Polychlorinated Diphenyl Ethers Research Articles

Human Exposure to Polychlorinated Naphthalenes and Polychlorinated Diphenyl Ethers from Foods in Catalonia, Spain: Temporal Trend

Although polychlorinated naphthalenes (PCNs) and polychlorinated diphenyl ethers (PCDEs) are pollutants that have been detected in a number of environmental samples, information concerning human exposure to these compounds through the diet is very scarce. In this study, the concentrations of PCNs and PCDEs were determined in samples of foodstuffs widely consumed by the population of Catalonia, Spain. The dietary intake of PCNs and PCDEs also was estimated for the population of this Spanish region, and the results were compared to those of a previous survey performed during 2000. The highest sigmaPCNs corresponded to fish and seafood (47.1 ng/kg wet wt), followed by oils and fats (21.5 ng/kg wet wt), bakery products (15.3 ng/kg wet wt), and dairy products (11.7 ng/ kg wet wt). The highest sigmaPCDEs corresponded also to fish and seafood (1094.7 ng/kg wet wt), a value that was notably higher than those concerning the remaining food groups. For a standard male adult of 70 kg body weight, the dietary intakes of PCNs and PCDEs were 7.25 and 51.68 ng/day, respectively (or 0.10 and 0.74 ng/kg body wt/day). These results mean a reduction of 84% for PCNs with respect to the daily intake of these pollutants in the 2000 survey, mainly due to the decreases in the contribution of cereals and oils and fats. By contrast, the intake of PCDEs increased to 26%, fish and seafood being the main contributors to this increase.

Use of a column leaching test to study the mobility of chlorinated HOCs from a contaminated soil and the distribution of compounds between soluble and colloid phases

An equilibrium and recirculation column test for hydrophobic organic chemicals (ER-H test) was used to study the leaching behaviour of chlorophenols (CPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzofurans (PCDFs) and polychlorinated dibenzo- p-dioxins (PCDDs) from contaminated soil. A 50% increase in the pore water velocity was shown to have little or no effect on the mobility of CPs, PCDEs, PCDFs and PCDDs. The standard deviations of truly dissolved compounds, CPs, were between 19% and 65% between the tests. However, the repeatability of the ER-H test decreased with increases in the hydrophobicity of the studied compounds; the standard deviations for PCDEs, PCDFs and PCDDs ranged from 53% to 110%, 57% to 77% and 110% to 130%, respectively. The influence of colloids on the release of these compounds was also examined. Up to 30% of the CPs in the soil were leached, of which 1–3% were associated with colloids. The PCDEs, PCDFs and PCDDs were found to be preferably associated with the particulate fraction of the leachate, and less than 0.2% of these compounds were mobilised.

Comprehensive two-dimensional gas chromatography in the screening of persistent organohalogenated pollutants in environmental samples

Separations of eight persistent organohalogenated classes of pollutants, organochlorinated pesticides (OCPs), polychlorinated biphenyls (PCBs), polychlorinated diphenyl ethers (PBDEs), polychlorinated dibenzo- p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated naphthalenes (PCNs), polychlorinated terphenyls (PCTs) and toxaphene (CTT) by comprehensive two-dimensional gas chromatography (GC × GC) were evaluated. Columns with different polarity and selectivity, including ZB-5, HT-8, DB-17 and BP-10, were selected as first dimension and combined with columns of increasing polarity in the second dimension, i.e. HT-8, BPX-50 and Carbowax (or Supelcowax-10). In total nine column combinations were tested. Because the main interest of the study was fast screening of the test xenobiotic families in complex matrices, in all cases, attention was primarily focussed on group-type separation. Nevertheless, within-group separation was also considered, especially for those classes containing particularly toxic congeners, such as PCBs and PCDD/Fs. Although none of the assayed column sets allowed the simultaneous and complete separation of all pollutants classes, some column combinations provided satisfactory separations among selected families and the rest of pollutants investigated. That was, for instance, the case of HT-8 × BPX-50 for PBDEs and PCDD/Fs, DB-17 × HT-8 for PCNs and OCPs and BP-10 × BPX-50 for CTT, PCDD/Fs and PBDEs. The feasibility of the proposed approach for the fast screening of the target classes of pollutants in complex samples was illustrated by the analysis of food and marine fat samples prepared using simplified miniaturised sample treatment methods.

