Determination of phenolic organohalogens in human serum from a Belgian population and assessment of parameters affecting the human contamination.

Many in vitro or in vivo studies highlighted the potential deleterious effects of phenolic organohalogenated compounds (POHs) on the health, particularly on the thyroid system homeostasis, however few large scale human epidemiological studies have been carried out, especially in Europe. Further studies monitoring the human contamination by POHs, the sources of exposure and the influence of these compounds on thyroid health are still needed. Therefore we determined the concentrations of 16 POHs (pentachlorophenol (PCP), tetrabromobisphenol A (TBBPA), 4 bromophenols (BPs), 3 hydroxy-polybromodiphenylethers (OH-PBDEs) and 7 hydroxy-polychlorobiphenyls (OH-PCBs)) in serum from 274 people aged from 18 to 76years old living in Liege (Belgium) and the surrounding area. A questionnaire about their alimentary habits, life style and home environment was also administered to the volunteers. The predominant compound measured in the population was PCP (median concentration of 593.0pgmL-1). 4-OH-CB 107, 4-OH-CB 146 and 4-OH-CB 187 were detected in all samples and contributed for 75% of the sum of OH-PCBs (ΣOH-PCBs). The median measured in our population for ΣOH-PCBs was 143.7pgmL-1. TBBPA and 2,4,6-tribromophenol were detected in 31% and 63.8% of the samples respectively while the detection frequency observed for the other BPs and the OH-PBDEs was close to zero. We computed multivariate regression models in order to assess the influence of demographic and lifestyle parameters on the PCP and ΣOH-PCBs contamination levels. Significant correlation was found between the PCP concentration and sex, smoker status, sea fish consumption and level of education, although the model seemed to be a poor (R2=0.14) predictor of the PCP concentration. The model computed for ΣOH-PCBs was more explanatory (R2=0.61) and involved age, BMI and sea fish consumption. Finally, we assessed the parameters affecting the ΣOH-PCBs/ΣPCBs ratio. The model proposed involved age, BMI, smoker status and parent PCB level, and explained 41% of the variability of the ΣOH-PCBs/ΣPCBs ratio.

Validation of a novel and rapid method for the simultaneous determination of some phenolic organohalogens in human serum by GC-MS.

Over the last decades, more and more studies focused on the impact of endocrine disruptors on the environment and human health. Among them, phenolic organohalogens (POHs) are a particular concern because of their structural resemblance with natural hormones. There are different methods that are known to quantify these compounds in human serum, however, the current extraction techniques are long, fastidious and using harmfull chemicals such as diazomethane and sulfuric acid. Consequently, we developed an alternative, sensitive and faster method to simultaneously quantify pentachlorophenol (PCP), tetrabromobisphenol A (TBBPA), 4 bromophenols, 7 hydroxypolychlorinated biphenyls (OH-PCBs) and 3 hydroxy-polybrominated diphenyl ether (OH-PBDEs) in human serum sample. The clean-up and the enrichment of the sample were performed in a single extraction step using strong anion-exchange solid phase cartridge. After a rapid liquid-liquid extraction step to remove acidic traces, the extract was derivatized using trimethylsilyldiazomethane (TMSD) and finally analyzed by a gas-chromatograph coupled with an electron negative capture chemical ionization source combined with a triple quadrupole mass spectrometer (GC-ENCI-MS) operating in single ion monitoring. The whole procedure was validated according to the total error approach. The inter and intra assay precision were demonstrated to be lower than 20% and the relative bias to be lower than 15% in the dosing range of concentrations. The limit of quantification (LOQ) ranged from 2pgmL-1 and 5pgmL-1, except for the PCP (44.6pgmL-1) and for the 2,4,6-tribromophenol (49.6pgmL-1). Finally, the method was successfully applied to measure the POH background contamination in serum samples collected from 20 Belgian blood donors recruited in CHU Mont-Godinne (Namur, Belgium) aged between 21 and 69 years old.

Bioaccumulation of hydroxylated polychlorinated biphenyls and pentachlorophenol in the serum of northern elephant seal pups (Mirounga angustirostris).

