Atmospheric deposition and canopy exchange processes in alpine forest ecosystems (northern Italy)

Throughfall and bulk precipitation chemistry were studied for five years (June 1994–May 1999) at two high elevation forest sites (Val Gerola and Val Masino) which were known to differ in terms of tree health, as assessed by live crown condition. The ion concentration of bulk precipitation samples did not differ significantly between sites, except for Mg²⁺, while the throughfall concentrations differed in the measured values of H⁺, N-NO₃⁻, Cl⁻, Na⁺, K⁺, DOC and weak organic acids. The results of the application of the canopy exchange model indicated a higher contribution from the dry deposition of N-NO₃⁻, N-NH₄⁺ and H⁺ at Val Gerola, where the damage symptoms were more evident. In addition, the canopy leaching of Ca²⁺, K⁺ and weak organic acids were 47%, 21% and 27% higher at Val Gerola than at Val Masino. Annual SO₄²⁻ deposition fluxes (21.3 kg ha⁻¹ yr⁻¹ at Val Masino and 23.6 kg ha⁻¹ yr⁻¹ at Val Gerola) were similar to those reported for moderately polluted European and U.S. sites. Annual N loads were 13.6 and 13.1 kg ha⁻¹ yr⁻¹ in the bulk input, and 15.0 and 18.0 kg ha⁻¹ yr⁻¹ in throughfall inputs, at Val Masino and Val Gerola, respectively. The contribution of the organic fraction to the total N atmospheric deposition load is significant, constituting 17% of the bulk flux and 40% of the throughfall flux. Measured nitrogen loads exceed the critical nutrient loads by several kg N ha⁻¹ at both stations. In particular the nitrogen throughfall load at Val Gerola was about 3 times higher than the critical values.     

Concentrations of pesticide residues in grasses and sedges due to point source contamination and the indications for public health risks, Vikuge, Tanzania

The concentrations of organochlorine pesticide residues were determined in roots and leaves of giant sedges (Cyperus exaltatus), fresh leaves and dry hay of guinea grasses (Panicum maximum), and in stems and leaves of elephant grasses (Pennisetum purpureum) in the vicinity of a point source of contamination, an old storage site at Vikuge farm in Tanzania. The GPC-cleaned extracts were analyzed by GC-ECD and GC/MS. The concentrations of total DDT ranged from 83 to 18274 ng/g, 166 to 7922 ng/g, and 68 to 405 ng/g, on fresh weight basis, in C. exaltatus, P. maximum and P. purpureum, respectively. The concentrations of total HCH were up to 74 ng/gfw in leaves of C. exaltatus, 43 ng/gdw in dry hay of P. maximum, and 10 ng/gfw in stems of P. purpureum. Aldrin and dieldrin were only detected in C. exaltatus and their concentrations were up to 11 and 8 ng/gfw, respectively. The strong positive correlations between the concentrations of the detected compounds suggest a common source. The concentrations of total DDT were far above the Australian extraneous maximum residue limit in primary animal feedstuffs. These findings indicate potential risks and concerns for livestock and public health. The concentrations of aldrin, dieldrin and lindane were lower than the Australian limits.     

Pesticides and metabolites in cassava, eucalyptus, plum and cashew leaves and roots in relation to a point source in Kibaha, Tanzania

Leaves of Eucalyptus sp., Prunus domestica (plum), and Anacardium occidentale (cashew), as well as roots and leaves of Manihot esculenta (cassava) were used to study the local distribution of pesticides and metabolites from a point source, an old storage site at Vikuge farm in Tanzania. The GPC-cleaned extracts were analyzed by GC-ECD and GC/MS. Eleven organochlorine pesticide residues namely pentachloroanisole, p,p'-DDT, o,p'-DDT, p,p'-DDE, o,p'-DDE, p,p'-DDD, o,p'-DDD, alpha-HCH, beta-HCH, delta-HCH and epsilon-HCH were detected in the samples. The concentrations of total DDT were 818 ng/g fw in Eucalyptus sp., 16 ng/g fw in A. occidentale and 4 ng/g fw in P. domestica. In M. esculenta, total DDT ranged from 191 to 586 ng/g fw in roots and 7 to 425 ng/g fw in leaves. The concentrations of total HCH were up to 15 ng/g fw in Eucalyptus sp., while the concentrations of pentachloroanisole were up to 2 ng/g fw in leaves of M. esculenta. There are very strong positive correlations in the concentrations of the detected compounds, suggesting that they have a common source. The low DDE/DDT ratios (0.02-0.07) in all samples indicate input of non-degraded DDT from the source. The high alpha-HCH/gamma-HCH ratios in some samples (>3.1-10) indicate input of technical HCH. The concentrations of total DDT in cassava roots were either very close to, or greater than, the FAO/WHO limit, indicating risks and concern to public health.     