Chlorinated Diphenyl Ethers in Sediments, Biota, and the Water Column from Coastal British Columbia, Canada

Polychlorinated diphenyl ethers (PCDEs) are impurities in technical chlorophenol mixtures, are used as dielectric fluids in capacitors and as herbicides, antiseptics, food preservatives, and papers and textiles, and can be formed through the chlorination of organics in water and wastewater streams. Samples from semipermeable membrane devices (SPMDs), sediments, English sole, mussels, and Dungeness crab were collected from urban/industrial and remote sites along the marine coast of British Columbia and analyzed by congener-specific GC-MS analysis for mono- through deca-substituted PCDEs. Higher concentrations in biota and sediments were observed near urban/industrial areas, with evidence for food-chain biomagnification within major harbours. Correlations between size distributions and PCDE levels indicate these hydrophobic contaminants tend to preferentially partition into sediments with higher clay/silt fractions. Multivariate analysis of congener patterns shows distinct PCDE profiles among different species and environmental matrices, and evidence for favoured dechlorination pathways among the most commonly observed congeners in aquatic systems.

Formation of polychlorinated diphenyl ethers from condensation of chlorophenols with chlorobenzenes

Polychlorinated diphenyl ethers (PCDEs), which are among the members of persistent organic pollutants, and PCDEs have been determined in a number of environmental samples. The main possible sources are the technical production of chlorinated phenols and all processes of incomplete combustion. PCDEs were observed in the fly ash from a municipal waste incinerator (MWI). It was speculated that the condensation of chlorophenols with chlorobenzenes occurred via PCDEs to form polychlorinated dibenzofurans (PCDFs). Nevertheless, PCDEs formation from condensation of chlorophenols with chlorobenzenes has not been confirmed by experimental observation. The objective of this paper is to investigate the formation mechanism of PCDEs from the condensation of chlorophenols with chlorobenzenes. The results are expected to be helpful in understanding the formation of PCDEs and in controlling and abating PCDEs emissions from MWI. The pyrolysis of pentachlorophenol (PCP) and/or polychlorobenzenes (PCBz) was carried out in a sealed glass tube. The reaction products were extracted and purified with K2CO3 solution. The samples were concentrated and then cleaned up on an alumina column. GC/MS was used for identification and quantification of reaction products. The results showed that the pyrolysis of hexachlorobenzene (HCB) at 340 degrees C for 6 h led to the formation of decachlorodiphenyl ether (DCDE) (2.41 microg/mg) and octachlorodibenzo-p-dioxins (OCDD) (0.24 micropg/mg), while the pyrolysis of PCP yielded DCDE (13.08 microg/mg) and OCDD (180.13 microg/mg). In addition, the amount of DCDE formation from the pyrolysis of the mixture of PCP and HCB was 4.65 times higher than the total amount of DCDE formation from the pyrolysis of HCB and PCP, respectively. This indicated that PCP and HCB were prone to condensation and formation of DCDE. DCDE was the main congener of PCDEs from condensation of PCP with HCB at 340, 400 and 450 degrees C. A small amount of nonachlorodiphenyl ether (NCDE) was formed by dechlorination reaction at 450 degrees C. The condensation of PCP with 1,2,4,5-tetrachlorobenzene (Cl4Bz) formed 2,2',3,4,4',5,5',6-octachlorodiphenyl ether (OCDE). Small amounts of heptachlorodiphenyl ether (HpCDE) and hexachlorodiphenyl ether (HxCDE) were detected at 450 degrees C. Meanwhile, polychlorinated dibenzo-p-dioxins (PCDDs) and PCDFs were detected from the condensation of PCP and PCBz. Experimental studies clarified the behavior of the formation of PCDEs from condensation of polychlorophenols and PCBz. The condensation of polychlorophenols with PCBz formed PCDEs through elimination of HCl between polychlorophenols and PCBz molecules. Another pathway of PCDEs formation was elimination of H2O between two polychlorophenol molecules. In addition, dechlorination processes had caused the specific homologous pattern of PCDEs under higher temperatures.

