Toxaphene in standard solutions and cleaned biota extracts--results of the first QUASIMEME interlaboratory studies. Quality Assurance of Information for Marine Environmental Monitoring in Europe

Two interlaboratory studies on individual toxaphene congeners have been organised by the project Quality Assurance of Information for Marine Environmental Monitoring in Europe (QUASIMEME). Fifteen laboratories analysed two standard solutions in the first study and 13 laboratories analysed a standard solution and two cleaned biota extracts in the second study. The coefficients of variation obtained for the standard solutions were 6-21% and for the cleaned extracts 16-39%. Although the results were comparable to those of other studies, further improvement in the level of agreement between the participating laboratories was considered possible.     

Polybrominated diphenyl ethers in surface sediments of the Yangtze River Delta: Levels, distribution and potential hydrodynamic influence

A total of 32 surface sediments collected from the Yangtze River Estuary, Hangzhou Bay and the Qiantang River were analyzed for polybrominated diphenyl ethers (PBDEs). The concentrations of summation operatorPBDEs (sum of 12 PBDE congeners without BDE 209) and BDE 209 varied from n.d. to 0.55 and from 0.16 to 94.6 ng/g, respectively. The spatial variability of summation operatorPBDEs concentrations indicated that waste discharge from the urban areas might been the main source of PBDEs in the Yangtze River Delta. BDE 209 was the predominant congener (approximately 90-100%) detected among the 13 congeners, consistent with the fact that technical deca-BDE mixtures are presently the dominant technical PBDE mixtures used in China. Compared to published data acquired from other locales, PBDE congeners with less than four bromines were more abundant in the present study area. The hydrodynamic conditions may likely be a significant factor in dictating the observed levels and congener distribution patterns of PBDEs.     

Polychlorinated naphthalenes (PCNs) in Irish foods: Occurrence and human dietary exposure

The concentrations of selected polychlorinated naphthalene (PCN) congeners (PCNs 52, 53, 66/67, 68, 69, 71/72, 73, 74 and 75) were determined in 100 commonly consumed foods, in the first study on occurrence of these contaminants in the Republic of Ireland. Congener selection was based on current knowledge on PCN occurrence and toxicology, and the availability of reliable reference standards. The determinations were carried out using validated analytical methodology based on 13C10 labelled internal standardisation and measurement by HRGC-HRMS. The results showed PCN occurrence in the majority of studied foods--milk, fish, dairy and meat products, eggs, animal fat, shellfish, offal, vegetables, cereal products, etc. ranging from 0.09 ng kg(-1) whole weight for milk to 59.3 ng kg(-1) whole weight for fish, for the sum of the measured PCNs. The most frequently detected congeners were PCNs 66/67, PCN 52, and PCN 73. The highest concentrations were observed in fish, which generally showed congener profiles that reflect some commercial mixtures. The data compares well with other recently reported data for Western Europe. The dioxin-like toxicity (PCN TEQ) associated with these concentrations is lower than that reported for chlorinated dioxins or PCBs in food from Ireland. The dietary exposure of the Irish adult population to PCNs was calculated following a probabilistic approach, using the full dataset of occurrence and current consumption data. The estimates of dietary intakes at approximately 0.14 pg TEQ kg bw(-1) month(-1) for adults on an average diet, reflects the relatively lower occurrence levels.     

Analysis of some polyhalogenated organic pollutants in sediment and sewage sludge

A laminated sediment core collected in the southern part of the Baltic Proper was analysed for DDT compounds, polychlorinated biphenyls (PCB) including the coplanar congeners, polybrominated diphenyl ethers (PBDE) and polychlorinated naphthalenes (PCN). Two sewage sludge samples were also analysed for the same compounds.

