Bioaccumulation and toxic potencies of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in tidal flat and coastal ecosystems of the Ariake Sea,Japan

Sediment and marine biota comprising several species of tidal flat and coastal organisms were analyzed for polychlorinated biphenyls (PCBs) including non- and mono-ortho coplanar congeners and polycyclic aromatic hydrocarbons (PAHs) to examine bioaccumulation profiles and toxic potencies of these contaminants. Concentrations of PCBs in tidal flat organisms ranged from 3.6 ng/g (wet wt) in clams to 68 ng/g (wet wt) in omnivore tidal flatfishes, a discernible trend reflecting concentrations and trophic levels. In contrast, PAHs concentrations were the highest in lower trophic organisms, such as crabs and lugworms from tidal flat, whereas those in coastal fishes, squid, and finless porpoises were less than detection limit. Greater bioaccumulation of PAHs was found in lugworms and crabs, which might be due to their direct ingestion of sediment particulates absorbed with PAHs. TCDD toxic equivalents (TEQs) were calculated for PCBs and PAHs in sediments and biota. PCBs accounted for a greater proportion of total TEQs (sum(TEQs): sum of TEQ(PCB) and TEQ(PAH)) in coastal and tidal flatfishes (>95%), while PAHs occupied a considerable portion of sum(TEQs) in sediment (>97%). Interestingly, TEQ(PAH) accounted for 37% and 81% of the sum(TEQs) in crabs and clams, respectively. Benzo[b]fluoranthene was the dominant contributor to TEQ(PAH) in both the species. Considering these observations, the environmental risks of PAHs may not be ignored in benthic tidal flat organisms due to their greater bioaccumulation through sediments.     

A survey of perfluorooctane sulfonate and related perfluorinated organic compounds in water,fish, birds,and humans from Japan

Occurrence of perfluorooctane sulfonate (PFOS) in the tissues of humans and wildlife is well documented. In this study, concentrations and distribution of PFOS, perfluorohexane sulfonate (PFHS), and perfluorobutane sulfonate (PFBS) were determined in samples of surface water, fish and bird blood and livers, and human blood collected in Japan. Notable concentrations of PFOS were found in surface water and fish from Tokyo Bay. PFOS was found in all of the 78 samples of fish blood and liver analyzed. Based on the concentrations of PFOS in water and in fish livers, bioconcentration factors were calculated to range from 274 to 41 600. Concentrations of PFOS in the blood of Japanese human volunteers ranged from 2.4 to 14 ng/mL. PFHS was detected in 33% of the fishes analyzed, at concentrations severalfold less than those of PFOS.     

Occurrence of perfluorooctane sulfonate and other perfluorinated alkylated substances in harbor porpoises from the Black Sea

Perfluorooctane sulfonate (PFOS) and other perfluorinated alkylated substances (PFAS) were determined in liver, kidney, muscle, brain, and blubber samples of 31 harbor porpoises (Phocoena phocoena relicta) of different age and sex stranded along the Ukrainian coast of the Black Sea. In all individuals and in all tissues, PFOS was the predominant PFAS, accounting for on average 90% of the measured PFAS load. PFOS concentrations were the highest in liver (327+/-351 ng/g wet wt) and kidney (147 +/-262 ng/g wet wt) tissue, and lower in blubber (18+/-8 ng/g wet wt), muscle (41+/-50 ng/g wet wt), and brain (24 +/-23 ng/g wetwt). No significant differences could be determined between males and females, nor between juvenile and adult animals (p > 0.05). Perfluorononanoic acid, perfluorodecanoic acid, perfluoroundecanoic acid, and perfluorododecanoic acid could be detected in liver tissue of approximately 25% of the individuals. Perfluorobutane sulfonate, perfluorobutanoic acid, and perfluorooctanoic acid were not detected in any of the porpoise livers. Although we investigated a potential intraspecies segregation according to the source of prey, using stable isotopes, no statistically significant correlation between PFOS concentrations and stable isotopes could be determined. It is, however, noteworthy that the contamination by PFOS in the Black Sea harbor porpoises is comparable to levels found in porpoises from the German Baltic Sea and from coastal areas near Denmark and, therefore, might pose a threat to this population.     

