Bioaccumulation and trophic transfer of dioxins in marine copepods and fish

Despite the great concerns about dioxins in the marine environments, the biokinetics and bioaccumulation of these compounds in marine organisms remains little known. Using radioactive tracers the aqueous uptake, dietary assimilation efficiency, and elimination of dioxins were measured in marine phytoplankton, copepods and seabream. The calculated uptake rate constant of dioxins decreased with increasing trophic levels, whereas the dietary assimilation efficiency (AE) was 28.5-57.6% in the copepods and 36.6-70.2% in the fish. The dietary AE was highly dependent on the food concentrations and food type. The elimination rate constant of dioxin in the copepods varied with different exposure pathways as well as food concentration and food type. Biokinetic calculation showed that dietary accumulation was the predominant pathway for dioxin accumulation in marine copepods and fish. Aqueous uptake can be an important pathway only when the bioconcentration of dioxins in the phytoplankton was low.     

Levels of dioxins in fish and fishery products on the German market

In 1995-1998 the contents of polychlorinated dibenzodioxins and dibenzofurans of 184 pooled fish samples were analysed. Sampling focused on fish and fishery products with a market share of more than 1% and covered all fishing grounds important for the supply of the German market. Investigation included 15 different fish species, shrimp, mussel and squid samples and various fishery products, typically on the German market. Generally lean fish species like cod, saithe or Alaska pollock were less contaminated on fresh weight basis than fat fish species like herring, Greenland halibut and sardine. In herring the dioxin content is related to the fishing ground. Low concentrations were found in North Sea herring, high concentrations measured in samples from the Baltic Sea. Dioxin contents in fishery products did not differ significantly from the raw fish samples. Results allow an estimation of the daily intake of dioxins and furans via fish consumption in Germany. Based on a daily fish consumption of 20 g the average intake of dioxins via fish is 6.2 pg WHO-PCDD/F-TEQs per person and day.     

An enzyme-linked immunosorbent assay for the determination of dioxins in contaminated sediment and soil samples

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.     

High-throughput screening of dioxins in sediment and soil using selective pressurized liquid extraction with immunochemical detection

A high-throughput screening method using selective pressurized liquid extraction (SPLE) and enzyme-linked immunosorbent assay (ELISA) for monitoring dioxins in sediment and soil is described. SPLE conditions were developed by extracting sediment or soil together with alumina, 10% AgNO₃ in silica, and sulfuric acid impregnated silica (acid silica) using dichloromethane (DCM) as the solvent at 100 °C and 2000 psi. Post-extraction cleanups were not required for ELISA. Two reference sediments (National Institute of Standards and Technology SRM 1944 and Wellington Laboratories WMS01) were analyzed by the SPLE–ELISA method. The ELISA utilized a polyclonal antibody and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) as the calibrant. Recoveries of ELISA-derived TCDD equivalents (EQ) relative to the expected gas chromatography/high resolution mass spectrometry (GC/HRMS) derived dioxin toxic equivalent (TEQ) values were 116 ± 11% for SRM 1944 and 102 ± 13% for WMS01. ELISA TCDD EQs were consistent with the dioxin TEQs as measured by GC/HRMS for 25 soil/sediment samples from seven different contaminated sites. The ELISA had an approximate method detection limit of 10 pg g⁻¹ with a precision of 2.6–29% based on the relative percentage difference (%RPD) for duplicate samples. Estimated sample throughput for the SPLE–ELISA was three times or more than that of the GC/HRMS method employing PLE with a multi-column cleanup.     

