Concentrations of Antifouling Biocides in Sediment and Mussel Samples Collected from Otsuchi Bay,Japan

Organotin compounds (OTs) and representative booster biocides were measured in sediment and mussels from Otsuchi Bay, Japan. The mean amounts of tributyltin (TBT) and triphenyltin (TPT) compounds in sediment were 13 μg kg⁻¹ dry and 3 μg kg⁻¹ dry, respectively. Representative booster biocides (Sea-Nine 211, Diuron, Dichlofluanid, Irgarol 1501, M1, which is a degradation compound of Irgarol 1051, and Copper pyrithione) were also detected in sediment from Otsuchi Bay. OT concentrations were higher than those of the measured booster biocides. Otsuchi Bay was divided into four parts by cluster analysis based on OT concentrations in sediment sampled from the bay. These areas included the vicinity of a shipyard, a small fishing port, the closed inner area of the bay, and the mouth of the bay. Higher concentrations of TBT and TPT and a higher ratio of TBT to total BTs were observed in the vicinity of the shipyard. A higher concentration of TPT in comparison with TBT was detected in a small fishing port. Furthermore, OT concentrations in the mouth of the bay were higher than those in the closed-off section. OT concentrations in mussels decreased with distance from the shipyard. Otsuchi Bay was then divided into three parts by cluster analysis based on the concentrations of representative booster biocides found in the bay’s sediment. These areas included the vicinity of a shipyard, a small fishing port, and other sites. Concentrations of Diuron and Irgarol 1051 in the vicinity of a shipyard and a small fishing port were dramatically high in comparison with the other sites. Copper pyrithione and Dichlofluanid in addition to Diuron and Irgarol 1051 were also detected in the area of a small fishing port. The concentrations of antifouling biocides were highest in the water in front of the shipyard and showed a marked decrease with distance from the shipyard.     

Occurrence of Antifouling Biocides and Fluorinated Alkyl Compounds in Sediment Core from Deep Sea: Suruga Bay,Tosa Bay,and Nankai Tough,Japan

Contamination profiles of antifouling biocides were investigated in a deep-sea environment in Suruga Bay Japan. Significant differences in the tributyltin (TBT) and triphenyltin (TPT) concentrations in subsurface sediment between 850 and 800 m of water depth were not observed (p < 0.05). Organotin (OT) concentrations in sediment core of 0–30.5 cm from a water depth of 800 m were investigated. The butyltins (BTs) and phenyltins (PTs) concentrations were constant between 0 and 15 cm, and, subsequently, the concentration of these compounds increased. The peaks of the BTs and PTs concentrations were observed between 18 and 19 cm. The concentrations of Irgarol 1051 decreased until a core depth of 9 cm, and, the values then became near the detection limit under the 10 cm of core depth. Perfluorooctane sulfonate (PFOS) and perfluorooctanic acid (PFOA) were detected in the sediment core (0–30.5 cm) of Suruga Bay. The concentration of PFOS was high in the 0–5-cm core depth and then decreased. The concentrations of PFOA, however, were at the values near the detection limit throughout the sediment core. The BTs and PTs concentrations in surface sediment from Tosa Bay decreased with water depth. Although Irgarol 1051 was the only alternative compound detected, the value was near the detection limit. PFOS and PFOA were detected in sediment core from Tosa Bay. The concentrations of PFOS became low as the water depth became deeper. TBT, TPT, Sea Nine 211, Diuron and Irgarol 1051 were detected in sediment core (core depth: 10 cm) from the Nankai trough (water depth: 4010 m).     

Monitoring of Antifouling Booster Biocides in Water and Sedimentfrom the Port of Osaka, Japan