The results of the sediment analyses indicate the presence of PCB, DDT and PBDE compounds in sediment layers dating from the 1950s and later. Neither coplanar PCB nor PCN were detected at any level of the sediment core. The PCB concentrations indicate a slight increase in levels during the last decades, while there were no changes in the levels of DDT compounds. In contrast, TeBDE levels increase 4- to 8-fold and one PeBDE congeners levels increase 10- to 20-fold. The results of sewage sludge analyses showed the concentration of the individual PBDE to be at about the same level as for the individual PCB congeners. The congener pattern in sludge samples indicates low-chlorinated products to be the main PCN source.     

Identification and characterization of the atmospheric emission of polychlorinated naphthalenes from electric arc furnaces

Electric arc furnaces (EAF) are well recognized as significant sources of dioxins. EAFs have also been speculated to be sources of polychlorinated naphthalenes (PCNs) due to the close correlation between dioxin and PCN formation. However, assessment on PCN emissions from EAFs has not been carried out. The primary aim of this preliminary study is to identify and characterize the atmospheric emission of PCNs from EAFs. In this preliminary study, stack gas samples from two typical EAFs with different scales (EAF-1, 160?t batch(-1); and EAF-2, 60?t batch(-1)) were collected by automatic isokinetic sampling technique, and PCN congeners in samples were analyzed by isotope dilution high-resolution gas chromatography combined with high-resolution mass spectrometry method. Emission concentrations of PCNs were 458 and 1,099?ng?m(-3) for EAF-1 and EAF-2, respectively. The emission factors of PCNs to air were 21.6 and 30.1?ng toxic equivalent t(-1) for EAF-1 and EAF-2, respectively, which suggested that EAF is an important source of PCN release. With regard to the characteristics of PCNs from EAFs, lower chlorinated homologues were dominant. The PCN congeners comprised of CN27/30, CN52/60, CN66/67, and CN73 were the most abundant congeners for tetra-, penta-, hexa-, and hepta-chlorinated homologues, respectively. EAFs were identified to be an important PCN source, and the obtained data are useful for developing a PCN inventory. The congener profiles of PCNs presented here might provide helpful information for identifying the specific sources of PCNs emitted from EAFs.     

Levels and distribution of polybrominated diphenyl ethers in plant, shellfish and sediment samples from Laizhou Bay in China

Polybrominated diphenyl ethers (PBDEs) are potentially harmful and persistent environmental pollutants. PBDEs concentrations are reported in plant, shellfish and sediment samples collected from Chinese Laizhou Bay. The summation operator(11)PBDE concentrations in plant and shellfish samples from Laizhou Bay were in the range of 70-5900ngg(-1) and 230-720ngg(-1) lipid, respectively. The summation operator(11)PBDEs concentrations in river sediment intervals samples ranged from 1.3 to 1800ng g(-1) dry weight. Pearson correlation analyses were performed on concentrations of PBDEs congeners of different sediment sample intervals. There were significant positive correlations for BDE 28 and BDE 100 (r=0.945, p<0.01), BDE 47 and BDE 99 (r=0.879, p<0.01), BDE 153 and BDE 154 (r=0.934, p<0.01), nona-BDEs and BDE 209 (r>0.934, p<0.01). BDE 209 was the predominant congener in all analyzed samples, consistent with the fact that deca-BDE technical mixtures are the dominant PBDEs product in Laizhou Bay. Data showed that PBDEs should be considered as an increasing pollution problem in the Laizhou Bay region.     

Human exposure to polychlorinated naphthalenes through the consumption of edible marine species

The concentrations of polychlorinated naphthalenes (PCNs) were determined in samples of 14 edible marine species (sardine, tuna, anchovy, mackerel, swordfish, salmon, hake, red mullet, sole, cuttlefish, squid, clam, mussel and shrimp), which are widely consumed by the population of Catalonia, Spain. The daily intake of PCNs associated with this consumption was also determined. A total of 42 composite samples were analyzed by HRGC/HRMS. The highest PCN levels (ng/kg of fresh weight) were found in salmon (227) followed by mackerel (95) and red mullet (68), while the lowest levels of total PCNs corresponded to shrimp (4.9) and cuttlefish (2.7). With the exception of cephalopods and shellfish species, in which tetra-CN was the predominant homologue, penta-CN (60%) was the predominant contributor to total PCNs. For a standard male adult, PCN intake through the consumption of edible marine species was 1.53 ng/day. The highest contributions to this intake (ng/day) corresponded to salmon (0.41), sole (0.28) and tuna (0.24). Concerning health risks, species-specific TEFs such as those reported by WHO and NATO for PCDD/Fs and dioxin-like PCBs are not currently available for PCN congeners. Although in general terms the results of the present study do not seem to suggest specific risks derived from exposure to PCNs through fish and seafood consumption, to establish the contribution of individual PCN congeners to total TEQ is clearly necessary for the assessment of human health risks.     

Polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs) in breast milk from the Pacific Northwest

Breast milk samples from 40 first-time mothers from the Pacific Northwest of the US and Canada were analyzed for polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs). Total PBDEs (summation operator PBDEs), calculated by summing values for the 12 PBDEs congeners analyzed, ranged from 6 to 321 ppb (lipid weight) (mean=96 ppb; median=50 ppb). In approximately 40% of the women (15/40), summation operator PBDEs>100 ppb lw in their milk, and four samples had levels >250 ppb lw. PBDE 47 was the dominant congener in most samples, whereas PBDE 153 was predominant in a few (3/40). summation operator PCBs were calculated by summing values for the 82 PCB congeners analyzed, and ranged from 49 to 415 ppb (lipid weight) (mean=147 ppb; median=126 ppb). approximately 30% of the mothers (13/40) have summation operator PBDEs> summation operator PCBs in their milk samples, and approximately 65% (25/40) have BDE 47>PCB 153 in breast milk samples, with BDE 47 averaging 3-fold greater levels than PCB 153. Clearly, the lower brominated PBDEs are surpassing PCBs as a major environmental concern in North America, and are likely affecting significant portions of the populations in these regions. PBDEs have become a major persistent organic pollutant. However, there are no positive correlations between levels of summation operator PBDEs and summation operator PCBs, or between levels of PBDE 47 and PCB 153, suggesting there may be some differences in exposure pathways for PBDEs and PCBs in humans.     

Polychlorinated naphthalenes in human adipose tissue from New York, USA

Polychlorinated naphthalenes (PCNs) are persistent, bioaccumulative, and toxic contaminants. Prior to this study, the occurrence of PCNs in human adipose tissues from the USA has not been analyzed. Here, we have measured concentrations of PCNs in human adipose tissue samples collected in New York City during 2003-2005. Concentrations of PCNs were in the range of 61-2500 pg/g lipid wt. in males and 21-910 pg/g lipid wt. in females. PCN congeners 52/60 (1,2,3,5,7/1,2,4,6,7) and 66/67 (1,2,3,4,6,7/1,2,3,5,6,7) were predominant, collectively accounting for 66% of the total PCN concentrations. Concentrations of PCNs in human adipose tissues were 2-3 orders of magnitude lower than the previously reported concentrations of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs). Concentrations of PCNs were not correlated with PCB concentrations. The contribution of PCNs to dioxin-like toxic equivalents (TEQs) in human adipose tissues was estimated to be <1% of the polychlorinated dibenzo-p-dioxin/dibenzofuran (PCDD/F)-TEQs.     

Flux estimates and sedimentation of polychlorinated naphthalenes in the northern part of the Baltic Sea

The concentrations and fluxes of polychlorinated naphthalenes (PCNs) were measured in surface sediments, and settling particulate matter collected in sediment traps, at two coastal and two offshore sampling stations in the Gulf of Bothnia, northern Baltic Sea, Sweden. The PCN concentrations (of tetra- to hepta-chloro congeners) in the surface sediments ranged from 0.27 to 2.8 ng/g dry weight and were of the same order of magnitude as background concentrations reported previously in Europe. The PCN fluxes in the southern basin (0.93 and 0.86 microg/m2/year) of the Gulf of Bothnia were higher than those in the northern basin (0.58 and 0.49 microg/m2/year); they were also higher near the coast than in the open sea. These PCN fluxes are similar to the pre-industrial levels determined from lake sediments in northwest England. The PCN homologue distribution changed from a relatively even distribution in samples collected near the coast, to TeCNs dominating in the samples from the open sea. This indicates that higher chlorinated PCNs are deposited and retained in sediments to a higher degree near the coast. The total annual deposition of PCNs in sediments in the Gulf of Bothnia was estimated to be 91 kg/year.     