Organochlorine pesticides and metabolites in young leaves of Mangifera indica from sites near a point source in Coast region, Tanzania

Young leaves of Mangifera indica (mango tree) from nine sites were used as bioindicators of local atmospheric contamination by organochlorine pesticides and metabolites from a point source, an old storage site at Vikuge farm in Tanzania. Sample extracts were analysed by GC-ECD and GC-MS. The concentrations ranged 2.7-649 ng g(-1)p,p'-DDT, below detection limit (bdl)-290 ng g(-1) o,p'-DDT, 0.4-13 ng g(-1) p,p'-DDE, bdl to 4 ng g(-1) o,p'-DDE, 1-231 ng g(-1) p,p'-DDD and 0.5-55 ng g(-1) o,p'-DDD. The concentrations of other compounds were up to 3.9 ng g(-1) pentachloroanisole, 1.3 ng g(-1) alpha-HCH, 12 ng g(-1) beta-HCH and 2 ng g(-1) gamma-HCH, on fresh weight basis. The compounds p,p'-DDT, p,p'-DDE, p,p'DDD and o,p'-DDD were found in 100% of the samples, while pentachloroanisole, o,p'-DDT and o,p'-DDE were detected in 78%, 56% and 67% of the samples, respectively. The low DDE/DDT ratios (0.01-0.20) in all samples indicate recent input of significantly non-degraded DDT from the point source. The low alpha-/gamma-HCH ratios (<0.3-0.7) in most samples indicate recent input of lindane (99% gamma-HCH). The slightly high alpha-/gamma-HCH ratios in some samples might be due to photochemical or bacterial transformation of gamma-HCH to alpha-HCH, or could reflect input of technical HCH. The very strong positive correlations in the concentrations of p,p'-DDT, p,p'-DDE, p,p'-DDD, o,p'-DDT, o,p'-DDE and o,p'-DDD (r=0.91-0.98, n=18, p<0.01) indicate that they have a common source. The results suggest that young mango leaves are suitable bioindicators of recent inputs of organochlorine contaminants from a point source.     

Organochlorine pesticides and polychlorinated biphenyls in air and soil across Azerbaijan

Concentrations of selected organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) are reported in air and surface soil in an extensive spatial survey across Azerbaijan, a country bordering the Caspian Sea with a history of OCP production and extensive use. Polyurethane foam disc passive air samplers (PAS) were deployed during October-November 2008 with soil samples collected in July 2009. Levels of Σ(7)PCB in ambient air were generally low (mean of 0.046 ng m(-3), n?=?13) and comparable to concentrations reported in countries within Eastern Europe and similar to or lower than concentrations reported in urban air in the UK and other western countries. Surprisingly, PCB concentrations in rural/background soil fell below the method detection limits at most sites, although concentrations were 0.209 and 0.071 ng Σ(7)PCB g(-1) dry weight (dw) for two urban sites, again comparable to PCB levels measured at background sites in Europe. Levels of α-HCH, β-HCH, γ-HCH and p,p'-DDT/E were elevated in ambient air across Azerbaijan in comparison to PAS-derived concentrations reported elsewhere, with concentrations of α-HCH in air ranging from 0.085 to 2.699 ng m(-3) and p,p'-DDE, 0.037-2.290 ng m(-3). High concentrations of OCPs occurred at several of the urban sites and at sites in proximity to old pesticide storage facilities with concentrations in soil >0.1 μg g(-1) dw for p,p'-DDE and p,p'-DDT at several sites. The ratio of p,p'-DDT/p,p'-DDE was close to unity in the soil at these sites, but elsewhere, the ratio was <1, indicating a weathered DDT pattern, which was also reflected in the air at all sites. A fugacity approach revealed the strong likelihood of net soil-to-air transfer at the majority of sites for all OCPs. The calculated annual fluxes or loading to the atmosphere from a rural/agricultural area (representing land as vineyards and cotton cultivation) were estimated to be on the order of ≈10-100 kg year(-1) for the HCH isomers (including the β -isomer) and p,p'-DDE. The high levels of OCPs in soils, particularly in the vicinity of obsolete-pesticide storage facilities and at select urban sites are of concern and warrant regular monitoring activities and the development of containment or mitigation strategies.     

