Use of semipermeable membrane devices (SPMDs)

Triolein-containing semipermeable membrane devices (SPMDs) were employed as passive samplers to provide data on the bioavailable fraction of organic, waterborne, organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and polynuclear aromatic hydrocarbons (PAHs) in streams flowing through a highly polluted industrial area of Bitterfeld in Saxony-Anhalt, Germany. The contamination of the region with organic pollutants originates in wastewater effluents from the chemical industry, from over one-hundred years of lignite exploitation, and from chemical waste dumps. The main objective was to characterise time-integrated levels of dissolved contaminants, to use them for identification of spatial trends of contamination, and their relationship to potential pollution sources. SPMDs were deployed for 43 days in the summer of 1998 at four sampling sites. The total concentration of pollutants at sampling sites was found to range from a low of 0.8 microgram/SPMD to 25 micrograms/SPMD for PAHs, and from 0.4 microgram/SPMD to 22 micrograms/SPMD for OCPs, respectively. None of the selected PCB congeners was present at quantifiable levels at any sampling site. A point source of water pollution with OCPs and PAHs was identified in the river system considering the total contaminant concentrations and the distribution of individual compounds accumulated by SPMDs at different sampling sites. SPMD-data was also used to estimate average ambient water concentrations of the contaminants at each field site and compared with concentrations measured in bulk water extracts. The truly dissolved or bioavailable portion of contaminants at different sampling sites ranged from 4% to 86% for the PAHs, and from 8% to 18% for the OCPs included in the estimation. The fraction of individual compounds found in the freely dissolved form can be attributed to the range of their hydrophobicity. In comparison with liquid/liquid extraction of water samples, the SPMD method is more suitable for an assessment of the background concentrations of hydrophobic organic contaminants because of substantially lower method quantification limits. Moreover, contaminant residues sequestered by the SPMDs represent an estimation of the dissolved or readily bioavailable concentration of hydrophobic contaminants in water, which is not provided by most analytical approaches.     

Effect of solid waste landfill organic pollutants on groundwater in three areas of Sicily (Italy) characterized by different vulnerability

The aim of this study was to obtain information on the presence and levels of hazardous organic pollutants in groundwater located close to solid waste landfills. Eighty-two environmental contaminants, including 16 polycyclic aromatic hydrocarbons (PAHs), 20 volatile organic compounds (VOCs), 29 polychlorinated biphenyls (PCBs), 7 dioxins (polychlorinated dibenzo-p-dioxins, PCDDs) and 10 furans (polychlorinated dibenzofurans, PCDFs) were monitored in areas characterised by different geological environments surrounding three municipal solid waste landfills (Palermo, Siculiana and Ragusa) in Sicily (Italy) in three sampling campaigns. The total concentrations of the 16 PAHs were always below the legal threshold. Overall, the Fl/Fl + Py diagnostic ratio revealed that PAHs had a petrogenic origin. VOC levels, except for two notable exceptions near Palermo landfill, were always below the legal limit. As concerns PCB levels, several samples were found positive with levels exceeding the legal limits. It is worth noting that the % PCB distribution differs from that of commercial compositions. In parallel, some samples of groundwater containing PCDDs and PCDFs exceeding the legal threshold were also found. Among the 17 congeners monitored, the most abundant were the highest molecular weight ones.

     

Distribution and spatial trends of PAHs and PCBs in soils in the Seine River basin, France

Persistent organic pollutants (PAHs and PCBs) in soil samples from seven sites across the Seine basin were analysed. Samples were taken from industrialized, urban, suburban and remote sites. Results showed spatial differences, in terms of concentrations and congener profiles. PAH (Sigma14 PAHs) and PCB (Sigma 7 PCBs) concentrations ranged from 450 to 5650 microg kg(-1) and 0.09 to 150 microg kg(-1), respectively. A clear gradient from industrial to remote sites was highlighted, with a ratio of up to one order of magnitude for PAHs and two orders of magnitude for PCBs. Fluoranthene and pyrene were predominant, while the carcinogenic PAHs represented 15-46% of the total PAH content. Using hierarchical cluster analysis, soil samples profiles were compared and the influence of site location and potential sources were identified: automobile traffic, domestic heating, and industrial emissions were the prevalent PAHs sources in the Seine basin. PCB profiles suggested different transport patterns among congeners. For remote sites, the congener fingerprint showed a relatively higher proportion of the most volatile congeners, which were attributed to increased atmospheric residence times. Thus, PAH and PCB distributions in soils provided information on sources and evidence for short-range transport, and profiles of compounds reflected differences between regional and local emissions. This study demonstrates that soil sampling can be used to investigate spatial differences in atmospheric inputs of persistent organic pollutants based on differences in the mixtures of compounds, reflecting differences in regional and local atmospheric emissions.     

Heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in surface sediments of the Naples harbour (southern Italy)

The Naples's harbour is one of the largest and most important commercial and tourist port of the Mediterranean basin. It is located on the southeast coast of Italy and receives industrial and municipal wastewaters from the city of Naples. Due to its social and economic impact, a comprehensive assessment of levels and sources of contamination of bottom sediments in this area of the Mediterranean basin is essential to identify potential danger due to mobilization of contaminants produced by managing of the same sediments. In this study, superficial sediments collected from 189 sampling sites were analyzed for grain size, heavy metals (Cr, Cu, Ni, Pb, V, Zn, Co, Sn, Cd, Hg, As, Al and Fe), 16 priority polycyclic aromatic hydrocarbons (PAHs) and perylene and 38 individual polychlorinated biphenyl (PCB) congeners. Compared to the estimated local background, Cu, Zn, Pb, Cd, Sn and Hg show enrichment factors >3 and only Hg evidences a median value higher than the NOAA (effects range - median) guidelines. Principal component analysis allowed us to clearly discriminate two areas mainly affected by heavy metals contamination and influenced by different sources related to industrial, commercial and/or urban activities. Priority PAHs are predominantly represented by three-five-ring compounds with concentrations ranging between 9 and 31774 ng g(-1) and frequently higher than the NOAA ER-M index. A prevalent pyrolitic origin of PAH was assessed on the basis of the relative abundance of the different congeners and selected isomer ratios. The concentrations of PCBs, as sum of the 38 congeners, ranged from 1 to 899 ng g(-1), with a predominance of highly chlorinated (tetra- and penta-chlorobiphenyls) congeners. WHO-TEQ values, calculated for the PCDD-like PCB congeners, suggest a relatively high level of toxicity. Generally, the concentration of PAHs and PCBs were higher near the sites of intense industrial, shipping and/or commercial activities suggesting a direct influence of these sources on the pollutant distribution patterns.     

Occurrence of priority organic pollutants in Strymon river catchment, Greece: inland, transitional, and coastal waters

Twenty-five sampling stations were selected in order to monitor persistent organic pollutants (polycyclic aromatic hydrocarbons (PAHs), organochlorine (OC) pesticides and total polychlorinated biphenyls (PCBs)) in surface water from Kerkini Lake, the Strymon River, its main tributaries and estuary in N. Aegean Sea during January to July, 2008, according to recent European Union (EU) guidelines. The data were divided among the high (January to April) and the low flow season (May to July). Generally, the values for organic pollutants were within the range reported worldwide for surface water. Elevated PAHs concentrations were observed compared with other places in Greece. Anthracene and benzo(a)pyrene exceeded maximum allowable concentration (MAC) of the relative EU guideline. Also, concentrations above MAC were observed for OCs, γ-HCH, and a-endosulfan. Despite the fact that it is banned since 1972, Aldrin was detected during the monitoring season (from limit of detection (LOD) to 15 ng L(-1)). Total PCB concentrations ranged from LOD to 162 ng L(-1). In addition, the load of organic pollutants was estimated in April (high flow) and June (low flow) in selected sampling stations. According to this estimation, napthalene, anthracene, and fluoranthene (PAHs), total dichlorodiphenyltrichloroethane (DDT), aldrin, and total PCBs had the highest load. Taking into account the relative EU guidelines concerning the pollutants studied, the water quality in the Strymon River catchment could be characterized as poor, which can lead to negative impacts to its biota.     