QSPR modeling of n-octanol/water partition coefficients and water solubility of PCDEs by the method of Cl substitution position

The number of Cl substitution positions (N(PCS)) of all 209 possible molecular structure patterns of polychlorinated diphenyl ethers (PCDEs) were correlated with their partition properties n-octanol/water partition coefficient (lgK(ow)) and sub-cooled liquid water solubilities (-lgS(w,l)). The correlation coefficients (R) and the leave-one-out (LOO) cross-validation correlation coefficients (R(cv)) of all the 6-descriptor models for lgK(ow) and -lgS(w,l) are more than 0.98. By using stepwise multiple regression (SMR), the best two models of lgK(ow) with three descriptors (R=0.9,913) and lgS(w,l) with four descriptors(R=0.9,818) were obtained respectively. Based on these equations, the two properties of all 209 PCDEs were predicted. Model validation showed that the two models exhibit optimum stability and high predictive power. Moreover, results of prediction were further compared with data from similar studies by molecular connectivity indices (MCIs) and PM3 methods.

Intake of chemical contaminants through fish and seafood consumption by children of Catalonia, Spain: Health risks

The intake of arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb), polychlorinated dibenzo- p-dioxins and dibenzofurans (PCDD/Fs), polychlorinated biphenyls (PCBs), polychlorinated naphthalenes (PCNs), polybrominated diphenylethers (PBDEs), polychlorinated diphenylethers (PCDEs), hexachlorobenzene, and polycyclic aromatic hydrocarbons through fish and seafood consumption by children of Catalonia, Spain, was assessed. In 2005, samples of the 14 most consumed marine species in Catalonia were randomly acquired in various cities of the country. Analysis of the above chemical contaminants were determined according to the appropriate analytical techniques and the daily intakes were estimated. For most pollutants, intake was higher in boys than in girls. Average exposure of children to contaminants through fish and seafood consumption did not exceed the respective tolerable daily intake of those pollutants for which it has been already established (metals, PCDD/Fs plus dioxin-like PCBs, HCB, and PAHs). In relation to body weight, intake by children of most contaminants was higher than that found for other age groups of the general population of Catalonia.

Bioindikation mit Wanderfalken

The Stockholm convention bans 12 prominent persistent organic pollutants (POPs), and the pertinent global monitoring programme recommends birds’ eggs as bio-indicators for the terrestrial food web. As top predators, Peregrine falcons are uniquely suited indicators because of their accumulating power for persistent and lipophilic compounds. On the other hand, the Peregrine falcon as a sentinel species was closer to extinction than other birds of prey. Only unremitting efforts of private omithologists throughout the past four decades in conjunction with the timely banning of organochlorine pesticides like DDT succeeded in saving the Peregrine population of Baden-Wueriternberg from extinction, in contrast to the Peregrine falcons of other German states or other European countries. See vd Trenck et al. (2006). New results confirm the findings of the past long-term bio-monitoring. The main pollutants are PCBs (ca. 20 μg/g) and pp′-DDE (ca. 11 μg/g), the latter contributing >96% of all organochlorine pesticide residues (all concentrations on a dry matter basis). Both substances have followed a slightly increasing trend since 2004. The sum of the polychlorinated diphenyl ethers (PBDE) has fluctuated strongly in the past four years, and in 2006 amounted to 0.6 μg/g (mean without outliers), just as the mercury contamination of the eggs. PCB-156 as the main dioxin-like PCB followed with an average concentration of 0.35 μg/g. Only 10 out of 23 eggs analysed contained hexabromocyclododecane (HBCD) in measurable concentrations; the mean concentration of these eggs was 0.024 μg/g. Tetrabromobisphenol A (TBBA) was detected in all egg samples with a mean of 0.004 μg/g. Due to the many and diverse effects exerted by PCBs; the assessment of this group of compounds, with the aid of European and German regulations for food, proves to be a complex matter, which is currently in a state of flux. There is no doubt, however, that the mean pollution of the Peregrine eggs with toxic dioxin equivalents (WHO TEQ) has reached the no observed adverse effect level (NOAEL) known for chickens and osprey chicks, and the most polluted eggs exceed this threshold considerably. The toxic profile of PBDEs is similar to that of PCBs. They are known to promote tumour growth, to interfere with the thyroid hormone system resulting in toxicity for the neuronal development, to suppress the immune system, and to trigger stress reactions. Tests with highly purified BDE-47 have ruled out dioxin-like effects via Ah-receptor binding for this congener and such effects are therefore very unlikely for the whole class of compounds. At the present time, quantitative criteria for the assessment of the risk posed by PBDEs are not sufficiently reliable, and less so for HBCD and TBBA. It is necessary to continue the bio-monitoring of POPs and similar pollutants in the terrestrial food web and to establish NOAELs as quantitative criteria for their assessment. Possible sources of dioxin-like PCBs and PCDD/Fs are to be pinpointed, and abatement measures are to be considered where background concentrations are significantly exceeded.