HCHs and DDTs in sediment-dwelling animals from the Yangtze Estuary, China

HCHs and DDTs in sediment-dwelling animals including mollusks and crabs from the Yangtze Estuary were determined by GC-ECD. Levels of t-HCH were in the range of 1.2-5.5 ng g(-1) and averaged 3.5 ng g(-1) in mollusks, while t-DDT concentrations ranged from 26.0 to 68.8 ng g(-1), with a mean of 34.5 ng g(-1). In crabs t-HCH concentrations varied from 2.0 to 25.7 ng g(-1) and averaged 13.8 ng g(-1), whereas the concentrations of t-DDT were in the range of 1.5-24.8 ng g(-1) with a mean value of 5.9 ng g(-1). The HCHs and DDTs levels depend on geographical position and sources, showing the high levels at fresh water area in the estuary, such as XP, CM and LHK sites, and lower at brackish water area, such as FX site, and little difference between species. Results also indicate there was no significant relationship between t-HCH (t-DDT) concentrations and lipid contents both in mollusks and crabs because of non-equilibrium state under a specific estuarine dynamics; smaller individuals accumulated more HCHs and DDTs than larger individuals of mollusks at LHK site, showing different uptake rate for these pesticides; moreover, HCHs and DDTs levels were lower in female crab bodies than male crab bodies suggesting that the release of spawning. BSAFs (Biota- Sediment Accumulation Factors) from sediment-dwelling animals for HCHs and DDTs show a significant "one high with two low" and "one low with two high" effect in the Yangtze Estuary.     

Inhibition of retinoid activity by components of a paper mill effluent

Few studies have evaluated PCB concentrations in alligators. This is the first comparison of PCB concentrations in alligators eggs from the southeastern United States. Eggs were collected from Bear Island and Winyah Bay, South Carolina and from the Rockefeller Wildlife Refuge, Louisiana. Mean PCB concentrations in eggs from Bear Island (333 ng/g) were the same (P > 0.45) as those found at the Rockefeller Wildlife Refuge (218 ng/g). However, eggs from Winyah Bay contained 3176 ng/g PCBs which is higher (P < 0.008) than concentrations from the other two sites. These data indicate the ubiquitous nature of PCBs and their bioaccumulation even in remote habitats.     

Chlorinated pesticides and PCBs in sediments and molluscs from freshwater canals in the Hanoi region

The concentrations of organochlorine pesticides and PCBs were determined in surface sediments and freshwater molluscs (Angulyagra sp.) from water canals in the region of Hanoi city. Results obtained show that the concentration of sigma DDT compounds in sediments range from 7 to 80 ng/g (dry weight) and from 6 to 864 ng/g (dry weight) in the soft tissues of molluscs. The concentrations of sigma DDTs were higher in populated sites and much lower in rural sites, indicating that the DDT has been used for mosquito control and not as a crop protection chemical. Hexachlocyclohexanes (HCHs) have also been widely used in the region but the current environmental concentrations are much lower than those of DDT's, which is due to the less persistence of those compounds. Polychlorinated biphenyls (PCBs) were measured, for example as aroclor 1254, in concentrations up to 40 ng/g (dry weight) and up to 76 ng/g (dry weight) in sediments and molluscs, respectively. Molluscs from water canals are a very popular food in the region. Taking into consideration the high DDT levels measured in these molluscs their consumption is worrisome and may expose the population to high levels of endocrine disrupting substances. Current PCB levels in sediments are lower than usually measured in industrialized countries. Therefore, PCB concentrations in aquatic molluscs are still also relatively low. These snails do not have enzyme ability to metabolize most of the CB congeners and, thus, are passive accumulators and a significant transfer pathway of CBs to consumers. Therefore, measures to phase out the use of these persistent and bioaccumulable chemicals should be adopted in order to prevent further environmental contamination.     

Olive tree, Olea europaea L., leaves as a bioindicator of atmospheric PCB contamination

Olive tree leaf samples were collected to investigate their possible use for biomonitoring of lipophilic toxic substances. The samples were analyzed for 28 polychlorinated biphenyls (PCB) congeners. Twelve congeners were detected in the samples. PCB-60, 77, 81, 89, 105, 114, and 153 were the most frequently detected congeners ranging from 32 % for PCB-52 to 97 % for PCB-81. Σ₁₂PCBs concentration varied from below detection limit to 248 ng/g wet weight in the sampling area, while the mean congener concentrations ranged from 0.06 ng/g (PCB-128?+?167) to 64.2 ng/g wet weight (PCB-60). Constructed concentration maps showed that olive tree leaves can be employed for the estimation of spatial distrubution of these congeners.     