Concentrations of booster antifouling compounds in the port of Osaka, Japan were assessed. Concentrations of Sea-Nine 211 (4,5-dichloro-2-n-octyl-3-isothiazolone), thiabendazole (2-(4-thiazolyl)-benzimidazole), IPBC (3-iodo-2-propynyl butylcarbamate), Diuron (3,4-dichlorophenyl-N, N-dimethylurea), Irgarol 1051 (2-methylthio-4-t-butylamino-6-cyclopropylamino-s-triazine), and M1 (2-methylthio-4-t-butylamino-6-amino-s-triazine) in port water samples were in the range of <0.003–0.004 g L^–1, <0.0008–0.020 g L^–1, <0.0007–1.54 g L^–1, <0.0008–0.267 g L^–1, and <0.0019–0.167 g L^–1, respectively. IPBC was not detected in the water samples, but the concentration of Diuron was higher than any previously reported. The concentrations of Sea-Nine 211, thiabendazole, Diuron, Irgarol 1051, and M1 in sediment samples were in the range of <0.04–2.4 g kg^–1 dry, <0.08–1.2 g kg^–1 dry, <0.64–1350 g kg^–1 dry, <0.08–8.2 g kg^–1 dry, and <0.18–2.9 g kg^–1 dry, respectively. IPBC was again not detected. The levels of Sea-Nine 211, Diuron, and Irgarol 1051 in water and sediment samples were high in a poorly flushed mooring area for small and medium-hull vessels. Levels of Diuron and Irgarol 1051 were highest in summer. The concentration of Sea-Nine 211 in water increased between August and October 2002. Except for M1, increases in the levels of booster biocides in sediment were observed during the study period. The sediment–water partition (Kd) was calculated by dividing the concentrations in sediment by the concentrations in water. The Kd values for Sea-Nine 211, thiabendazole, Diuron, Irgarol 1051, and M1 were 690, 180, 2700, 300, and 870. The Kd value for these alternative compounds was lower than for TBT.     

Contamination Profiles of Antifouling Biocides in Selected Coastal Regions of Malaysia

The concentrations of butyltins (BTs) in sediment from Peninsular Malaysia along the Strait of Malacca and their spatial distribution are discussed. The concentrations of BTs were high in the southern part of Peninsular Malaysia where there is a lot of ship traffic, because trade is prosperous. The concentrations of monobutyltin (MBT), dibutyltin (DBT), and tributyltin (TBT) in sediment from the coastal waters of Peninsular Malaysia were in the range 4.1–242 μg/kg dry weight (dw), 1.1–186 μg/kg dw, and 0.7–228 μg/kg dw, respectively. A higher percentage of TBT was observed in the area where TBT concentrations were high. The concentrations of monophenyltin (MPT), diphenyltin (DPT), and triphenyltin (TPT) were in the range <0.1–121 μg/kg dw, 0.4–27 μg/kg dw, and 0.1–34 μg/kg dw in sediment from Peninsular Malaysia, respectively. MPT was the dominant phenyltin species. MBT, DBT, and TBT in green mussel (Perna viridis) samples were detected in the range 41–102 μg/kg, 3–5 μg/kg, and 8–32 μg/kg, respectively. A tolerable average residue level (TARL) was estimated at 20.4 μg/kg from a tolerable daily intake (TDI) of 0.25 μg TBTO/kg body weight/day. The maximum value of TBT detected in green mussel samples was the value near the TARL. TPTs were not detected in green mussel samples. The concentrations of Diuron and Irgarol 1051 in sediment from Peninsular Malaysia were in the range <0.1–5 μg/kg dw and <0.1–14 μg/kg dw, respectively. High concentrations of these compounds were observed in locations where the concentrations of TBT were high. Sea Nine 211, Dichlofluanid, and Pyrithiones were not detected in sediment. The concentrations of antifouling biocides in Melaka and the Strait of Johor were investigated in detail. BTs were found in similar concentrations among all sampling sites from Melaka, indicating that BT contamination spread off the coast. However, Sea Nine 211, Diuron, and Irgarol 1051 in the sediment from Melaka were high at the mouth of the river. BT concentrations at the Strait of Johor were higher than those in Peninsular Malaysia and Melaka and were high at the narrowest locations with poor flushing of water. The concentrations of antifouling biocides were compared among Malaysia, Thailand, and Vietnam. A higher concentration and wide variations of TBT and TPT in sediment from Malaysia were observed among these countries. The Irgarol 1051 concentrations in sediment from Malaysia were higher than those in Thailand and Vietnam.     