Atmospheric emission of polychlorinated naphthalenes from iron ore sintering processes

Iron ore sintering processes constitute significant sources of dioxins, and studies have confirmed a close correlation between polychlorinated naphthalenes (PCNs) and dioxin formation. Thus, iron ore sintering processes are thought to be a potential source of PCNs, although intensive investigations on PCN emissions from sintering processes have not been carried out. Therefore, the aim of the present study was to qualify and quantify PCN emissions from nine sintering plants operating on different industrial scales. PCN concentrations ranged from 3 to 983 ng m⁻³ (0.4-23.3 pg TEQ_PCN m⁻³) and emission factors ranged from 14 to 1749 μg t⁻¹ (0.5-41.5 ng TEQ_PCN t⁻¹), with a geometric mean of 84 μg t⁻¹ (2.1 ng TEQ_PCN t⁻¹). The estimated annual emission of PCNs from sintering processes in China was 1390 mg TEQ_PCN. These figures will assist in the development of a PCN emissions inventory. Regarding emission characteristics, PCNs mainly comprised low-chlorinated homologs. The ratios of several characteristic PCN congeners were also measured and compared with those from other sources. Taken together, these results may provide useful information for identifying the sources of PCNs produced by iron ore sintering processes.     

First world-wide interlaboratory study on polybrominated diphenylethers (PBDEs)

The first world-wide interlaboratory study on PBDEs, organised between November 1999 and April 2000, involved five biological samples, two sediments and two standard solutions. These materials were sent to 26 participants in nine different countries. Results were returned from 18 laboratories. The results reported for BDE 47 were acceptable with a range of relative standard deviations (Rsd) of 17-40%. Results for the BDEs 99 (Rsd 25-77%), BDE 100 (Rsd 19-48%), 153 (Rsd 30-48%) and 154 (Rsd 25-43%) showed that a further improvement of these analyses is needed. The BDE 209 analysis is not under the control of the participating laboratories. The data reported for the biota samples were very variable and for the two sediments Rsd values of 48% and 78% were obtained. It is recommended that analysts pay more attention to the special requirements for the BDE 209 analysis such as avoiding exposure to intensive light and exposure for too long times to too high temperatures.     

Atmospheric concentrations and phase partitioning of polybrominated diphenyl ethers (PBDEs) in Izmir, Turkey

Atmospheric concentrations of 7 PBDE congeners (BDE-28, -47, -99, -100, -153, -154 and -209) were determined at four sites (i.e. Suburban, Urban 1, Urban 2, Industrial) in Izmir, Turkey and their gas/particle partitioning was investigated. Total PBDE ( summation operator(7)PBDE) concentrations ranged between 11 (Urban 1) and 149pgm(-3) (Industrial) in summer, while in winter, they ranged from 6 (Suburban) to 81pgm(-3) (Industrial). BDE-209 was the dominant congener at all sites, followed by BDE-99 and -47. Investigation of source profiles indicated that the air samples were dominated by congeners of the penta and deca-technical BDE mixtures. The measured PBDE particle fractions were compared to the predictions of the K(OA) (octanol-air partition coefficient)-based equilibrium partitioning model and to the dynamic uptake model developed by others for passive samplers, which was adapted to model gas-particle partitioning in this study. For BDE-28, good agreement was observed between the experimental particle fractions and those predicted by the equilibrium partitioning model. However, this model overestimated the particle fractions of other congeners. The predictions of the dynamic uptake model supported the hypothesis that the unexpectedly high partitioning of BDEs (except BDE-28) to the gas-phase is due to their departure from equilibrium partitioning. When congeners with very large octanol-air partition coefficients (i.e. BDE-100, -99, -154, -153, and -209) are emitted from their sources in the gas-phase, they may remain in that phase for several months before reaching equilibrium with atmospheric particles. This may also have important implications for the transport of atmospheric PBDEs. For example, in addition to particle-bound transport, the gas-phase transport of highly brominated congeners (i.e. BDE-209) may also be important.     