Flame retardants, surfactants and organotins in sediment and mysid shrimp of the Scheldt estuary (The Netherlands)

Sediment and mysids from the Scheldt estuary, one of the largest and most polluted estuaries in Western Europe, were analyzed for a number of contaminants that have been shown to possess endocrine-disrupting activity, i.e. organotins, polybrominated diphenyl ethers (PBDEs), hexabromocyclododecane (HBCD), tetrabromobisphenol A (TBBPA), nonylphenol ethoxylates (NPE) and transformation products, nonylphenol (NP) and nonylphenol ether carboxylates (NPEC). In addition, in vitro estrogenic and androgenic potencies of water and sediment extracts were determined. Total organotin concentrations ranged from 84 to 348 ng/g dw in sediment and 1110 to 1370 ng/g dw in mysid. Total PBDE (excluding BDE-209) concentrations ranged from 14 to 22 ng/g dw in sediment and from 1765 to 2962 ng/g lipid in mysid. High concentrations of BDE-209 (240-1650 ng/g dw) were detected in sediment and mysid (269-600 ng/g lipid). Total HBCD concentrations in sediment and mysid were 14-71 ng/g dw and 562-727 ng/g lipid, respectively. Total NPE concentrations in sediment were 1422 ng/g dw, 1222 ng/g dw for NP and 80 ng/g dw for NPEC and ranged from 430 to 1119 ng/g dw for total NPE and from 206 to 435 ng/g dw for NP in mysid. Significant estrogenic potency, as analyzed using the yeast estrogen assay, was detected in sediment and water samples from the Scheldt estuary, but no androgenic activity was found. This study is the first to report high levels of endocrine disruptors in estuarine mysids.     

Mercury concentrations in deer mouse (Peromyscus maniculatus) tissues from Isle Royale National Park.

We used deer mice (Peromyscus maniculatus) to investigate variation in mercury exposure across the terrestrial ecosystem of Isle Royale National Park (Michigan, USA). Although previous work suggested that mercury (Hg) levels may be higher inside the Sargent Lake watershed of Isle Royale than outside the watershed, Hg concentrations in livers were higher outside the Sargent Lake watershed (100.13 ng Hg/g dry tissue) than inside the watershed (35.50 ng Hg/g dry tissue; P = 0.06). Mercury levels in kidneys did not differ significantly (P = 0.57) between samples collected outside (443.23 ng Hg/g dry tissue) and inside (360.62 ng Hg/g dry tissue) the Sargent Lake watershed. Mean Hg concentrations in the livers of mice at some sites in Isle Royale are not significantly lower (P = 0.62) than Hg concentrations considered by some government agencies to be unhealthy for human consumption. Although Hg concentrations in mouse tissues were not remarkably high (compared to heavily polluted sites), concern is warranted because: (1) Isle Royale National park is a protected area in a remote location; (2) any exposure in deer mice represents a path for biomagnification in the terrestrial food web; and (3) the source of this mercury remains unidentified.     

Butyltin concentrations in oysters from the Gulf of Mexico from 1989 to 1991

Oyster samples from 53 Gulf of Mexico coastal sites were collected and analyzed for butyltins during 1989, 1990, and 1991. The geometric-mean tributylin concentrations were 85, 30, and 43 ng Sn/g for 1989, 1990, and 1991, respectively. The tributyltin concentrations are best represented by a log-normal distribution. A decline in the butyltin concentrations at sites with relatively low butyltin concentrations for 1989 compared with 1990 and 1991 was observed, and, at relatively high butyltin concentrations (> 400 ng Sn/g), there was hardly any difference between 1989 and 1991, but lower concentrations were present in 1990. Continued monitoring is needed in order to determine if butyltin contamination of the coastal marine environment is decreasing in response to use limitations.     