Seasonal variations of hydrophobic organic contaminant concentrations in the water-column of the Seine Estuary and their transfer to a planktonic species Eurytemora affinis (Calanoïda, copepoda). Part 1: PCBs and PAHs

Hydrophobic organic contaminants (HOC) (i.e. PAHs and PCBs) were measured in the water column and in Eurytemora affinis samples from the Seine Estuary collected from November 2002 to February 2005. Results showed seasonal variations of both total PCB and PAH levels in the suspended particulate matter (SPM) and in the copepods with maximum levels during winter times. PAH and PCB concentrations in the SPM ranged from 499 to 5819ngg(-1) and from 58 to 463ngg(-1), respectively. Phenanthrene, pyrene and benzo[b+j+k]fluoranthene (B[b+j+k]F) were the predominant PAH compounds in the water column, while CB 101, 118, 153 and 138 were the most abundant PCB congeners. PCBs and PAHs bioaccumulated by E. affinis (EA) varied between 383 and 1785ngg(-1) and 165-3866ngg(-1). CB101, 153, 138 and B[b+j+k] were, respectively, the major compounds of PCB and PAH fingerprints in EA. Thereby, the copepods could reach high accumulation factor (ACF) (91000 for PCBs and 17000 for PAHs). The principal component analyses of contaminant concentrations and environmental parameter datasets distinguished two groups of copepods. The winter time cluster, with high percentage of adult copepods, which bioaccumulated the highest PCB and PAH body-burdens, and the second cluster with juveniles showing the lowest HOC concentrations. Thus, PAH and PCB concentrations in EA exhibited significant correlations with the percentage of adults making up the samples.     

Levels of persistent organic pollutants in the Neretva River (Bosnia and Herzegovina) determined by deployment of semipermeable membrane devices (SPMD)

The main objective of this study was to determine levels of certain persistent organic pollutants (POPs) in Neretva River, Bosnia and Herzegovina (BiH), which is currently facing implementation of the Stockholm Convention on persistent organic pollutants (POPs) and environmental protection strategies. This is the very first report on the deployment of semipermeable membrane devices (SPMDs) in BiH. SPMDs were used for continuous 3-weeks sampling of POPs at three locations, covering 220 km long stream of the Neretva River. Water concentrations of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polybrominated diphenylethers (PBDEs) were calculated using performance reference compounds (PRCs). The total OCP concentrations ranged from 40 to 140 pg L^?1 and most of compounds were detected only in lower course of the river. Total PAH ranged from 160 to 4000 pg L^?1 and show a clear spatial variation. Dominant PAHs were phenanthrene, fluoranthene, fluorene and acenaphthene. Total PCB ranged from undetectable to 120 pg L^?1. From the group of 15 PBDE congeners investigated, only PBDE-47 and PBDE-99 were detected. Since the concentrations of broad spectrum of POPs found in the Neretva River are quite low, future actions should be focused on preservation rather than on sanitation measures. Regular monitoring should anyhow be established.     

Partitioning of polychlorinated biphenyls in octanol/water, triolein/water, and membrane/water systems

The use of the octanol/water partition constant (Kow) as a surrogate parameter for lipid/water partitioning of persistent organic pollutants (POPs) was reassessed by comparing the measured Kow of 12 selected polychlorinated biphenyl congeners (PCBs) with partition constants in triolein/water (Ktw) and membrane/water (Kmw) systems. Kow and Ktw were measured by the slow-stirring method. Kmw was measured by an adaptation of the slow-stirring method using suspensions of phosphatidylcholine and phosphatidylserine liposomes. Partitioning of POPs to octanol, triolein, and liposomes is similar but not equal. The log-log correlation for Kow and Ktw is excellent (r2 = 0.982) and that for Kow and Kmw is somewhat weaker (r2 = 0.856). Ktw values are greater than Kow by a factor of 1.6. Kmw of some PCB congeners exceed both Kow and Ktw by an order of magnitude. The differences are attributed to different PCB activity coefficients in the different lipid phases. The results imply that Kow can be used as a reasonable conservative estimate of lipid/water partitioning. But the observed differences between Kow and Kmw also indicate that using Kow to predict accumulation of POPs, particularly highly hydrophobic ones, in the polar lipids of organisms will underestimate their concentrations at equilibrium.     