Occurrence of Antifouling Biocides in Sediment and Green Mussels from Thailand

Various antifouling biocides were surveyed in sediment and green mussels (Perna viridis) from the coastal area of Thailand. The concentrations of butyltin (MBT), dibutyltin (DBT), and tiributyltin (TBT) in sediment from Thailand were in the range of 1–293 μg kg⁻¹ dry wt., 1–368 μg kg⁻¹ dry wt., and 2–1246 μg kg⁻¹ dry wt., respectively. A higher concentration of TBT was observed in industrial areas, where many tankers and cargo ships sail and moor. Phenyltin (PT) compounds were not detected in most of the sampling sites. The concentrations of MBT, DBT, and TBT in green mussels from Thailand were in the range of 8–20 μg kg⁻¹ wet wt., 4–9 μg kg⁻¹ wet wt., and 4–45 μg kg⁻¹ wet wt., respectively. The concentration of TBT was high in an area where aquaculture practice is common. The detection frequencies of TPT were low. Representative booster biocides were surveyed in sediment. The detection frequencies of Sea Nine 211 were low (2/13). Furthermore, Sea Nine 211 concentrations in the detected samples were at values near the detection limit (0.051–0.094 μg kg⁻¹ dry wt.). Diuron was detected at the highest level among the booster biocides in the range of 0.07–25 μg kg⁻¹ dry wt. Irgarol 1051 was detected in the range of 0.03–3.2 μg kg⁻¹ dry wt., and concentrations of the degradation product’s M1 were 0.03–4.9 μg kg⁻¹ dry wt. Diuron and Irgarol 1051 showed higher concentrations in industrial areas and fishery sites, respectively. Diuron was only detected among green mussels in the range of <0.64–9.6 μg kg⁻¹ wet wt. The lower ratio of Diuron and Irgarol 1051 for TBT concentration suggests that TBT is still being used in Thailand.     

Distribution of Antifouling Biocides and Perfluoroalkyl Compounds in Sediments From Selected Locations in Indonesian Coastal Waters

The goal of this article is to verify the applicability of two different biological assays for studying a coastal area that is subject to anthropogenic inputs. Phytochelatins in the marine diatom Thalassiosira weissflogii were used as a biomarker of metal bioavailability. The frequency of genetic damage in the sensitive D7 strain of the yeast Saccharomyces cerevisiae was used to estimate the mutagenic potential. Biological assays were carried out using sediment elutriates. Sediments were collected at three selected sites located in the Gulf of Follonica (Tuscany, Italy), during a 2-year sampling period: Cala Violina (reference site) and the mouths of the rivers Pecora and Cornia, named sites V, P and C, respectively. The chemical characterization of each site was determined in terms of metal concentrations (As, Cd, Cr, Cu, Ni, Pb), measured in 11 sediment samples for each site. The results showed that metal concentrations in sediments from sites C and P were 2–10 times higher than the reference values (site V, year 2004). In addition, we found generally higher metal concentrations in the 2007 sediments than in the 2008 ones, including those of site V, due to the occurrence of an unexpected pollution event. This enabled us to obtain a pollution gradient to validate the proposed bioassays. In fact, the bioassays showed a potential biological hazard in the 2007 elutriates. Significant mutagenic effects were found in samples exhibiting higher concentrations of Cd and Cr. The induction of phytochelatins in T. weissflogii correlated positively with the Cd concentration in the elutriates.     

Screening of Antifouling Biocides Around a Pleasure Boat Marina in the Baltic Sea After Legal Restrictions

Copper, zinc, and Irgarol 1051 concentrations were determined around a pleasure boat marina in the Stockholm Archipelago. Copper concentrations in water were twice as high (6.62 μg L⁻¹) in 2004 as 1992–1993, zinc concentrations six times higher (20.0 μg L⁻¹). Concentrations in bladder wrack (Fucus vesiculosus) had also risen. Irgarol concentrations in water were similar (~0.17 μg L⁻¹) in 1996 and 2004, while concentrations in bladder wrack halved from 1993 to 2004. The peak concentrations of copper and Irgarol in water have shifted indicating that the main source in the 1990 s were local boats, but in 2004 visiting boats.     

An outbreak of adenovirus serotype 41 infection in infants and children with acute gastroenteritis in Maizuru City, Japan.