Study of transportation and distribution of PCBs using an ecologically simulated growth chamber

This study was designed to investigate the transportation, distribution, and bioaccumulation of PCBs in various environmental media and compartments using an ecologically simulated growth chamber. Spatial and temporal trends of PCBs in the growth chamber were discussed. The release of PCB congeners in soil was affected by the amount of rainfall with the transporting direction moving away from PCBs contaminated point. Two pathways of PCBs accumulation in plants were the uptake of roots and the deposition on shoots/leaves. There were 29 PCB congeners been found in the lalang grass. Higher concentrations of lower chlorinated PCBs were identified than higher chlorinated PCBs because of relatively higher vapor pressure for lower chlorinated congeners. After 10months of monitoring, PCBs were detected in water samples which were contributed by the release of PCBs from leached soil. Analysis of sediment showed that the percentages of low- and mid-chlorinated biphenyls were decreased 1% and 13%, respectively compared to the increase (14%) of high-chlorinated biphenyls. The increase of high-chlorinated PCBs was possibly caused by their low hydrophilicity which had resulted higher adsorption rate in sediment. All of five species of fish had been found significant amount of PCBs accumulation ( summation operatorPCBs: 21.7-102.1 microg/g-lipid). The concentrations of PCBs in fish were varied significantly among species. The range of bioaccumulation factors (BAFs) among different species of fish could be as much as 5 times depending on the consumption habits of fish. The mass balance of PCBs distribution in the growth chamber was also discussed.     

Bioavailable DDT residues in sediments: laboratory assessment of ageing effects using semi-permeable membrane devices

We describe the reduction in bioavailability of DDT in contaminated soil after it was incubated as sediment for 365 d. Bioavailability was assessed using semi-permeable membranes. Contaminated soils from three cattle dip sites, one spiked paired uncontaminated site, and one spiked OECD standard soil were studied. Sandy soil with residues of 1880 mg/kg summation operator DDT incurred since 1962, initially had 4.6% of summation operator DDT available, reducing to 0.6% following 365 d. Clay soil (1108 mg summation operator DDT/kg) had 4.1% initially available, reducing to 0.3% after 365 d. Freshly spiked soils had a greater amount of DDT initially available (10.9%), but this reduced to 1.5% by the end of the incubation. Of the DDT congeners, both o,p'-DDD and p,p'-DDD were most bioavailable in the soils, but also had the most significant decrease following incubation.     

Chlorinated naphthalene formation from the oxidation of dichlorophenols

Polychlorinated naphthalenes (PCNs) formed along with dibenzo-p-dioxin and dibenzofuran products in the slow combustion of dichlorophenols (DCPs) at 600 degrees C were identified. Each DCP reactant produced a unique set of PCN products. Major PCN congeners observed in the experiments were consistent with products predicted from a mechanism involving an intermediate formed by ortho-ortho carbon coupling of phenoxy radicals; polychlorinated dibenzofurans (PCDFs) are formed from the same intermediate. Tautomerization of the intermediate and H2O elimination produces PCDFs; alternatively, CO elimination to form dihydrofulvalene and fusion produces naphthalenes. Only trace amounts of tetrachloronaphthalene congeners were formed, suggesting that the preferred PCN formation pathways from chlorinated phenols involve loss of chlorine. 3,4-DCP produced the largest yields of PCDF and PCN products with two or more chlorine substituents. 2,6-DCP did not produce tri- or tetra-chlorinated PCDF or PCN congeners. It did produce 1,8-DCN, however, which could not be explained.     