Analysis of polychlorinated dibenzo- p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls in vegetable oil samples by gas chromatography–ion trap tandem mass spectrometry

Gas chromatography coupled to ion trap tandem mass spectrometry (CG–MS–MS) has been evaluated for the analysis of polychlorinated dibenzo- p-dioxins (PCDDs) and dibenzofurans (PCDFs) and dioxin-like polychlorinated biphenyls (dl-PCBs) in vegetable oil samples containing different concentration levels (0.2–6 pg WHO-TEQ g −1 for both PCDD/Fs and dl-PCBs) of the 29 toxic congeners of PCDD/F and dioxin-like PCBs. The effect of potential interfering compounds such as polychlorinated naphthalenes (PCNs), polychlorinated biphenyls (PCBs) and polychlorinated diphenylethers (PCDEs) on the quantification of mono-ortho PCBs has been investigated. In addition, the influence of the clean-up procedure on the final determination by CG–MS–MS was studied, showing that the quality of the results depends to a great extent on this analytical step. Quality parameters have been established and good precisions (CV: 3–19%) and low limits of detection for PCDD/Fs (0.04–0.20 pg g −1 oil) and dl-PCBs (0.08–0.64 pg g −1 oil) were obtained. The method was validated by a comparison of the CG–MS–MS results with those obtained by GC–HRMS.

Partitioning of chloroaromatic compounds between the aqueous phase and dissolved and particulate soil organic matter at chlorophenol contaminated sites

The retention and mobility of hydrophobic organic contaminants (HOCs) in soil is mainly determined by hydrophobic partitioning to dissolved and particulate organic matter (DOM and POM, respectively). The aqueous phase, DOM, and POM fractions were extracted and separated from soils at three sites contaminated with technical chlorophenol formulations. Concentrations of chlorophenols (CP), polychlorinated phenoxyphenols (PCPP), polychlorinated diphenyl ethers (PCDE) and polychlorinated dibenzo- p-dioxins and furans (PCDD/F) were determined. The partitioning to POM, in relation to DOM, increased in all three soils with increasing hydrophobicity in the order CP < PCPP ∼ PCDE ∼ PCDF < PCDD. Differences in partitioning to DOM (log K DOC) and POM (log K POC) could not be explained by differences in gross organic C chemistry. Black carbon did not contribute significantly to the sorption of PCDDs, whereas >70% wood fibre in one soil resulted in a decrease of log K POC of 0.5 units for CPs and PCDDs. We conclude that log K OC for both DOM and POM need to be explicitly determined when the retention and mobility of HOCs is described and modelled in soils.

Quantitative structure–property relationships for predicting subcooled liquid vapor pressure ( PL) of 209 polychlorinated diphenyl ethers (PCDEs) by DFT and the position of Cl substitution (PCS) methods

Optimization of the molecular geometry of 209 polychlorinated diphenyl ethers (PCDEs) and diphenyl ether (DE) were carried out at the B3LYP/6-31G* level with Gaussian 98 program. Based on the theoretical linear solvation energy relationship (TLSER) model, the obtained structural parameters were taken as theoretical descriptors to establish the first novel QSPR model (I) for predicting subcooled liquid vapor pressure ( P L) of PCDEs. The model (I) achieved in this work contains three variables: most negative atomic partial charge in molecule ( q − ), dipole moment of the molecules ( μ) and mean molecular polarizability ( α), of which r 2=0.988, SD=0.134. Meanwhile, it was found that there was significant correlation between the Cl substitution positions and some structural parameters. Consequently, the numbers of Cl substitution positions were also taken as theoretical descriptors to establish the second novel QSPR model (II) for predicting P L of all PCDE congeners, of which r 2=0.991, SD=0.112. In addition, the t-values of two models are both large and the variation inflation factors (VIF) of variables herein are all less than 5.0, suggesting significant statistics of the P L predicting models. And the results of cross-validation test also showed that the second model exhibited optimum stability and better predictive power. Moreover, results of prediction were further compared with data from similar studies by semi-empirical PM3 method, molecular connectivity indices (MCIs) method and molecular descriptors method.