Mercury in sediment and fish from North Mississippi Lakes

Sediments and/or fish were collected from Sardis, Enid and Grenada Lakes, which are located in three different watersheds in North Mississippi, in order to assess mercury contamination. The mean total mercury concentration in sediments from Enid Lake in 1997 was 0.154 mg Hg/kg, while 1998 sediment concentrations in Sardis, Enid and Grenada Lakes were 0.112, 0.088 and 0.133 mg Hg/kg, respectively. Sediment mercury concentrations in 1999 were similar in all three lakes but, generally lower than 1998. Mean total mercury concentrations in edible fillets of fish collected from Enid Lake in 1998 were above the human health FDA action level (>1.0 mg Hg/kg) for bass (1.40), crappie (1.69) and gar (1.89); however, tissue concentrations were less than 1.0 mg Hg/kg in carp (0.63) and catfish (0.82). Human hazard indexes for each species was 1 for both adults and children, indicating that there is a potential for toxic effects to occur. In addition, calculated consumption limits indicate that adults may consume 4–12 oz. of fish per month, depending on the species consumed. For children, 2 oz. per month may be consumed. Further studies are needed to determine the exact environmental consequences and human health impacts associated with mercury contamination in North Mississippi and the Southeastern United States.     

Contamination status of dioxins in sediment cores from the Three Gorges Dam area, China

In order to screen dioxin pollution in sediment of Three Gorges Dam (TGD) area, three sediment cores were obtained from two sites in 2010~2011; each core was divided into different samples with every 10 cm depth. Sediment dating determined by radiometry (¹³⁷Cs, ²¹⁰Pb) and concentrations of dioxins were analyzed by high-resolution gas chromatography/mass spectrometry. The results indicated: Sediment dating showed no significant difference among all the samples from the same core and the two locations (ANOVA, p?>?0.05). The total amount of polychlorinated dibenzo-p-dioxins (PCDD)/Fs in all sample ranged from 30.7 to 371 pg/g dry weight (d.w.), with the mean value of 66.2 pg/g d.w. PCDDs occupied 60.33~85.22 % of dioxins in each sample, and PCDFs contributed to a very small extend. There was no significant difference in the dioxin concentration between 2010 and 2011 and in the two locations (t test, p?>?0.05), but the vertical distribution of dioxins showed significant different in different depths. Toxic equivalent (TEQ) (WHO 2005, Humans) of samples ranged from 0.15 to 1.60 pg/g d.w.; the mean was 0.41 pg/g d.w. No significant difference was found in TEQ between 2010 and 2011(t test, p?>?0.05). It could be concluded that the distribution of dioxins showed the spatial heterogeneous which resulted from the strong mixing and sediment deposition characteristics. Dioxin concentration in sediment cores was low with very low environmental risk potential. Dioxins at the two sites had the same origin, and exogenous input was the main source. It is the first report on the dioxins concentrations in sediment cores in the TGD area.     

Trace metal levels in freshwater fish, sediment and water

The trace metal concentrations in water, sediment and aquatic organisms, such as fish, could indicate the level and tendency of the pollution. This is important not only for the protection of the environment, but for evaluation of the quality of fish meat either captured from natural waters or cultured in fishponds. The total trace metal concentrations in samples of fish from different regions of Hungary and from different species have been determined by using an X-ray fluorescence technique (EDXRF). Water, sediment and fish samples from fishpond systems with different feeding and stocking has also been analyzed. In the case of zinc contents, differences have been traced between the cultured and wild common carp. In the case of common carp reared under different feeding conditions, differences were also observed in the zinc concentration. The retention of the trace metals in the fish has been studied by measuring the levels in sediment, water and feed. The different retention can be explained by the different availability of zinc in the applied feeds, which can be related to the presence of different metal species in the feeds.     

Sample purification for analysis of organochlorine pesticides in sediment and fish muscle

The methods of sample purification for determinations of organochlorine pesticides (OCPs) in sediment and fish muscle were investigated in this study. A two-step procedure with preliminary cleanup and florisil column fraction was adopted. The working conditions of florisil column were firstly optimized. As to preliminary cleanup, liquid-liquid extraction by mixture of dimethyl formamide (DMF) and hexane and sulphonation by concentrated sulfuric acid were applied respectively and compared for the studied samples. The results indicated that liquid-liquid distribution could effectively separate lipids from fish muscle extracts, while failed in elimination of chlorophyll extracted from the relicts of hydrophytes in the sediment sample. In view of the sample appearance and clarity of gas chromatogram, sulphonation was more suitable to purify the sediment sample, however, the recoveries of the spiked standards were poor. The use of eluting solvent with stronger polarity could improve the corresponding recoveries significantly. Due to complete loss of Dieldrin, Endrin, and Endrin aldehyde after sulphonation, this pretreatment was improper to the three components. Sulfur, as the particular disturbing element in sediment, could be removed sufficiently by addition of activated copper powder. The relevant detection limits of the selected methods for OCPs in the studied substrates were also provided.     