Occurrence,profile and possible sources of PCNs in Hong Kong soils,and a comparison with PCBs,PCDDs and PCDFs

Polychlorinated naphthalenes (PCNs) have been proposed for inclusion in the annexes of the Stockholm Convention by the European Union, signifying a probable increase in monitoring PCN levels at a global level. Investigations on PCN levels in the environment of Hong Kong have not been reported. In this preliminary investigation, PCN levels in surface soils samples were determined by isotope dilution HRGC/HRMS techniques, and compared with those of polychlorinated biphenyl (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs). The concentrations of PCNs in the soil samples were 35–883 pg g^?1 (average, 201; and median, 94 pg g^?1), which were lower than those of PCBs PCDDs and PCDFs. This comparison suggested that PCNs are currently not priority POPs compared with dioxins and PCBs in Hong Kong soils. PCDDs were the most important contributor to the sum of toxic equivalents of PCNs, PCBs, PCDDs and PCDFs. OCDD was the most dominant dioxin congener in Hong Kong surface soils. PCB-118 was the most abundant in 12 dl-PCB congeners. PCN congeners indicating thermal related sources (CN52/60, CN66/67 and CN73) were relatively abundant in their respective homologs, which suggested PCN contamination from thermal sources. The ratio of CN73 to CN74 in soil samples suggested the contribution of PCN contaminations in soils from both thermal-related sources and evaporative emissions of technical PCN mixtures.     

Occurrence and concentrations of polybrominated diphenyl ethers in sewage sludge from three wastewater treatment plants in Kuwait

Polybrominated diphenyl ether (PBDE) concentrations were measured in sewage sludge samples collected from three wastewater treatment plants in Kuwait over a six month period. PBDEs were detected in all samples analyzed and there were significant differences between the three wastewater treatment plants. The mean (and range) of summation PBDEs concentrations measured are as follows: Jahra 52.5 ng g(-1) (5.7-169.5 ng g(-1)); Reqqa, 144 ng g(-1) (32-296 ng g(-1)); Umm Haylaman, 377 ng g(-1) (23-1599 ng g(-1)). The differences in concentrations of the sum of penta congeners were consistently different at the three treatment plants with values increasing in the order: Jahra相似文献   

Organochlorine residue levels in livers of birds of prey from Spain: inter-species comparison in relation with diet and migratory patterns

Livers from 130 specimens corresponding to 18 species of raptors from Spain were analysed for persistent organochlorine (OC) residues. In all species, p,p'-DDE was the most abundant individual OC compound detected, with geometric means ranging from 61 to 40,086 ng/g ww. The geometric mean for summation operator PCB ranged from 225 to 9184 ng/g ww. Migration to Africa, south of Sahara, where p,p'-DDT is still in use, was not associated with higher liver concentrations of its metabolite, p,p'-DDE. The presence of birds in the diet of the species was an important species-specific factor determining the mean liver concentrations of p,p'-DDE and summation operator PCB. The effect of the diet on OC concentrations in liver is explained by the lower metabolising capacity of OC compounds in birds, especially for p,p'-DDE.     

Polybrominated diphenyl ethers in two species of marine top predators from England and Wales

During an earlier study, polybrominated diphenyl ethers were detected at high concentrations in fish and sediments downstream of a manufacturing site in NE England. We have now undertaken analysis of 14 tri- to heptabromodiphenyl ether congeners in tissues of two species of marine top predators exposed to these compounds through their consumption of fish. In this paper we report data for 47 cormorants and 60 harbour porpoises from England and Wales, sampled during the period 1996-2000. Concentrations of the summed congeners ranged from 1.8 to 140 microg kg(-1) wet weight in cormorant livers, and from not detected to 6900 microg kg(-1) wet weight in porpoise blubber. The major congeners present were generally BDE47, BDE99 and BDE100. There was little correlation between concentrations of chlorobiphenyls (as the sum of 25 individual congeners) and the sum of the 14 BDE congeners determined, particularly for the porpoises.