Alkylphenols and their ethoxylates in seafood from the Tyrrhenian Sea

The present study reports the results of an investigation on occurrence of octylphenols (OPs), nonylphenols (NPs) and their respective ethoxylates (with 1-6 ethoxylic group) in aquatic species of commercial interest from the Tyrrhenian Sea. Samples were collected at Livorno, Fiumicino and Salerno commercial harbors, during September-October 2003. The data obtained showed that almost all of the tested compounds were found in all the samples. NP was generally detected at the highest concentrations. Among the tested species common to the three sampling sites, mullets and seabreams generally showed high values of total alkylphenols (APs) and alkylphenol ethoxylates (APEOs) (44-55 ng g(-1) and 27-525 ng g(-1) fw), yet, the maximum concentrations were found in shrimps from Fiumicino (1255 ng g(-1) fw). On the contrary, the lowest concentrations were observed in hakes and anchovies (34-36 ng g(-1) and 6-37 ng g(-1) fw). Tuna, exhibited very high concentrations of total alkylphenolic compounds (APEs) (889 ng g(-1) fw). Seafood from Fiumicino fishing area, which is under the influence of the River Tiber, showed a degree of contamination of at least one order of magnitude higher than the other two sites. On the basis of the results of this study, the corresponding daily intakes of NPs are much lower than the TDI proposed by the Danish Environmental Agency.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Concentrations of methylmercury in invertebrates from wetlands of the Prairie Pothole Region of North America

Prairie wetlands may be important sites of mercury (Hg) methylation resulting in elevated methylmercury (MeHg) concentrations in water, sediments and biota. Invertebrates are an important food resource and may act as an indicator of MeHg exposure to higher organisms. In 2007-2008, invertebrates were collected from wetland ponds in central Saskatchewan, categorized into functional feeding groups (FFGs) and analyzed for total Hg (THg) and MeHg. Methylmercury and THg concentrations in four FFGs ranged from 0.2-393.5 ng · g(-1) and 9.7-507.1 ng · g(-1), respectively. Methylmercury concentrations generally increased from gastropods with significantly lower average MeHg concentrations compared to other invertebrate taxa. Surrounding land use (agricultural, grassland and organic agricultural) may influence MeHg concentrations in invertebrates, with invertebrate MeHg concentrations being higher from organic ponds (457.5 ± 156.7 ng · g(-1)) compared to those from grassland ponds (74.8 ± 14.6 ng · g(-1)) and ponds on agricultural lands (32.8 ± 6.2 ng · g(-1)).     

PCDDs, PCDFs, PCBs and DDE in edible marine species from the Adriatic Sea

Edible marine species from several areas of the Adriatic sea were analyzed for their content in persistent organic pollutants (POPs), such as polychlorinated dibenzodioxins (PCDDs), dibenzofurans (PCDFs), biphenyls (PCBs), and pp'-DDE (dichlorodiphenyldichloroethylene), a metabolite of the organochlorine pesticide dichlorodiphenyltrichloroethane (DDT). On the whole, PCDD/F contamination levels were low. In general, I-TEQ findings were greater for those species at higher levels in the trophic web (mackerel > red mullet > anchovy). Contamination levels were within 0.23 and 1.07 pg TEQ/g fw (fresh weight) in the aforesaid species, while all remaining species exhibited contamination levels ranging from approximately 0.07 to 0.25 pg TEQ/g fw. Besides, TEQ cumulative findings in species from the northern area were in general greater than those from the central and southern areas. PCB cumulative findings in the samples also revealed a detectable difference in contamination levels in species obtained from the northern, central, and southern sampling sites, between 7.6 and 177, 2.3 and 157, and 4.5 and 94 ng/g fw, respectively. The greatest PCB concentrations were found in mackerel (94-177 ng/g fw). Finally, DDE concentration levels varied from 0.7 to 32.4 ng/g fw. The highest levels of contamination were found in mackerel, red mullet and anchovy (17.7-32.4 ng/g fw, 8.1-9.8 ng/g fw, and 6.4-11.9 ng/g fw, respectively).     

Organic compounds temporal trends at some invertebrate species from the Balearics, Western Mediterranean

Concentrations of persistent organic pollutants (POPs) such as hexachlorobenzene (HCB), dichlore diphenyl trichloretane (DDT), polychlorinated biphenyls (PCBs), and gamma-hexachlorocyclohexane (gamma-HCH or lindane) were determined in tissue of marine benthic invertebrates such as Mytilus galloprovincialis, Chamelea gallina, Venus verrucosa, Lithophaga lithophaga and Paracentrotus lividus. Species were selected due to their habitat, trophic level, feeding behaviour and their consumption. Invertebrate species were systematically sampled from December 1996 to December 2005 from several sites along the Balearic Islands. The highest concentrations of PCBs (785ng/g lipid) were found in M. galloprovincialis while the lowest concentrations were found in the sea-urchin P. lividus (193ng/g lipid). Among the 7 PCB quantified congeners the higher values are mainly obtained for CB138 and CB153. All bivalves presented higher PCBs contents than the sea-urchin P. lividus are possibly linked with the bioaccumulation process of POPs throughout the food web and to differential detoxifying mechanisms. The concentration of SigmaDDT exceeds that of HCB and gamma-HCH at all species and sampling stations. DDT concentrations ranged from 0.4ng/g ww at the bivalve C. gallina in 2002, to values of 15.8ng/g ww at the bivalve L. lithophaga in 1998. The values obtained for the organic compounds (HCH, HCB, PCBs, DDT) depend upon the place and year of sampling and are compared to values found by other authors for the mussel M. galloprovincialis in other Mediterranean areas. gamma-HCH and HCB were found in lower concentrations than the other POPs.     

