected to influence irgarol toxicity. Based on these interactions, overlap of certain pesticide applications in the coastal zone may increase the toxicological risk to resident phytoplankton populations.  相似文献   

15.
A new sample treatment method for the determination of four common booster biocides (Diuron, TCMTB, Irgarol 1051 and Dichlofluanid) in harbour sediment samples has been developed that uses liquid chromatography-tandem mass spectrometry (LC-MS/MS) after microwave-assisted extraction, followed by clean-up and a solid phase extraction preconcentration step (MAE-SPE). The effects of different variables on MAE-SPE were studied. The recoveries obtained were greater than 75%, and the relative standard deviation was less than 7%. The detection limits ranged between 0.1 and 0.3 ng g−1. The developed methodology was successfully applied to the evaluation of the presence of booster biocides in sediment samples from different harbours and marinas of Gran Canaria Island (Canary Islands, Spain).  相似文献   

16.

This study examined the toxicity of irgarol, individually and in binary mixtures with three other pesticides (the fungicide chlorothalonil, and the herbicides atrazine and 2,4-D), to the marine phytoplankton species Dunaliella tertiolecta. Standard 96-h static algal bioassays were used to determine pesticide effects on population growth rate. Irgarol significantly inhibited D. tertiolecta growth rate at concentrations ≥ 0.27 μ g/L. Irgarol was significantly more toxic to D. tertiolecta than the other pesticides tested (irgarol 96 h EC50 = 0.7 μ g/L; chlorothalonil 96 h EC50 = 64 μ g/L; atrazine 96 h EC50 = 69 μ g/L; 2,4-D 96 h EC50 = 45,000 μ g/L). Irgarol in mixture with chlorothalonil exhibited synergistic toxicity to D. tertiolecta, with the mixture being approximately 1.5 times more toxic than the individual compounds. Irgarol and atrazine, both triazine herbicides, were additive in mixture. The toxicity threshold of 2,4-D was much greater than typical environmental levels and would not be expected to influence irgarol toxicity. Based on these interactions, overlap of certain pesticide applications in the coastal zone may increase the toxicological risk to resident phytoplankton populations.  相似文献   

17.
Lambert SJ  Thomas KV  Davy AJ 《Chemosphere》2006,63(5):734-743
Antifouling paints are used to reduce the attachment of living organisms to the submerged surfaces of ships, boats and aquatic structures, usually by the release of a biocide. Two 'booster' biocides in common use are the triazine herbicide Irgarol 1051 (N-2-methylthio-4-tert-butylamino-6-cyclopropylamino-s-triazine), and diuron (1-(3,4-dichlorophenyl)-3,3-dimethylurea), which are designed to inhibit algal photosynthesis. Previous research has been directed at the effects of these compounds in marine and estuarine environments. In 2001 we sampled the main rivers and shallow freshwater lakes (Broads) of East Anglia UK for Irgarol 1051, its metabolite GS26575 (2-methylamino-4-tert-butylamino-6-amino-s-triazine) and diuron in order to establish the baseline environmental concentrations of these compounds in freshwater systems of eastern UK and to investigate their possible effects on aquatic plants. Irgarol 1051, GS26575 and diuron were found in water samples collected from 21 locations. The highest concentrations were found in the Norfolk and Suffolk Broads in May. The rivers Great Ouse, Wissey, Bure and Yare also contained all three compounds, as did the Great Ouse Cut-off Channel. The toxicity of these biocides to three macrophyte species (Apium nodiflorum, Chara vulgaris, and Myriophyllum spicatum) was investigated. Deleterious effects on relative growth rate, the maximum quantum efficiency (Fv/Fm) of photosystem II and, for Apium, root mass production were found. C. vulgaris was generally most sensitive; growth, especially of roots, was strongly affected in A. nodiflorum; growth rate of M. spicatum was sensitive to diuron. No observed effect concentrations (NOEC) were interpolated using standard toxicological analysis. These were compared with measured environmental concentrations (MEC) to determine the ranges of risk quotients (MEC/NOEC). Both Irgarol 1051 and diuron represented significant risks to A. nodiflorum and C. vulgaris in this area.  相似文献   