Triclosan: occurrence and fate of a widely used biocide in the aquatic environment: field measurements in wastewater treatment plants,surface waters,and lake sediments

Triclosan is used as an antimicrobial agent in a wide range of medical and consumer care products. To investigate the occurrence and fate of triclosan in the aquatic environment, analytical methods for the quantification of triclosan in surface water and wastewater, sludge, and sediment were developed. Furthermore, the fate of triclosan in a wastewater treatment plant (biological degradation, 79%; sorption to sludge, 15%; input into the receiving surface water, 6%) was measured during a field study. Despite the high overall removal rate, the concentration in the wastewater effluents were in the range of 42-213 ng/L leading to concentrations of 11-98 ng/L in the receiving rivers. Moreover, a high removal rate of 0.03 d(-1) for triclosan in the epilimnion of the lake Greifensee was observed. This is due to photochemical degradation. The measured vertical concentration profile of triclosan in a lake sediment core of lake Greifensee reflects its increased use over 30 years. As the measured concentrations in surface waters are in the range of the predicted no effect concentration of 50 ng/L, more measurements and a detailed investigation of the degradation processes are needed.     

PCB congeners and dechlorination in sediments of Lake Hartwell, South Carolina, determined from cores collected in 1987 and 1998

Four sediment cores were collected from Lake Hartwell, SC, in 1987 and 1998 and analyzed for polychlorinated biphenyl (PCB) congeners. Total PCBs ranged from -0 to 58 microg/ g. Positive matrix factorization (PMF) was applied to the data sets to determine PCB source profiles. Two factors were determined for each data set. One factor resembled the original estimated PCB mixture of 80% Aroclor 1016 and 20% Aroclor 1254 and the other factor was a dechlorinated version of the mixture. Evidence of a dechlorination plateau is apparent from the PMF loading solutions because the dechlorinated congener profiles do not change from 1987 to 1998, butthe contribution to the profile from the dechlorinated factor increases from 73% (1987) to 87% (1998). PMF source contributions and plots of PCB concentration versus congener for individual samples provide evidence of enhanced dechlorination at high concentrations. After source apportionment an anaerobic dechlorination model was applied to the dechlorinated source profiles to quantify possible dechlorination pathways. It was found that dechlorination process M, extended to target biphenyl rings with up to six chlorines, provided the best fit for an individual process, and M + Q provides the best fit for combined processes, although M + LP also provides a similarfit. Process LP targets the higher chlorinated congeners and appears to dechlorinate PCBs in the sediments initially.     

DDE in sediments of the Palos Verdes Shelf, California: in situ transformation rates and geochemical fate

From 1947 to 1971 the world's largest manufacturer of DDT discharged process wastes into the sewers of Los Angeles County. Roughly 870-1450 t of DDT were released to the ocean off Palos Verdes, CA, a portion of which (approximately 100 t) resides in sediments on the continental shelf and slope. The most abundant DDT compound in the sediments, p,p'-DDE, is degrading by reductive dechlorination, but the rate of transformation and factors controlling it are not well understood. In order to estimate in situ transformation rates and predict the long-term fate of p,p'-DDE, box cores were collected in 1992 and 2003 from a single location on the Palos Verdes Shelf and analyzed for 8 DDT compounds and 84 polychlorinated biphenyl (PCB) congeners. The PCBs show no evidence of dechlorination, and inventories did not change between 1992 and 2003. By contrast, the inventory of p,p'-DDE decreased by 43%, whereas that of p,p'-DDMU, the putative reductive dechlorination product, increased by 34%. The first-order transformation rate for p,p'-DDE at the study site is 0.051 +/- 0.006 yr(-1). A multistep reaction model suggests that inventories of p,p'-DDE and p,p'-DDMU will continue to decline, whereas that of p,p'-DDNU will reach a maximum around 2014.     

Identification and quantification of 12 pharmaceuticals in water collected from milking parlors: Food safety implications

The introduction of drug residues into the food chain and their presence in drinking water has been recently investigated. The aim of this work was to monitor the presence of 19 active drugs in water samples collected from milking parlors of dairy farms located in Galicia (northwest Spain), one of the main Spanish milking areas. Overall, 65% of the samples tested positive for at least one of the compounds analyzed. A total of 12 drugs were measured, with concentrations ranging between 17 and 3,941 ng/L. Considering that a mixture of compounds may contribute to the overall effect of each compound and might increase or reduce its toxicity, it should be noted that 29% of the samples tested contained more than one pharmaceutical. To date, the effects of the continuous consumption of these mixtures of drugs in water or milk are unknown; however, antimicrobials may affect the human gut microbiota or have toxic effects in sensitive individuals.     