Purification of triolein for use in semipermeable membrane devices (SPMDs)

Analyses of triolein-containing semipermeable membrane devices (SPMDs) have sometimes been impeded by interferences caused by impurities endemic to triolein that codialyze with the analytes. Oleic acid and methyl oleate have been the most troublesome of these impurities because of their relatively high concentrations in triolein and because significant residues of both can persist even after size exclusion chromatographic (SEC) fractionation. These residues have also been blamed for false-positive signals during bioindicator testing of SPMD dialysates. To prevent these problems, a simple, cost-effective procedure was developed for purifying triolein destined for use in SPMDs: the bulk triolein is repeatedly (6x) partitioned against methanol. Tests of the procedure show that 14C-oleic acid is completely removed from the triolein. After SEC fractionation, dialysates of standard-size SPMDs made with the purified triolein contain less than 5 microg of methyl oleate as compared to sometimes more than 500 microg for dialysates (also after SEC) of SPMDs made with unpurified triolein. Gas chromatographic analyses with flame ionization and electron capture detection show that the purification treatment also greatly reduces the number and size of peaks caused by unidentified contaminants in the triolein. Microtox basic assay of dialysates of SPMDs shows that those made with the purified triolein have lower acute toxicities than dialysates of SPMDs made with unpurified triolein. Yeast estrogen screen (YES) testing of SPMDs fabricated with unpurified and purified triolein demonstrates that the purification process removes all background estrogenic activity.     

Polychlorinated biphenyls in surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in East China Sea

The spatial distribution and source of polychlorinated biphenyls (PCBs) in 30 surface sediments of Yueqing Bay, Xiangshan Bay, and Sanmen Bay in Eastern China were analysed. Total concentrations of PCBs ranged from 9.33 to 19.60 ng g⁻¹ dry weight for all the sampling stations. The observed PCB levels were lower than those in areas of high urbanisation or contamination in the bay. Low-chlorinated PCBs, dominated by tri-PCB, were identified as the prevalent contaminate of surface sediments, and the top three PCB congeners were lighter chlorinated congeners (PCB 8, PCB 18 and PCB 28). These results were in agreement with the fact that tri-PCB compounds are the dominant contaminants in China. The result of the principal component analysis revealed that all samples were similar in composition to Aroclor 1242, suggesting they might originate from electrical capacitors and transformers. The levels of PCBs were significantly correlated with the total organic carbon in the sediments.     

The identification of readily bioavailable pollutants in lake shkodra/skadar using semipermeable membrane devices (SPMDs), bioassays and chemical analysis

GOAL, SCOPE AND BACKGROUND: Lake Shkodra/Skadar is the largest lake in the Balkans region and located on the border between Albania to the south and Montenegro to the north. Because of the wide range of endemic, rare or endangered plant and animal species it supports, Lake Shkodra/Skadar and its extensive associated wetlands are internationally recognised as a site of significance and importance (Ramsar site). In recent years, social and economic changes in both Albania and Montenegro have lead to unprecedented levels of urban and industrial effluent entering the lake. Of particular concern is the increasing input of toxic hydrophobic organic pollutants (HOPs) into the lake and the degree to which these compounds are available for uptake by aquatic biota. Semipermeable membrane devices (SPMDs) have been shown to sample the readily bioavailable fraction (dissolved phase) of waterborne HOPs and in doing so provide relevant data for exposure assessment. The aim of the current study was to use SPMD-based sampling in conjunction with appropriate bioassays and chemical analysis to identify readily bioavailable HOPs in the lake. METHODS: SPMDs were constructed and deployed at three sites in the Albanian sector and three sites in the Montenegrin sector of Lake Skadar/Shkodra for 21 days. Following the dialytic recovery of target analytes and size exclusion chromatographic clean-up, aliquots of SPMD samples were subjected to GC-MS scan analysis for major components, GC-MS SIM analysis for 16 priority pollutant polycyclic aromatic hydrocarbons (PP-PAHs) and assayed for EROD-inducing, estrogenic and mutagenic potential using rainbow trout liver cells (RTL-W1), the yeast estrogen screen (YES) and the Ames Test, respectively. RESULTS AND DISCUSSION: A total of 39 compounds were tentatively identified in SPMD samples from the six sampling sites. Alkylated PAHs were the most abundant and ubiquitous compounds present along with various sterols and sterol derivatives. Numerous other compounds remain unidentified. 15 of the 16 targeted PP-PAHs were present in samples from one or more of the sampling sites indicating these compounds are both readily bioavailable and widely distributed in Lake Shkodra/Skadar. Total PP-PAH concentrations ranged between 3991 ng/SPMD and 10695 ng/SPMD. Bioassays carried out on SPMD samples revealed significant EROD-inducing and estrogenic potential at five of the six sampling sites indicating toxicologically relevant compounds are readily available for uptake by resident aquatic biota. EROD-inducing potential was positively correlated with targeted PP-PAH concentration (r2 = 0.74). However, comparison of bioassay- and analytically-derived toxicity equivalents revealed targeted PP-PAHs were responsible for less than 0.06% of the total EROD-inducing potential. CONCLUSIONS AND OUTLOOK: The combination of SPMD-based sampling with appropriate bioassays and chemical analysis provided an effective tool for the identification of environmentally relevant waterborne pollutants in Lake Shkodra/Skadar. Our results show that toxicologically relevant HOPs including EROD-inducing and potentially estrogenic compounds are widely distributed in the lake and readily available for uptake by aquatic biota. Our results also suggest that alkylated PAHs rather than parent compounds may be of greater toxicological relevance in the lake. As anthropogenic influences continue to increase, SPMD-based sampling is expected to play a central role in future research concerned with the identification, monitoring and assessment of the risk posed by HOPs to Lake Shkodra/Skadar's aquatic biota.     