Mobility of Chloroaromatic Compounds in Soil: Case Studies of Swedish Chlorophenol-contaminated Sawmill Sites

This paper summarizes recent studies on the environmental fate of chloroaromatic compounds in chlorophenol (CP)-contaminated soil and groundwater at Swedish sawmill sites. Relative proportions of CPs, polychlorinated phenoxy phenols (PCPPs), polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins (PCDDs), and polychlorinated dibenzofurans (PCDFs) were determined in preservatives, particulate organic matter (POM), dissolved organic matter (DOM), groundwater, and particles filtered from groundwater. All compound classes were found in the different compartments. The fraction of PCPPs, PCDEs, PCDDs, and PCDFs had increased in the soil samples relative to the proportions in the preservatives. This increase showed correlation with the hydrophobicity, that is, PCDDs had the largest increase. Similar correlation was found between hydrophobicity and the importance of partitioning to POM over DOM. The more water soluble compound group, CP, was found equally distributed between POM and DOM. For PCPPs, PCDEs, PCDDs, and PCDFs, the relative partitioning to POM increased with increased hydrophobicity. Despite the relative partitioning towards POM, compared with DOM, cotransport with DOM and suspended colloidal fractions was found to substantially increase the transport of these compounds in the groundwater samples.

QSPR study of polychlorinated diphenyl ethers by molecular electronegativity distance vector (MEDV-4)

Polychlorinated diphenyl ethers (PCDEs) have received more and more concerns as a group of ubiquitous potential persistent organic pollutants (POPs). By using molecular electronegativity distance vector (MEDV-4), multiple linear regression (MLR) models are developed for sub-cooled liquid vapor pressures ( P L), n-octanol/water partition coefficients ( K OW) and sub-cooled liquid water solubilities ( S W,L) of 209 PCDEs and diphenyl ether. The correlation coefficients ( R) and the leave-one-out cross-validation (LOO) correlation coefficients ( R CV) of all the 6-descriptor models for log P L, log K OW and log S W,L are more than 0.98. By using stepwise multiple regression (SMR), the descriptors are selected and the resulting models are 5-descriptor model for log P L, 4-descriptor model for log K OW, and 6-descriptor model for log S W,L, respectively. All these models exhibit excellent estimate capabilities for internal sample set and good predictive capabilities for external samples set. The consistency between observed and estimated/predicted values for log P L is the best ( R = 0.996, R CV = 0.996), followed by log K OW ( R = 0.992, R CV = 0.992) and log S W,L ( R = 0.983, R CV = 0.980). By using MEDV-4 descriptors, the QSPR models can be used for prediction and the model predictions can hence extend the current database of experimental values.

Benefits and risks of fish consumption: Part I. A quantitative analysis of the intake of omega-3 fatty acids and chemical contaminants

In recent years, and based on the importance of fish as a part of a healthy diet, there has been a notable promotion of fish consumption. However, the balance between health benefits and risks, due to the intake of chemical contaminants, is not well characterized. In the present study, edible samples of 14 marine species were analyzed for the concentrations of omega-3 fatty acids, as well as a number of metals and organic pollutants. Daily intakes were specifically determined for a standard adult of 70 kg, and compared with the tolerable/admissible intakes of the pollutants, if available. Salmon, mackerel, and red mullet were the species showing the highest content of omega-3 fatty acids. The daily intakes of cadmium, lead, and mercury through fish consumption were 1.1, 2.0, and 9.9 μg, respectively. Dioxins and furans plus dioxin-like polychlorinated biphenyls (PCBs) intake was 38.0 pg WHO-TEQ/day, whereas those of polybrominated diphenyl ethers (PBDEs), polychlorinated diphenyl ethers (PCDEs), polychlorinated naphthalenes (PCNs) and hexachlorobenzene (HCB) were 20.8, 39.4, 1.53, and 1.50 ng/day, respectively. In turn, the total intake of 16 analyzed polycyclic aromatic hydrocarbons (PAHs) was 268 ng/day. The monthly fish consumption limits for human health endpoints based on the intake of these chemical contaminants were calculated for a 70 years exposure. In general terms, most marine species here analyzed should not mean adverse health effects for the consumers. However, the type of fish, the frequency of consumption, and the meal size are essential issues for the balance of the health benefits and risks of regular fish consumption.