18.
Kitada Y  Kawahata H  Suzuki A  Oomori T 《Chemosphere》2008,71(11):2082-2090
To investigate the deteriorating health of coral reefs in Okinawa, Japan, natural sediment samples were analyzed for diuron, Irgarol 1051, chlorpyrifos, and bisphenol A (BPA) which are hazardous to corals. Samples were analyzed by solid-phase extraction (SPE) followed by high-performance liquid chromatography with tandem mass spectrometry (LC–MS–MS). Although diuron and chlorpyrifos usage is only well recorded for farms and not for cities, these chemicals were detected in both rural and urban areas. Additionally, diuron concentration in urban areas was in some cases higher than in rural areas, which might be caused by greater consumption of these chemicals in home gardens in city areas. Irgarol 1051 was detected in downstream river areas, which are situated far from the source sites such as pier or fishery harbor (0.6–3.2 km). This result suggested that Irgarol 1051 could be transported from the river mouths to the sampling sites during flood tides. High BPA concentrations were associated with urban areas (<1.2–22.0 μg kg−1), while low concentrations were associated with rural areas (nd–6.8 μg kg−1). The river sediments under study are delivered to coral reefs in large quantity through runoff caused by typhoons and other heavy rains. The highly hazardous chemicals are carried into coral reefs on these sediments. Therefore, these hazardous chemical substances may already be influencing the coral reefs.  相似文献   

19.
Huang PC  Tien CJ  Sun YM  Hsieh CY  Lee CC 《Chemosphere》2008,73(4):539-544
Phthalate compounds in sediments and fishes were investigated in 17 Taiwan's rivers to determine the relationships between phthalate levels in sediment and aquatic factors, and biota-sediment accumulation factor (BSAF) for phthalates. Mean concentrations (range) of di(2-ethylhexyl) phthalate (DEHP), butyl benzyl phthalate (BBzP) and di-n-butyl phthalate (DBP) in sediment at low-flow season were 4.1 (<0.05-46.5), 0.22 (<0.05-3.1) and 0.14 (<0.05-1.3)mgkg(-1)dw; those at high-flow season were 1.2 (<0.05-13.1), 0.13 (<0.05-0.27) and 0.09 (<0.05-0.22)mgkg(-1)dw, respectively. Trace levels of dimethyl phthalate (DMP), diethyl phthalate (DEP) and di-n-octyl phthalate (DOP) in sediment were found in both seasons. Concentrations of DEHP in sediments were significantly affected by temperature, suspended solids, ammonia-nitrogen, and chemical oxygen demand. The highest concentration of DEHP in fish samples were found in Liza subviridis (253.9mgkg(-1)dw) and Oreochromis miloticus niloticus (129.5mgkg(-1)dw). BSAF of DEHP in L. subviridis (13.8-40.9) and O. miloticus niloticus (2.4-28.5) were higher than those in other fish species, indicating that the living habits of fish and physical-chemical properties of phthalates, like logKow, may influence the bioavailability of phthalates in fish. Our data suggested that DEHP level in river sediments were influenced by water quality parameters due to their effects on the biodegradation processes, and that the DEHP level in fish was affected by fish habitat and physiochemical properties of polluted contaminants.  相似文献   

20.
We studied the effects of boating and navigation activities on the recruitment of coastal fish in the Stockholm archipelago in the NW Baltic proper. The impacts were quantified by sampling metamorphosed young-of-the-year (Y-O-Y) fish in inlets adjacent to i) routes for medium-sized passenger ferries; ii) berths (small marinas) with small boats; and iii) references. Species with high preference for vegetation were negatively influenced by boating and navigation activities and species with low preference positively influenced. Pike (Esox lucius) Y-O-Y were significantly more abundant in reference areas, while bleak (Alburnus alburnus) were more abundant in dredged marinas. No statistically significant patterns were identified for perch (Perca fluviatilis) although there was a trend of low abundance along ferry routes. Many species of nearshore fishes are dependent on submerged vegetation as spawning and larval substrate, structural refuge and feeding habitat. Our results suggest that the negative effects from boating and navigation activities on the coverage and height of vegetation, especially on species of Chara and Potamogeton spp., may contribute to changes in the Y-O-Y fish community.  相似文献   

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