Determination of tris(4-chlorophenyl)methanol and tris(4-chlorophenyl)methane in fish, marine mammals and sediment

Tris(4-chlorophenyl)methanol (TCP) and tris(4-chlorophenyl)methane (TCPMe) were determined in aquatic organisms and sediment by a method based on Soxhlet extraction, gel permeation chromatography, fractionation over silica and gas chromatography/mass spectrometry (GC/MS) analysis. TCPMe was identified as the 4-substituted isomer after synthesis of this compound. TCP could be determined by GC/MS with negative chemical ionistation (GC/NCI-MS) with a detection limit of 0.02 g kg(-1) and a recovery of 90%. TCP concentrations in marine mammals from the North Sea and Dutch Wadden Sea ranged from 0.2 to 2 mg kg(-1), and those in marine and freshwater fish samples from 0.005 to 0.4 mg kg(-1) on a lipid wt basis. TCP concentrations in two Rhine delta sediment samples were 1.2 and 3.0 microg kg(-1) dry wt, respectively. TCPMe concentrations, determined by GC/MS with electron impact (GC/EI-MS), were 10-50% of the TCP concentration in all samples analysed.     

Determination of toxaphenes in fish and marine mammals

An analytical method for the determination of toxaphene in biological materials using gas chromatography with an electron capture detector (GC-ECD) has been established and validated for three single congeners (chlorinated bornanes (CHB) 26, 50 and 62). The analytical method was based on a method for determination of PCB, DDT and other chlorinated pesticides. To include toxaphene congeners an extra step, adsorption chromatography on silica columns, was introduced to separate the pesticides from PCB. The recovery of CHB-26, 50 and 62 were 97+/-11%, 94+/-10% and 99+/-12%, respectively. Samples from cod, ringed seal and polar bear from the Norwegian arctic environment have been analysed. The levels of CHB-26 and 50 found were 13-55 ng/g fat in cod, 1.3-7.7 ng/g fat in ringed seal and 0.4-119 ng/g fat in polar bear. The levels of CHB-62 were 2.0-13, 0.8-3.4, 0.2-11 ng/g fat in cod, ringed seal and polar bear, respectively.     

Mercury species of sediment and fish in freshwater fish ponds around the Pearl River Delta, PR China: human health risk assessment

This study investigated total mercury (THg) and methylmercury (MeHg) concentrations in five species of freshwater fish and their associated fish pond sediments collected from 18 freshwater fish ponds around the Pearl River Delta (PRD). The concentrations of THg and MeHg in fish pond surface sediments were 33.1-386 ng g(-1) dry wt and 0.18-1.25 ng g(-1) dry wt, respectively. The age of ponds affected the surface sediment MeHg concentration. The vertical distribution of MeHg in sediment cores showed that MeHg concentrations decreased with increasing depth in the top 10 cm. In addition, a significant correlation was observed between %MeHg and DNA from Desulfovibrionacaea or Desulfobulbus (p<0.05) in sediment cores. Concentrations of THg and MeHg in fish muscles ranged from 7.43-76.7 to 5.93-76.1 ng g(-1) wet wt, respectively, with significant linear relationships (r=0.97, p<0.01, n=122) observed between THg and MeHg levels in fish. A significant correlation between THg concentrations in fish (herbivorous: r=0.71, p<0.05, n=7; carnivorous: r=0.77, p<0.05, n=11) and corresponding sediments was also obtained. Risk assessment indicated that the consumption of largemouth bass and mandarin fish would result in higher estimated daily intakes (EDIs) of MeHg than reference dose (RfD) for both adults and children.     