Partitioning of CPs, PCDEs, and PCDD/Fs between Particulate and Experimentally Enhanced Dissolved Natural Organic Matter in a Contaminated Soil

We determined the distribution of hydrophobic organic contaminants (HOCs) to fractions of natural organic matter in a soil contaminated by chlorophenol wood preservatives more than 30 years ago. The concentration of dissolved organic matter (DOM) was enhanced in soil suspensions by raising pH to 6.8-9.1. After 48 h of desorption/equilibration, the DOM fraction was separated from the particulate organic matter (POM) of the soil by filtration. In the next step, DOM was flocculated by Al-nitrate, and free concentrations of HOCs were determined in the aqueous phase. The HOCs associated with DOM and POM were extracted with toluene. No significant differences in gross carbon chemistry were detected between DOM and POM, using X-ray photoelectron spectroscopy (XPS). Normalized to organic C, chlorophenols (CPs) showed a similar degree of partitioning between DOM and POM, whereas the partitioning of polychlorinated diphenyl ethers (PCDEs), polychlorinated dibenzo-p-dioxins, and furans (PCDD/Fs) was highly shifted toward POM. The partitioning to POM, relative to DOM, increased in the order PCDE < PCDF < PCDD, reflecting the hydrophobicity of the compounds.

Health risks of dietary intake of environmental pollutants by elite sportsmen and sportswomen

The dietary intake of arsenic (As), cadmium (Cd), mercury (Hg), lead (Pb), hexachlorobenzene (HCB), polychlorinated naphthalenes (PCNs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated diphenyl ethers (PCDEs), polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), and polychlorinated dibenzo- p-dioxins and dibenzofurans (PCDD/Fs) by elite sportsmen and sportswomen of Catalonia, Spain, was assessed. In 2000, food samples were randomly acquired in various cities of Catalonia. Analysis of the above pollutants were determined according to the appropriate analytical techniques (ICP-MS, HRGC/HRMS, HPLC). In general terms, elite sportsmen and sportswomen showed a higher intake of Cd, Hg, Pb, HCB, PCNs, PCDD/Fs and PAHs than the general population, while it was lower for PCDEs (both sexes), and PCBs and PBDEs (women). According to the FAO/WHO provisional tolerable weekly intake (PTWI) for metals, the WHO tolerable daily intake (TDI) for HCB, and the US EPA’s reference dose (RfD) for PAHs, the dietary intakes of environmental pollutants should not mean a potential toxic hazard. However, the WHO-TDI for PCDD/Fs and “dioxin-like” PCBs is exceeded in sportsmen. The current results indicate that the consumption of those food groups showing the highest contribution to the intake of these pollutants should be diminished. In relation to this, the reduction of the consumption of dairy products and cereals would be important.

Formation of toxic chemicals including dioxin-related compounds by combustion from a small home waste incinerator