Northern elephant seals (NES) (Mirounga angustirostris) from the Año Nuevo State Reserve (CA, USA) were sampled at 1-, 4-, 7- and 10-week post-weaning. Concentrations of hydroxylated polychlorinated biphenyls (HO-PCBs) and their parent PCBs were measured in the serum of each individual. The ΣHO-PCB concentrations in the serum increased significantly between early and late fast (from 282 ± 20 to 529 ± 31 pg/mL). This increase might result from a mobilisation of HO-PCBs transferred from the mother during gestation and/or lactation and stored in the pup's liver. Food deprivation has been shown to exacerbate biotransformation capacities in mammals, birds and fish. The HO-penta-CBs was the predominant homologue group, followed by HO-hexa-CBs and HO-hepta-CBs. No preferential pathway for the metabolism of HO-PCBs (HO-direct insertion or NIH-shift of a chlorine atom) could be evidenced. The concentrations of pentachlorophenol (PCP) in the serum of weaned NES increased from 103 ± 7 pg/mL at early fast to 246 ± 41 pg/mL at late fast, which is within the range of PCP concentrations usually encountered in marine mammals.

Temporal trend and age-dependent serum concentration of phenolic organohalogen contaminants in Japanese men during 1989-2010.

The temporal trend in serum concentrations of phenolic organohalogen contaminants (POCs) were investigated in two age groups of men from Kyoto, Japan, from 1989 to 2010. These concentrations and trends were compared with neutral contaminants including polychlorinated biphenyls (PCBs) and pesticides. Serum concentrations of pentachlorophenol (PenCP) and 4-hydroxy-PCB187 were age-dependent and decreased to approximately one-half during the two decades, whereas no contamination trends were observed for 2,4,6-tribromophenol (TriBP), tetrabromobisphenol A (TBBPA) and 6-hydroxy-2,2',4,4'-tetrabromodiphenyl ether (6-OH-BDE47). 6-OH-BDE47 was found in all samples (up to 3000 pg/g wet weight), whereas TBBPA was detected in 17 of 60 serum samples (up to 950 pg/g wet weight). The concentrations of TriBP, TBBPA and 6-OH-BDE47 were not correlated to those of PenCP or 4-OH-PCB187 in either age group, suggesting the different kinetics on exposure routes and fate between these brominated and chlorinated POCs.

Biochemical study of retired pentachlorophenol workers with and without following dietary exposure to PCDD/Fs.

PCDD/Fs are found as impurities in commercial pesticide sodium pentachlorophenol (Na-PCP) salt. We compared, using multivariate logistic regression analysis adjusted for confounding factors, serum PCDD/F levels and biochemical examinations of retired Na-PCP workers and other inhabitants living near a closed Na-PCP plant that discharged PCP-contaminated wastewater into a nearby pond in Tainan, Taiwan. In this cross-sectional study from October 2006 through May 2009, 1167 participants were divided into groups according to their occupational (retired Na-PCP plant workers versus other residents) and dietary exposure (eating polluted fish versus not eating polluted fish) to PCDD/Fs, and a general population from a large-scale survey. Serum PCDD/F levels were significantly different between these groups (range: from 22.9±10.0pg WHO(98)-TEQ(DF) g(-1) lipid in the general population to 109.6±94.5pg WHO(98)-TEQ(DF) g(-1) lipid in retired Na-PCP workers eating polluted seafood; P(trend)<0.001). Distinct patterns of PCDD/Fs congener profiles, showing a significantly higher proportion of 1,2,3,7,8-PeCDD, 1,2,3,6,7,8-HxDD, and less 2,3,4,6,7,8-HpCDF, OCDF, were also found among workers and residents with different serum PCDD/F levels versus the general population. After adjusting for confounding factors, glucose (adjusted odds ratio [AOR] 7.22 [95% CI: 4.04-12.90]), triglycerides (AOR 4.31 [95% CI: 2.57-7.22]), blood urea nitrogen (AOR 2.90 [95% CI: 1.58-5.33]), creatine (AOR 5.83 [95% CI: 1.12-30.30]) and total protein (AOR 3.74 [95% CI: 1.91-7.31]) levels in retired workers were significantly higher than in the reference group. Occupational exposure to PCDD/Fs is associated with biochemical abnormalities that may persist for years after serum PCDD/F levels have declined.

Predictors of PCP, OH-PCBs, PCBs and chlorinated pesticides in a general female Norwegian population.