Tributyltin in environmental samples from the Former Derecktor Shipyard, Coddington Cove, Newport RI

Tributyltin (TBT) was detected in all 24 surface sediment (top 2 cm) samples collected from Coddington Cove, Newport, RI. TBT surface sediment concentrations ranged from 32 to 372 ng Sn/g with a mean concentration of 146 ng Sn/g. Analyses of selected core sections detected TBT in at least the top 18 cm at all 7 stations where cores were collected. No consistent TBT concentration trends with depth for these cores suggest mixing is an important process in the sediment column. In one core (station 28), TBT was found in the 76-86 cm section at a concentration of 141 ng Sn/g; thus sediments are a significant sink for TBT. However, sediment mixing processes can enhance releases of bioavailable TBT. Mussels, clams and fish from Coddington Cove contain TBT at concentrations ranging from 9.2 to 977 ng Sn/g. TBT concentrations in lobsters were below the detection limit (<6 ng Sn/g). Based on available screening criteria, TBT concentrations in Coddington Cove sediment is likely to be having an adverse effect on the biota at some locations.     

Antifouling paint booster biocide contamination in Greek marine sediments

Organic booster biocides were recently introduced as alternatives to organotin compounds in antifouling products, after restrictions imposed on the use of tributyltin in 1987. In this study, the concentrations of three biocides commonly used as antifoulants, Irgarol 1051 (2-methylthio-4-tertiary-butylamino-6-cyclopropylamino-s-triazine), dichlofluanid (N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenyl sulphamide) and chlorothalonil (2,4,5,6-tetrachloro isophthalonitrile) were determined in sediments from ports and marinas of Greece. Piraeus (Central port, Mikrolimano and Pasalimani marinas), Thessaloniki (Central port and marina), Patras (Central port and marina), Elefsina, Igoumenitsa, Aktio and Chalkida marinas were chosen as representative study sites for comparison with previous monitoring surveys of biocides in coastal sediments from other European countries. Samples were collected at the end of one boating season (October 1999), as well before and during the 2000 boating season. All the compounds monitored were detected at most of sites and seasonal dependence of biocide concentrations were found, with maxima during the period June-September, while the winter period (December-February) lower values were encountered. The concentrations levels ranged from 3 to 690 ng/g dw (dry weight). Highest levels of the biocides were found in marinas (690, 195 and 165 ng/g dw, for Irgarol, dichlofluanid and chlorothalonil respectively) while in ports lower concentrations were observed. Antifouling paints are implicated as the likely sources of biocides since agricultural applications possibly contributed for chlorothalonil and dichlofluanid inputs in a few sampling sites.     

Accumulation of butyl- and phenyltin compounds in starfish and bivalves from the coastal environment of Korea

Triphenyltin (TPT) and tributyltin (TBT) concentrations were determined in two starfish species (Asteria pectinifera and Asterias amurensis), bivalves (Crassostrea gigas or Mytilus edulis), and seawater samples from sites around the coasts of Korea. Both TPT and TBT concentrations in starfish ranged from 8 to 1560 ng/g and from <2 to 797 ng/g as Sn on a dry weight basis, respectively. TPT concentration accounted for 75.4% and 86.4% of total phenyltin concentration in A. pectinifera and A. amurensis, respectively, while monobutyltin, a degradation product of TBT, accounted for 86.3% and 57.2% of total butyltin, respectively. Triphenyltin concentrations in A. pectinifera were significantly correlated to water and bivalve TPT concentrations, which implies that dietary uptake of TPT from contaminated prey as well as direct uptake from surrounding water contribute to TPT body residues in the starfish. Starfish could be target organisms for monitoring TPT compound in the marine environment, due to their high accumulation and low degradation capacity towards TPT.