Actinomycete bacteria isolated from the sediments at coastal and offshore area of Nagasaki Prefecture, Japan: diversity and biological activity

About 800 strains of actinomycetes were isolated from marine environments around Nagasaki Prefecture, Japan. The isolates were compared with taxa and biological activities of their secondary metabolites. It is suggested that a variety of actinomycetes are isolated from different marine environments.     

Widespread occurrence of perchlorate in water,foodstuffs and human urine collected from Kuwait and its contribution to human exposure

Perchlorate is a thyroid hormone-disrupting compound and is reported to occur widely in the environment. Little is known on human exposure to perchlorate in Kuwait. In this study, 218 water samples, 618 commonly consumed foodstuffs and 532 urine samples collected from Kuwait were analysed to assess the exposure of the Kuwaiti population to perchlorate. For the estimation of daily intake of perchlorate, food consumption rates were obtained from the National Nutrition Survey in the State of Kuwait (NNSSK). The results showed that leafy vegetables accounted for a major share of perchlorate exposure among the Kuwaiti population at 0.062 µg kg^–1 bw day^–1 (36.2%), followed by fruits at 0.026 µg kg^–1 bw day^–1 (15.3%) and non-leafy vegetables at 0.017 µg kg^–1 bw day^–1 (10.1%). The urinary perchlorate geometric mean (GM) concentrations ranged from 8.51 to 17.1 µg l^–1 for the five age groups, which were higher than those reported in other countries. The estimated urinary perchlorate exposure for the Kuwaiti general population was 0.42 µg kg^–1 bw day^–1, which was higher than that reported for the United States. The dietary intake of perchlorate for the Kuwaiti population ranged from 0.14 to 0.67 µg kg^–1 bw day^–1 for the five age groups, with a mean total daily intake of 0.17 µg kg^–1 bw day^–1 for the general population. The highest estimated dietary mean daily intake of perchlorate (0.67 µg kg^–1 bw day^–1) was found for children at 3–5 years. The estimated dietary perchlorate exposure in Kuwait is higher than the recommended mean reference dose (RfD) but lower than that of provisional maximum tolerable daily intake (PMTDI) set by the Joint FAO/WHO Expert Committee on Food Additives (JECFA).     

Levels and distribution of polybrominated diphenyl ethers in water, surface sediments, and bivalves from the San Francisco Estuary

Polybrominated diphenyl ethers (PBDEs) were found in water, surface sediments, and bivalve samples that were collected from the San Francisco Estuary in 2002. sigmaPBDE concentrations in water samples ranged from 3 to 513 pg/ L, with the highest concentrations found in the Lower South Bay (range 103-513 pg/L) region, which receives approximately 26% of the Estuary's wastewater treatment plant effluents. The sigmaPBDEs in sediments ranged from below detection limits to 212 ng/g dry wt, with the highest concentration found at a South Bay station (212 ng/g dry wt), which was up to 3 orders of magnitude higher than other stations. The sigmaPBDE concentrations ranged from 9 to 64 ng/g dry wt in oysters (Crassostrea gigas), from 13 to 47 ng/g dry wt in mussels (Mytilus californianus), and from 85 to 106 ng/g dry wt in clams (Corbicula fluminea). Only three PBDE congeners were detected in bivalves, BDE-47, BDE-99, and BOE-100; these are the most bioaccumulative congeners from the commercial Penta-BDE mixture.     