Recolonization and succession of marine macrobenthos in organic-enriched sediment deposited from fish farms

High organic loading deposited on the sea bottom by marine fish farming activities often eliminates benthic organisms in the vicinity. In this study, organic-enriched sediment collected underneath a fish farm was defaunated, placed in settling trays and exposed to the subtidal area of a clean site of similar hydrography. Trays were sampled monthly for a consecutive period of 5 months, and recolonization and successional patterns of macrobenthos were studied using univariate and multivariate statistics. Recolonization occurred rapidly, and averages of 144 animals/tray and 26 species/tray were recorded within the first month. Molluscs accounted for 49% of species and polychaetes for 77% of abundance during the first month of recolonization. Temporal changes in abundance, diversity and species composition found in subsequent months resembled spatial changes of benthic community along a decreasing pollution gradient generalised by Pearson and Rosenberg (1978, Oceanography & Marine Biology Annual Review 16, 229-311). Abundance reached a peak after 3 months (434 animals/tray) and then declined. Species number also increased, peaked after 4 months (47 species/tray), and was followed by a decrease. The polychaete Prionospio malmgreni succeeded Pseudopolydora paucibranchiata as the dominant species after the first month, reached a peak (194 animals/tray) after 3 months, then declined sharply. The rapid recolonization and succession of the macrobenthic community on organic-enriched sediment suggested that present fish farming methods are unlikely to have a long-term impact on benthic communities once farming activities are reduced/ceased.     

Estimation of sources and inflow of dioxins and polycyclic aromatic hydrocarbons from the sediment core of Lake Suwa, Japan

To elucidate the historical changes in polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), coplanar polychlorinated biphenyl (co-PCB), and polycyclic aromatic hydrocarbon (PAH) inflows in Lake Suwa, their concentrations in the sediment core were analyzed in 5 cm interval. The maximum concentrations (depth cm) of PCDDs/DFs, co-PCBs, and PAHs were 25.2 ng/g dry (30-35 cm), 19.0 ng/g dry (30-35 cm), and 738, 795 ng/g dry (50-55 cm, 30-35 cm), respectively. Age and sedimentation rate of the sediment were estimated from the vertical changes in apparent density. Deposition rate of dioxins and PAHs were calculated from the concentration and sedimentation rate of the sediment. The results indicate that large amounts of dioxins and PAHs flowed into the lake in flood stage compared to normal stage.     

Atmospheric fate and transport of dioxins: local impacts

We conducted model simulations of the atmospheric fate and transport of PCDD/F to assess the fraction of emitted PCDD/F that would deposit within 100 km from the source. We considered eight major categories of PCDD/F emission sources and six different locations, to cover a wide range of source characteristics, PCDD/F congener profiles and particle size distributions, meteorological conditions and terrain configurations. These results suggest that for sources that have tall stacks and/or high plume rise (e.g., copper smelters, cement kilns, sinter plants), only a small fraction of PCDD/F emissions is deposited locally (typically, less than 10% within 100 km). Other source categories such as municipal solid waste incinerators, medical waste incinerators and diesel trucks lead to a greater fraction of PCDD/F being deposited locally; nevertheless, the majority of their PCDD/F emissions tends to be transported beyond 100 km. Although local impacts may need to be addressed for these latter source categories, it appears that the long-range potential impacts of PCDD/F need to be addressed for all source categories. Sensitivity studies were conducted to investigate the effect of various key model inputs on simulation results. These studies suggest that an advanced atmospheric dispersion model should be used for cases where PCDD/F emissions may present some local concerns because the results are very sensitive to the treatment of dispersion. Also, it is essential to obtain accurate characterizations of the particle size distribution of particulate PCDD/F because the dry deposition flux is very sensitive to the particle size distribution.     

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.     