Extraction of organic contaminants from marine sediments and tissues using microwave energy.

In this study, we compared microwave solvent extraction (MSE) to conventional methods for extracting organic contaminants from marine sediments and tissues with high and varying moisture content. The organic contaminants measured were polychlorinated biphenyl (PCB) congeners, chlorinated pesticides, and polycyclic aromatic hydrocarbons (PAHs). Initial experiments were conducted on dry standard reference materials (SRMs) and field collected marine sediments. Moisture content in samples greatly influenced the recovery of the analytes of interest. When wet sediments were included in a sample batch, low recoveries were often encountered in other samples in the batch, including the dry SRM. Experiments were conducted to test the effect of standardizing the moisture content in all samples in a batch prior to extraction. SRM1941a (marine sediment). SRM1974a (mussel tissue), as well as QA96SED6 (marine sediment), and QA96TIS7 (marine tissue), both from 1996 NIST Intercalibration Exercise were extracted using microwave and conventional methods. Moisture levels were adjusted in SRMs to match those of marine sediment and tissue samples before microwave extraction. The results demonstrated that it is crucial to standardize the moisture content in all samples, including dry reference material to ensure good recovery of organic contaminants. MSE yielded equivalent or superior recoveries compared to conventional methods for the majority of the compounds evaluated. The advantages of MSE over conventional methods are reduced solvent usage, higher sample throughput and the elimination of halogenated solvent usage.     

Contamination of an arctic terrestrial food web with marine-derived persistent organic pollutants transported by breeding seabirds

At Cape Vera, Devon Island (Nunavut, Canada), a colony of northern fulmars (Fulmarus glacialis) concentrates and releases contaminants through their guano to the environment. We determined whether persistent organic pollutants (POPs) from seabirds were transferred to coastal food webs. Snow buntings (Plectrophenax nivalis) were the most contaminated species, with ∑PCB and ∑DDT (mean: 168, 106 ng/g ww) concentrations surpassing environmental guidelines for protecting wildlife. When examined collectively, PCB congeners and DDT in jewel lichen (Xanthoria elegans) were lower in samples taken farther from the seabird colony, and increased with increasing δ¹⁵N values. However, only concentrations of p’p-DDE:∑DDT and PCB-95 were significantly correlated inversely with distance from the seabird cliffs. Linkages between marine-derived POPs and their concentrations in terrestrial mammals were less clear. Our study provides novel contaminant data for these species and supports biovector transport as a source of organic contaminants to certain components of the terrestrial food web.     