Salmonella and Shigella in freshly squeezed orange juice, fresh oranges, and wiping cloths collected from public markets and street booths in Guadalajara, Mexico: incidence and comparison of analytical routes

A survey of the presence of Salmonella and Shigella in freshly squeezed orange juice and related samples was conducted in Guadalajara, Mexico. One hundred samples of freshly squeezed orange juice were collected from 49 street booths and 51 small food service establishments. In addition, 75 fresh orange samples, each consisting of five orange units, and 75 wiping cloths were collected from the same establishments from which juice had been collected. Salmonella was isolated from 14, 20, and 23% of samples of orange juice, orange surfaces, and wiping cloths collected from street vendors, while Shigella was isolated from 6, 17, and 5% of these samples. In general, the frequency of isolation of these pathogens in samples from juice serving establishments at public markets was significantly lower than that found among street vendors (P < 0.05). Salmonella enterica serotypes Agona, Typhimurium, and Anatum were found in orange juice, fresh oranges, and wiping cloth samples, while serotype Mexico was found on fresh oranges and in wiping cloths and serotypes Muenchen and Panama were found only in wiping cloth samples. Regarding Shigella species, Shigella sonnei was found in all three types of sample tested; Shigella dysenteriae was found in juice and orange samples, Shigella boydii in orange and wiping cloth samples, and Shigella flexneri on oranges only. Thirty-one percent and 39% of the juice samples showed aerobic plate counts of > or = 5.0 log CFU/ml and Escherichia coli counts of > 3.0 log CFU/ml, respectively. These high counts may indicate poor sanitation and potential exposure to fecal contamination either in the raw materials or during the orange-crushing and juice-serving process. These data may be useful for a further risk assessment of Salmonella or Shigella in unpasteurized, freshly squeezed juice.     

Trophodynamic behavior of 4-nonylphenol and nonylphenol polyethoxylate in a marine aquatic food web from Bohai Bay, north China: comparison to DDTs

4-Nonylphenol (4-NP) is of particular concern because of its ubiquity in aquatic environment and its endocrine-disrupting effects in aquatic organisms. On the basis of its octanol-water partition coefficient (104.6), it has a potential to bioaccumulate in aquatic food webs. However, there are no reported field studies on the trophodynamics of 4-NP and its precursor, nonylphenol polyethoxylate (NPEOs) surfactants, in aquatic food webs. This study reports the trophodynamics of 4-NP and NPEOs (4 < s < 16) in a marine aquatic food web from Bohai Bay, North China. 4-NP and NPEOs (4 < s < 16) were determined in 14 marine species including plankton, benthic invertebrates, fish, and marine birds. This paper provides the first report on the occurrence of NPEOs with s > 5 in marine biota. Co-analysis of DDTs in all samples allowed a direct comparison of the bioaccumulation behavior of DDTs with that of NP and NPEOs. The lipid equivalent concentration of DDE and 2,2-bis(chlorophenyl)-1-chloroethylene (DDMU) increased with increasing trophic level, and the trophic level was determined by stable isotope ratios. The trophic magnification factors (TMFs) of DDE and DDMU were 3.26 and 3.7, respectively. Lipid equivalent concentrations of 4-NP and of all NPEOs did not exhibit a statistically significant correlation with trophic levels in the food web, and the TMF of NP was 0.83, which was similar to those of all NPEOs (0.45-1.22). These results show that in the studied aquatic food web, there was no trophic magnification for 4-NP and NPEOs, whereas DDE and DDMU biomagnified.     

Putative virulence properties of Aeromonas strains isolated from food, environmental and clinical sources in Italy: a comparative study

The distribution of virulence properties in 142 strains of Aeromonas isolated from diarrhoeic patients, food and surface water in Italy and identified by biochemical and molecular methods was investigated. The virulence properties studied were the presence of genes for the aerolysin (aerA), heat-stable cytotonic enterotoxin (ast), heat-labile cytotonic enterotoxin (alt), cytotoxic enterotoxin (act); and cytotoxicity for Vero cells and adhesion on Hep-2 cells. A. hydrophila and A. caviae were the species most commonly isolated from clinical and environmental samples (9/30; 30.0% and 5/27; 18.5%, respectively) while mesophilic A. salmonicida was most common in food samples (19/80; 23.7%). Out of 142 strains, 86 (60.6%) were positive for at least one of the virulence properties. All the toxin genes were present in 4/18 (22.3%) of clinical strains. Most of the food isolates (54/55; 98.2%) were cytotoxic and most of the environmental strains (12/13; 92.3%) were adhesive. The aerA gene was present in most toxigenic strains (72/86; 83.7%), irrespective of their origin. The growth temperature affected the expression of cytotoxicity and adhesivity. Aeromonas strains from food and surface water frequently had toxin gene patterns similar to those of clinical strains and expressed virulence properties at human body temperature. These findings indicate that aeromonads have the potential to cause human illness and confirm the role of food and water as vehicles for Aeromonas diseases.     