A total of 337 fecal specimens were collected from infants and children with acute gastroenteritis in Maizuru City, Japan from July 2004 to June 2005 and tested for the presence of rotavirus, norovirus, sapovirus, astrovirus, and adenovirus by RT-multiplex PCR. Among diarrheal viruses detected, norovirus was the most prevalent (13.6%, 46 of 337), followed by adenovirus (8%, 27 of 337), group A rotavirus (5%, 17 of 337), astrovirus (1.8%, 6 of 337), and sapovirus (1.8%, 6 of 337), respectively. Adenovirus was subjected to molecular genetic analysis by sequencing. Adenovirus detected in this study was classified into five serotypes, namely Ad1, Ad2, Ad3, Ad5, and Ad41. Of these, Ad41 was the most predominant serotype that accounted for 85.2% (23 of 27). It was noteworthy to point out that Ad41 infection was apparently confined only to the period of 4 months (October 2004 through January 2005). This pattern of infection implied the outbreak of Ad41 in these subjects, which was the first outbreak of acute gastroenteritis attributed to adenovirus in Maizuru City, Japan. Another interesting feature of the study was the existence of two Ad41 subtypes co-circulating in this outbreak. This report confirmed the presence of adenovirus as one of an important cause of acute gastroenteritis among Japanese infants and children.     

Effects of Five Antifouling Biocides on Settlement and Growth of Zoospores from the Marine Macroalga Ulva lactuca L.

Antifouling biocides are found in the marine ecosystem were they can affect non-target organisms. In this study the effects of five antifouling biocides on the settlement and growth of Ulva lactuca zoospores were investigated. The biocides investigated were copper (Cu²⁺), 4,5-dichloro-2-n-octyl-3(2H)-isothiazolone (DCOIT), triphenylborane pyridine (TPBP), tolylfluanid and medetomidine. Full concentration–response curves where determined for each compound. EC₅₀ values were determined for copper, DCOIT, TPBP and tolylfluanid, all of which inhibited settlement and growth in a concentration dependent manner with the following toxicity ranking; tolylfluanid (EC₅₀ 80 nmol L^?1) ~ DCOIT (EC₅₀ 83 nmol L^?1) > TPBP (EC₅₀ 400 nmol L^?1) > Cu²⁺ (EC₅₀ 2,000 nmol L^?1). Medetomidine inhibited settlement and growth only at the extreme concentration of 100,000 nmol L^?1 (93 % effect). The low toxicity is possibly a consequence of a lack of receptors that medetomidine can bind to in the U. lactuca zoospores.     

Polychlorinated biphenyl pollution from shipbuilding in Nagasaki Bay, Japan

Polychlorinated biphenyl (PCB) pollution from shipbuilding in Nagasaki Bay, Japan, was discussed by determining PCB concentrations in sediment, in water, and in biological samples. PCBs were detected in all samples, in which much higher concentrations, more than 10 micrograms/g, were found in three sediment samples where located near the shipyard drains. In general, PCB concentrations in sediments and organisms tended to increase toward the inner part of this bay. PCB isomer and congener compositions in organisms as well as sediments were composed mainly of higher chlorinated biphenyls and almost similar to Kanechlor 500 and 600 products (chlorine content 54 and 60%, respectively) that have been used for ship paints. These results strongly suggest that the shipbuilding is primarily responsible for the PCB pollution in Nagasaki Bay. Bioaccumulation factors of PCBs were different among the organisms according to their trophic levels. This might be a result of the predominant PCB transfer through the food chain in organisms and the discharge of bioaccumulative PCBs as higher chlorinated biphenyls from shipyards. These observations imply that the PCB pollution from shipbuilding would continue for a long time due to the accumulative characteristics of PCBs used for ship paints and the further discharge by scraping the stale paints in shipyards.     