Occurrence of PAHs, PCBs and organochlorine pesticides in the Tonghui River of Beijing, China

Tonghui River, a typical river in Beijing, People's Republic of China, was studied for its water and sediment quality, by determining the levels of 16 polycyclic aromatic hydrocarbons (PAHs), 12 polychlorinated biphenyls (PCBs) and 18 organochlorine pesticides in water and sediment samples. Total PAHs, PCBs and organochlorine pesticides concentrations in water varied from 192.5 to 2651 ng/l, 31.58-344.9 ng/l and 134.9-3788 ng/l, respectively. The total PAHs, PCBs and organochlorine pesticides concentrations in surficial sediments were 127-928 ng/g, 0.78-8.47 ng/g and 1.79-13.98 ng/g dry weight, respectively. The results showed that the concentration of these selected organic pollutants in sediment was higher than those in surface water. It may be due to the fact that organic hydrophobic pollutants tend to stay in the sediments. The PAHs were dominated by 2-, 3-ring components in water samples and by 3- and 4-ring compounds in sediment. For organochlorines, alpha-HCH, delta-HCH, Heptachlor, Endosulfan II, DDT are the major organochlorine pesticides in water while Heptachlor, Dieldrin and DDE composed of 95% of total organochlorine pesticides in sediment. For HCHs (HCHs=alpha-HCH+beta-HCH+gamma-HCH+delta-HCH), the predominance of alpha-HCH of total HCHs were clearly observed in water and sediment. PCB18, PCB31 and PCB52 were predominant in water, on average these compounds collectively accounted for 67% of total PCBs. But in sediment, the predominant compounds were PCB28, PCB31 and PCB153, which accounted for 71% of total PCBs in sediment. The levels of micro pollutants in our study areas were compared with other studies.     

Levels, persistence and bioavailability of organic contaminants present in marine harbor sediments impacted by raw sewage

As part of a program to investigate the levels, fate and bioaccumulation of organic contaminants in a polluted marine harbor, organochlorine compounds including the polychlorinated biphenyls (PCBs), dichloro diphenyltrichloroethane and metabolites (DDTs), chlordanes, dibenzo-p-dioxins (Ds) and dibenzofurans (Fs), polycyclic aromatic hydrocarbons (PAHs) and sulphur hetero cycles were analysed in sediments spiked with St. John's Harbor sludge. Winter flounder (Pseudopleuronectes americanus) were exposed to these sediments containing six levels of harbor sludge during four winter months. Following exposure, sediments were reanalysed to investigate the persistence of the contaminants. The primary contaminants detected were PAHs (approximately 5000 ng/g), predominantly alkylated phenanthrenes, fluoranthene and pyrene; PCBs with a predominance of Aroclor 1260 signature (approximately 64 ng/g), DDTs (approximately 5 ng/g), hepta and octachloro dioxins and furans (approximately 0.5 ng/g) with very low levels of less chlorinated congeners. The PAHs degraded with an estimated half life of 2 to 3 months, while no significant degradation could be attributed to the other compounds. Bioaccumulation to muscle showed the potential uptake of contaminants in biota inhabiting the harbor. A dose-response relationship was observed between spiked sediments and the concentrations of PCB congener 153 and unresolved congeners 138/163/164 in muscle. Of the dioxins and furans, only 2, 3, 7, 8-tetrachlorofuran was detectable in muscle and at a similar concentration in all exposures indicating a similar bioavailability independent of the fraction of sludge in sediments. Of the PAHs, only naphthalene and methyl naphthalenes were detected in muscle, but did not display a dose-response. One bile metabolite of pyrene was quantified and demonstrates metabolism. Biota-sediment accumulation factors were of 0.2 to 7 indicating that equilibrium was approached, with the exception of the hepta and octachloro dioxins and furans which were not significantly bioaccumulated.     

Solid phase extraction with pyrenebutyric acid-bonded silica for analysis of polychlorinated biphenyls in sewage water by gas chromatography-mass spectrometry

A solid phase extraction (SPE) method using pyrenebutyric acid-bonded silica (PYB) as sorbent was developed to determine 23 polychlorinated biphenyls (PCBs) in sewage water by gas chromatography-mass spectrometry (GC-MS). Factors were optimized in SPE procedures including elution solvent, pH, and cartridge burden. The recoveries of 23 PCB congeners were 69.44-111.91% under optimized conditions. Comparisons were also conducted among PYB-SPE, C(18)-SPE and United States Environmental Protection Agency 608 (USEPA608) methods in the analysis of PCBs in sewage water samples. The results showed that the performance of PYB-SPE method was similar with USEPA608 method and better than C(18)-SPE method. Both PYB-SPE and USEPA608 methods were then employed to analyze PCBs in real spiked sewage water samples. The recoveries of PCB congeners determined by PYB-SPE method ranged from 70.6% to 92.4% in real spiked sewage water samples which were identified to be in accordance with USEPA608 method. Limits of detection (LOD) were in the range of 0.06-0.22ngL(-1) for PCB congeners. The optimized PYB-SPE method was successfully applied to the determination of PCBs in sewage water samples.     