We investigated combustion in a small home waste incinerator and analyzed both flue gas and residual ash for formation of the dioxin-related compounds polychlorinated dibenzo- p-dioxins, polychlorinated dibenzofurans, and coplanar polychlorinated biphenyls and their precursors polychlorinated benzenes, polychlorinated phenols, polychlorinated diphenyl ethers, and polychlorinated biphenyls. Particularly, we investigated the effect of the incinerated material’s composition on both the congener ratios of released compounds and the total concentration of all congeners of each compound. Eight different samples were prepared for incineration with four samples consist entirely paper, dead leaves, natural wood, or building materials. The remaining four samples contained mostly paper, but also other components such as fiber, non-chlorine-containing plastics, chlorine-containing plastics, and copper electric wire. The presence of non-chlorine-containing plastic in combustion samples did not increase overall dioxin or dioxin-precursor emissions. In contrast, chlorine-containing plastic resulted in a several-fold increase in total polychlorinated dioxins released, in both flue gas and residual ash. Copper wire resulted in a further several-fold increase in total polychlorinated dioxins and dioxin precursors released, with one exception: the addition of chlorine-containing plastic resulted in a many-fold increase in polychlorinated biphenyls, but only a modest further increase (∼52%) with the further addition of copper. Homologue ratios tended toward higher-chlorine compounds as chlorine-containing plastic and Cu were added, but the results were far from uniform. Our results show that toxic dioxin release from small home waste incinerators must be considered significant, especially if even small amounts of chlorine-containing plastics or copper are burned.

Human exposure to polychlorinated diphenyl ethers through the diet in Catalonia, Spain.

Although polychlorinated diphenyl ethers (PCDEs) are recognized environmental pollutants, information concerning human exposure to these organic substances is very scarce. For the present study the concentrations of PCDEs in a number of foodstuffs acquired in Catalonia, Spain, were determined. The dietary intake of PCDEs was estimated for various age groups of the general population living in this Spanish region. With the exception of fish and shellfish, PCDE concentrations were under the limit of detection in the 10 remaining food groups analyzed. For an adult (20-65 years old) male of 70 kg average body weight, the estimated total dietary intake of PCDEs was 41 ng/day. It was assumed that if a PCDE congener was below the detection limit, the concentration was equal to half of the limit of detection. The highest exposure to PCDEs through the diet corresponded to the group aged 51-65 years, whereas the lowest intake corresponded to the youngest group (4-9 years). With the exception of the group aged >65 years, PCDE intake was always higher in males than in females. The results of this study should be of interest for future assessments of time trends in human exposure to PCDEs through the diet.

Bioavailability of sediment-associated PCDD/Fs and PCDEs: relative importance of contaminant and sediment characteristics and biological factors.

Factors that determine accumulation of sediment-associated polychlorinated dibenzo-p-dioxins and furans and polychlorinated diphenyl ethers into semipermeable membrane devices (SPMDs) and benthic oligochaete worms (Lumbriculus variegatus) were examined. These factors included both physical-chemical and structural characteristics of the contaminants (water solubility, lipophilicity, dipole moment, molecular size, and conformation) and sediment characteristics (organic carbon content, particle size, aromaticity, and polarity of organic carbon). The results of partial least squares regression analysis indicated that lipophilicity alone is not a sufficient predictor for contaminant bioaccumulation potential, even though it is a significant contributor. It was shown that contaminant molecular size and conformation (specifically planarity/nonplanarity) as well as sediment characteristics also have a significant role. The studied factors contributed up to 63-88% of the variation in accumulation data for SPMDs and 50-65% for oligochaetes. Comparison of (bio)accumulation factors (BAF28d for oligochaetes and AF28d for SPMDs) revealed that accumulation of contaminants in oligochaetes is largely influenced by biological factors (e.g., feeding habits), while the physical-chemical nature of the process is emphasized for SPMDs.

Modeling the transport of PCDD/F compounds in a contaminated river and the possible influence of restoration dredging on calculated fluxes.

River Kymijoki, the fourth largest river in Finland, has been heavily polluted by pulp mill effluents as well as by chemical industry. Loading has been reduced considerably, although remains of past emissions still exist in river sediments. The sediments are highly contaminated with polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), polychlorinated diphenyl ethers (PCDEs), and mercury originating from production of the chlorophenolic wood preservative (Ky-5) and other sources. The objective of this study was to simulate the transport of these PCDD/F compounds with a one-dimensional flow and transport model and to assess the impact of restoration dredging. Using the estimated trend in PCDD/F loading, downstream concentrations were calculated until 2020. If contaminated sediments are removed by dredging, the temporary increase of PCDD/F concentrations in downstream water and surface sediments will be within acceptable limits. Long-term predictions indicated only a minor decrease in surface sediment concentrations but a major decrease if the most contaminated sediments close to the emission source were removed. A more detailed assessment of the effects is suggested.