Polychlorobiphenyis (PCBs) in sediments of Tokyo Bay,Japan

Sediment cores were collected from five sites in Tokyo Bay. The sediment age was estimated by the²¹⁰Pb method and the polychlorobiphenyls (PCBs)(2,5,2,4,5 — pentachlorobiphenyl,3,4,2,4, 5-pentachlorobiphenyl, 3,4,2,3,4-pentachlorobiphenyl, 2,3,6,2,3,6-hexachlorobiphenyl, 2,4, 5,2,4,5-hexachlorobiphenyl, and 2,4,5,2,3,4, 5-heptachlorobiphenyl) profiles in the sediments were determined quantitatively by gas chromatography. With respect to the horizontal distribution of PCBs, the levels were highest off Tokyo and Kawasaki, the inner western part of the bay off the mouths of the Tama and Arakawa Rivers, and declined in the direction of the eastern and southern parts of the bay. It was assumed that most of the PCBs supplied to the bay from the adjacent rivers and the industrial zones along the western coast were coprecipitated with suspended particles near the river mouths and the western coast, while PCBs adsorbed by fine particles are carried throughout the bay by the current. The accumulation rate of PCBs in Tokyo Bay sediments gradually increased, starting about 1936, and reached a maximum value in 1972 and declined moderately thereafter. The time-dependent changes in the quantity released into the environment were estimated from the amount of PCBs manufactured and used. The accumulation rate of PCBs in Tokyo Bay sediments was then compared with the estimated rate of release into the environment.     

Identification of polychlorinated dibenzo-p-dioxin,dibenzofuran, and coplanar polychlorinated biphenyl sources in Tokyo Bay,Japan

A dated sediment core collected from Tokyo Bay, Japan, was used to assess the historical inputs of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (Co-PCBs) from multiple sources. The levels, patterns, and profiles of these compounds in the core were congener-specifically investigated, and the results show that the PCDD and PCDF (PCDD/F) and the Co-PCB inputs increased abruptly from the late 1950s and peaked during the period 1967 to 1972. From 1972 to 1981, the inputs decreased continuously and then generally leveled off. Using principal component analysis, two herbicides widely used in the past, pentachlorophenol (PCP) and chloronitrofen (CNP), as well as combustion processes were identified as the major dioxin sources in Tokyo Bay. The PCB formulations and combustion processes were estimated to be the major sources of Co-PCBs. Furthermore, multiple regression analysis was performed for dioxin-source apportioning, and it was found that the herbicides PCP and CNP have mainly contributed to the PCDD/F burdens since the late 1950s. This study suggests that herbicide-derived PCDD/Fs remaining in agricultural land will continue to run off and pollute the aquatic environment in Japan for a long time.     

Historical Distribution of PCDDs, PCDFs, and Coplanar PCBs in Sediment Core of Ariake Bay, Japan

Persistent organic pollutants, particularly polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), coplanar polychlorinated biphenyls (co-PCBs) and toxic equivalent quantity (pg TEQ g⁻¹) were determined in sediment samples collected from Ariake Bay, Japan. The total concentration of PCDDs/DFs in surface sediment of the Yabe River (17,000 pg g⁻¹ dry wt) was approximately 2.5-fold higher than that of the Chikugo River (7,000 pg g⁻¹ dry wt) which has the highest flow amount of about 40% inputting to the northern Bay. The congener profile suggested that dioxin sources could be close to the study area. The PCDDs concentration (12,000 pg g⁻¹ dry wt) in the sediment layer, which was corresponding to the 1960s, was reflected on the pentachlorophenol (PCP) contamination occurring at that time in Ariake Bay. The reflecting of PCP in the sediment core was significantly considered by hierarchical cluster analysis. Based on isomer-specific analysis, the tetrachlorodibenzo-p-dioxin composition showed a gradual increase from 1978–1982 toward the surface, indicating that the pollution source at that period might be more influenced by chloronitrofen than PCP. This fact was supported, based on the ratio of ΣPCDD to ΣPCDF concentration. The PCDDs/DFs-derived TEQ contributed more than 90% of the ΣTEQ (PCDDs/DFs and co-PCBs) in all the detected sediment layers. The contribution of PCBs to the total TEQ was low; however, an increasing historical trend of concentration was clearly observed.     