Tributyltin distribution and producing androgenic activity in water,sediment, and fish muscle

This study investigated the concentrations of Tributyltin (TBT) in water, sediment, and fish muscle samples taken from Kaohsiung Harbor and Kaoping River estuary, Taiwan. TBT concentrations in water and sediment samples ranged from less than 18.5 to 34.1 ng Sn L^?1 and from 2.44 to 29.7 ng Sn g^?1 weight per weight (w/w), respectively. Concentrations in the TBT‐contaminated fish muscle samples ranged from 10.8 to 79.6 ng Sn g^?1 w/w. The TBT concentrations in fish muscle were higher than those in water and sediment samples. The fish muscle/water TBT bioconcentration factor (BCF) ranged from 590 to 3363 L kg^?1. Additionally, the water samples were assessed for androgenic activity with an MCF7‐AR1 human breast cancer cell line. The androgenic activity ranged from 0.94 to 3.1 ng‐dihydrotestosterone per litre water (ng‐DHT L^?1). Higher concentrations of TBT in water and sediment samples occurred in the dry season, but the androgenic activity had higher values in the rainy season.     

Tetrabromobisphenol A: tissue distribution in fish, and seasonal variation in water and sediment of Lake Chaohu, China

Tetrabromobisphenol A (TBBPA) is the most widely used brominated flame retardants (BFRs). It has been detected in various environment media and has been approved to be high toxic to aquatic organisms. However, the exposure levels of TBBPA in the main watersheds in China have not been investigated sufficiently. In this study TBBPA concentrations in water, sediment and tissues of four fish species from Lake Chaohu were determined. Spatial and temporal distribution patterns of TBBPA in water and sediment, and the relationship among TBBPA concentrations in fish tissues and fish size were analyzed. The results showed that the maximum TBBPA concentration in sediment was 518 ng/g in March 2008. It is almost the highest value than those ever reported anywhere in the world. In lake water, TBBPA level reached the maximum value of 4.87???g/L in July. Tissue distributions of TBBPA in four fish species were similar, and the mean concentrations in the fish were in the range of 28.5?C39.4 ng/g, much higher than those reported in Japan, Europe, and the United States. The maximum concentrations of TBBPA were found in kidneys where TBBPA concentration was positively correlated with fish size of Cyprinus carpio. Results demonstrated a widespread distribution of TBBPA in Lake Chaohu. The source was mainly inflow rivers near the cities. The distribution coefficient among water, fish, and sediment was 1:28:117. This indicated that sediment was the main repository for TBBPA within Lake Chaohu. Furthermore, TBBPA may pose a potential ecological risk in the lake during summer.     

Determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin in fresh water fish

Validated sample preparation procedures and high resolution gas chromatography-high resolution mass spectrometry techniques were utilized for the quantitative measurement of 4 to 695 pg/g (ppt) levels of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2378-TCDD) in the edible portions of fish from the state of Michigan. The methodology and the analytical results are presented.     

Decabrominated diphenyl ether in river fish and sediment samples collected downstream an industrial park

Fish, sediment and water samples from different places along the Spanish River Vero, a tributary of the Cinca River in the Ebro River basin, were collected in two different sampling campaigns, the first one during November 2004 and the second one in November 2005. The samples were collected up- and downstream from an industrial park. A total of 29 fishes, 6 sediments and 3 water samples were analyzed for polybrominated diphenyl ethers (PBDEs). Analytical work included 23 congeners, from tri- to deca-BDEs. The highest values for both sediment and fish samples were found downstream of the industrial park. High BDE-209 contamination was found in these sediment samples, with values up to 12 microg g(-1) dry weight. Moreover, BDE-209 was detected in 14 out of 15 biota samples collected downstream the industrial park, at concentration levels ranging from 20 to 707 ng g(-1) lipid weight, whereas it was not detected in samples collected upstream. These fish concentrations proved the bioavailability of BDE-209 and represented the highest deca-BDE values found in aquatic biota. The analysis of industrial effluents revealed that some industries contribute in some way to the BDE-209 contamination found in this area, but the industry focused on the polyamide polymerization is the main responsible.