Serum concentrations and profiles of polychlorinated biphenyls in Taiwan Yu-cheng victims twenty years after the incident

In 1979, about 2000 people in central Taiwan were intoxicated via rice oil consumption that was contaminated with polychlorinated biphenyls (PCBs). This "Yu-cheng" incident was one of the two known major human PCB intoxication episodes. Twenty years after the intoxication, serum samples of 435 Yu-cheng victims, 414 adults and 21 children, were collected. Sixteen PCB congeners were analyzed with a gas chromatograph-electron capture detector. We found the median concentration of total PCBs in the adult serum was 1500 ng/g lipid, still substantially higher than that of the general population in Taiwan (3.7-fold) and most seafood consumers in the world. Most of analyzed PCB congeners in children were below or around the detection limits. Congener #138, however, had the highest concentrations, approximately accounting for 55% and 29% in the child and adult groups, respectively. Given that PCBs are persistent organic pollutants and endocrine disruptors, the concentrations and congener-specific profiles regarding the Yu-cheng victims provide valuable information for the investigation of such chemicals in humans.     

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.     

Temporal evolution of polycyclic aromatic hydrocarbons (PAHs) in sludge from wastewater treatment plants: comparison between PAHs and heavy metals

This paper presents results on the presence and temporal variability of the 16 PAHs recommended by the EPA in primary, secondary and digested sewage sludge over a year. The sewage sludges originated from the Guadalete wastewater treatment plant (WWTP) site in Jerez de la Frontera (Cádiz, Spain). These organic pollutants have been extracted from the sewage sludge by microwave energy. High performance liquid chromatography coupled with diode array (HPLC-DAD) or fluorescence (HPLC-FL) detectors have been used. The results showed that total PAHs concentration varied between 1,945 ng g(-1) dry matter (DM) for primary sludges collected in March and 10,100 ng g(-1) DM for primary sludge collected in June. Generally, concentrations of PAHs were higher in compost and digested sludge than in fresh one. On the other hand, the highest concentration of PAHs were found on summer. This thing is associated to the traffic increase from inland zones to the coast (Jerez de la Frontera is very near to beaches). Finally, this paper present a comparative study of the American an European legislation concluding that the limits of concentrations established are not exceeded. In addition heavy metals were analysed. The origin of PAHs and heavy metals seems to be different.     

Monitoring PAHs in the Brisbane River and Moreton Bay, Australia, using semipermeable membrane devices and EROD activity in yellowfin bream, Acanthopagrus australis

Two water quality monitoring strategies designed to sample hydrophobic organic contaminants have been applied and evaluated across an expected concentration gradient in PAHs in the Moreton region. Semipermeable membrane devices (SPMDs) that sequester contaminants via passive diffusion across a membrane were used to evaluate the concentration of PAHs at four and five sites in spring and summer 2001/2002, respectively. In addition, induction of hepatic cytochrome P4501, EROD activity, in yellowfin bream, Acanthopagrus australis, captured in the vicinity of SPMD sampling sites following deployment in summer was used as a biomarker of exposure to PAHs and related chemicals. SPMDs identified a clear and reproducible gradient in PAH contamination with levels increasing from east to west in Moreton Bay and upstream in the Brisbane River. The highest PAH concentrations expressed as B(a)P-toxicity equivalents (TEQs) were found in urban areas, which were also furthest upstream and experienced the least flushing. Cytochrome P4501 induction in A. australis was similar at all sites. The absence of clear trends in EROD activity may be attributable to factors not measured in this study or variable residency time of A. australis in contaminated areas. It is also possible that fish in the Moreton region are displaying enzymatic adaptation, which has been reported previously for fish subjected to chronic exposure to organic contaminants. These potential interferences complicate interpretation of EROD activity from feral biota. It is, therefore, suggested that future monitoring combine the two methods by applying passive sampler extracts to in vitro EROD assays.