Horizontal and Vertical Distribution of Estrogenic Activities in Sediments and Waters from Tokyo Bay, Japan

Endocrine-disrupting chemicals with estrogenic activity (e.g., alkylphenols) have been detected in coastal Japan. We aimed to determine estrogenic activity in extracts of river water, seawater, sediments, and sediment cores from Tokyo Bay by in vitro gene expression assay. Fifty-one of 57 extracts had some estrogenic activity. E₂ equivalents (ng E₂ equivalents per gram dry weight or per liter above the limit of detection) in river water samples ranged from 0.70 to 4.01 ng/L; in seawater samples from 0.34 to 2.52 ng/L; and in surface sediments from 2.07 to 12.1 ng/g. The relationship between salinity and estrogenic activity in water samples suggested that fresh water is one source of environmental estrogens in Tokyo Bay. Fractionation of sediment extracts showed that the highest estrogenic activity was observed in the midpolar fraction. The observed activities were compared with activities mediated by known concentrations of nonylphenol, bisphenol-A, estrone, and 17-estradiol. In sediment collected near the sewage treatment plants, the estrogenic activity of the midpolar fraction could be explained about 34% by nonylphenol and estrone contained in this fraction. Core sediment measurements detected estrogenic activity from as far back as the 1960s. The regulations on the industrial wastewater in early 1970s would be one of the main reasons for the lower estrogenic activity in the upper section of the sediment core. The high estrogenic activities as measured in water and sediment samples from Tokyo might be restricted to certain coastal areas.     

Mercury Distribution in Seawater of Kagoshima Bay near the Active Volcano, Mt. Sakurajima in Japan

Kagoshima bay has a highly active volcano in its center. In the filtered seawater and suspended matter collected from 200-m deep fumaroles at the bottom of the inner bay, the geometric mean concentrations of total mercury were 7.6 and 65.0 ng/L, respectively. The surface seawater collected at the inner bay had a higher concentration of mercury when compared to that in the bay entrance (average: 1.0 vs. 0.5 ng/L). In July, however, no such difference was observed. The fumaroles seem to contribute to relatively high concentrations of mercury in the inner bay except in summer, when thermal cline is formed.     

Evaluation of ecotoxicity and fate of methylated butyltins in sediments and seawater from Tokyo Bay, Japan

We analyzed the fate of organotins in seawater and sediments from Tokyo Bay, Japan, by gas chromatography/inductively coupled plasma mass spectrometry. We also measured the toxicity of methylated butyltins by in vitro bioassays, the retinoid X receptor (RXR) activation method, and the marine luminescent bacterium Vibrio fischeri. Concentrations of tributyltin (TBT) and tributylmonomethyltin (TBMMT) in seawater were 0.0636 to 0.419 and 0.0050 to 0.108 ng Sn/L and in sediment were 7.51 to 17.8 and 3.67 to 6.87 ng Sn/wet weight g, respectively. Methylated butyltins did not activate RXR and were not toxic to bacteria. Tributylmonomethyltin in seawater would elute from sediment since TBMMT-to-TBT ratios showed a positive correlation (r(2) = 0.858) between sediment and deep seawater. Both methylation and debutylation of TBT seem to be major routes of decomposition of TBT in sediment. Methylation of TBT would not only cause subsequent volatilization but also decrease the toxicity of TBT species in the marine environment.     

Contaminations of Metal in Tissues of Siberian Gull Larus heuglini: Gender, Age, and Tissue Differences

The objective of the present study was to investigate the levels of metals, namely cadmium, lead, and zinc, in Siberian gull (Larus heuglini) (n = 15), in order to: (1) examine the sex and gender related variation in trace metal accumulation, and (2) to determine the significant between metal concentrations in the kidney, liver, and pectoral muscle. The concentrations were different between the tissues of bird as well as among the interaction (sex × age), but this difference (except cadmium in liver and zinc in kidney) between the gender (male and female) and age (adult and juvenile) didn’t exist. Results showed that the metal concentrations in the Siberian gull were decreased in sequence of kidney > liver > muscle. The cadmium, lead, zinc concentration overall means they were measured as 2.2 ± 0.7, 8.8 ± 2.5, and 91.1 ± 37. 1 μg/g for kidney, 1.1 ± 0.2, 5.1 ± 0.8, and 68.3 ± 27.8 μg/g for liver, and 0.8 ± 0.1, 3.4 ± 0.6, and 34.4 ± 23.2 μg/g for pectoral muscle, respectively.