Use of caustic magnesia to remove cadmium, nickel, and cobalt from water in passive treatment systems: column experiments

In the present study caustic magnesia obtained from calcination of magnesium carbonate was tested in column experiments as an alternative material for passive remediation systems to remove divalent metals. Caustic magnesia reacts with water to form magnesium hydroxide, which dissolves increasing the pH to values higher than 8.5. At these pH values, cadmium is precipitated as otavite and to a minor amount as a hydroxide. Cobalt and nickel are precipitated as hydroxides which form isostructural solids with brucite. Thus, metal concentrations as high as 75 mg/L in the inflowing water are depleted to values below 10 microg/L. Magnesia dissolution is sufficiently fast to treat flows as high as 0.5 m3/m2 x day. For reactive grain size of 2-4 mm, the column efficiency ends due to coating of the grains by precipitates, especially when iron and aluminum are present in the solution.     

Pyrogenic inputs of anthropogenic Pb and Hg to sediments of the Hood Canal, Washington, in the 20th century: source evidence from stable Pb isotopes and PAH signatures

Combustion-derived PAHs and stable Pb isotopic signatures ((206)Pb/(207)Pb) in sedimentary records assisted in reconstructing the sources of atmospheric inputs of anthropogenic Pb and Hg to the Hood Canal, Washington. The sediment-focusing corrected peak fluxes of total Pb and Hg (1960-70s) demonstrate that the watershed of Hood Canal has received greater atmospheric inputs of these metals than its mostly rural land use would predict. The tight relationships between the Pb, Hg, and organic markers in the cores indicate that these metals are derived from industrial combustion emissions. Multiple lines of evidence point to the Asarco smelter, located in the Main Basin of Puget Sound, as the major emission source of these metals to the watershed of the Hood Canal. The evidence includes (1) similar PAH isomer ratios in sediment cores from the two basins, (2) the correlations between Pb, Hg, and Cu in sediments and previously studied environmental samples including particulate matter emitted from the Asarco smelter's main stack at the peak of production, and (3) Pb isotope ratios. The natural rate of recovery in Hood Canal since the 1970s, back to preindustrial metal concentrations, was linear and contrasts with recovery rates reported for the Main Basin which slowed post late 1980s.     

Detection of hydroxylated polychlorinated biphenyls (OH-PCBs) in the abiotic environment: surface water and precipitation from Ontario, Canada

Hydroxylated PCBs (OH-PCBs) are well-known metabolites of PCBs in organisms, but there has been no direct study of their presence in the abiotic environment. In this study, OH-PCBs were determined in samples of rain, snow, and surface waters from sites in Ontario, Canada. OH-PCBs were quantified by gas chromatography with high-resolution mass spectrometry (GC-HRMS)in order to provide complete characterization of all OH-PCB homolog groups. OH-PCBs and PCBs were detected in all the samples analyzed, although half of the sigmaOH-PCBs could not be identified even with 71 individual congener standards. Total concentrations of OH-PCBs (sigmaOH-PCBs) in water ranged from 0.87 to 130 pg/L and from 230 to 990 pg/g in particulate organic matter. Total fluxes of those compounds in snow and rain were from < 1 to 100 pg/m2 and from < 1 to 44 pg/ m2/day, respectively. Higher sigmaOH-PCB fluxes in rain were found in southern Ontario than in a remote north-central Ontario site possibly reflecting greater sources of precursor PCBs near urban areas. Relatively higher sigmaOH-PCB concentrations were found in surface waters from sites near sewage treatment plant (STP) outfalls in the cities of Toronto (130 pg/L) and Hamilton (35 pg/L) than in offshore samples from Lake Ontario (1.6 pg/L). The results indicate that STPs are one of the sources of OH-PCBs for lake waters in this region. Similar homolog and congener profiles in rain and offshore surface water samples suggest that atmospheric deposition is the predominant source at offshore sites. This is the first report to detect the OH-PCBs in the abiotic environment.