The aims of the current study were to assess plasma concentrations and predictors of halogenated phenolic compounds (HPCs), polychlorinated biphenyls (PCBs) and chlorinated pesticides in a representative group of postmenopausal Norwegian women (n=311, mean age: 56 years). In addition to delivering a blood sample, the participants had also filled out a detailed questionnaire regarding their current health status, use of medication and dietary habits, etc. The association between a large number of dietary variables, lifestyle factors and plasma concentration of organic pollutants were investigated using multivariate statistics. Within the current study group, p,p'-DDE (median: 903 ng/L w.w.) and pentachlorophenol (PCP, median: 711 ng/L w.w.) were the dominating compounds on a wet weight basis and were present in considerable higher concentrations than the PCBs, the hydroxylated PCBs (OH-PCBs) and the remaining chlorinated pesticides. Of the PCBs, PCB 153 was detected in highest concentrations, whereas 4-OH-PCB187 was present in highest concentration of the selected OH-PCBs. The ratio of ΣOH-PCB to ΣPCB varied between 0.06 and 0.77 ng/L and were significantly lower in individuals with higher ΣPCB concentration. PCP did not co-vary with the other contaminants, indicating a different route of exposure. No clear food cluster was positively associated with PCP exposure; however intake of marine food was negatively linked to PCP concentration and age and being a non-smoker were positive predictors of PCP. The other investigated contaminants co-varied and were positively associated with age, plasma concentrations of marine derived omega-3 fatty acids and a traditional Norwegian fish and bread based diet. The difference in contaminant concentration between high, medium and low consumers of total marine food were however marginal for the dominating PCBs and chlorinated pesticides. The current results indicate however that marine food in itself could be a source of some of the OH-PCBs, regardless of their PCB precursors. As PCP is one of the dominating organic contaminants within the general female Norwegian population, future research on human concentrations, exposure routes and potential health effects of PCP is encouraged. Continued monitoring of human OH-PCB levels should also be performed as they could be present at levels almost as high as the PCBs and they are expected to be more toxic than their mother substances.

Global trends and diversity in pentachlorophenol levels in the environment and in humans: a meta-analysis.

Pentachlorophenol (PCP) was banned or restricted in many countries worldwide because of its adverse effects on the ecological environment and humans. However, the endocrine disrupting effects caused by low environmental PCP exposure levels has warranted more analysis. We reviewed 80 studies conducted in 21 countries and published between 1967 and 2010, using meta-regression analysis to examine the time trends and regional differences in PCP levels. The results suggested that in indoor air, bodies of water, freshwater sediments in western countries, invertebrates and freshwater vertebrates, PCP levels had declined over time, with half-lives ranging from 2.0 years to 11.1 years. However, in marine sediments/vertebrates and Chinese surface water/sediments, PCP levels increased over time. PCP levels in human blood and urine had decreased since the 1970s, with population half-lives of 3.6 years and 5.7 years, respectively. The intervals for global population blood and urine reference values decreased to 1.1-6.3 µg/L (2002-2008) and 2.5-7 µg/L (1995-2003), respectively. The possible thyroid disrupting effects and other health risks correlated with low environmental PCP exposure should be concerning. This study can help to ascertain the effects of the banning/restriction policy, providing data for cost-benefit analysis in policy-making and further control of health risks caused by low environmental exposure to PCP.

Changes in serum concentrations of polychlorinated biphenyls (PCBs), hydroxylated PCB metabolites and pentachlorophenol during pregnancy.

We studied pregnancy-related changes in serum concentrations of five polychlorinated biphenyls (PCBs, CB 118, CB 138, CB 153, CB 156, CB 180), three hydroxylated PCB metabolites (4-OH-CB107, 4-OH-CB146, 4-OH-CB187), and pentachlorophenol (PCP). Median serum lipid content increased 2-fold between early (weeks 9-13) and late pregnancy (weeks 35-36) (N=10), whereas median PCB levels in serum lipids decreased 20-46%, suggesting a dilution of PCB concentrations in serum lipids. Nevertheless, strong positive intra-individual correlations (Spearman's r=0.61-0.99) were seen for PCBs during the whole study period. Thus, if samples have been collected within the same relative narrow time window during pregnancy, PCB results from one single sampling occasion can be used in assessment of relative differences in body burdens during the whole pregnancy period. Concentrations of OH-PCBs in blood serum tended to decline as pregnancy progressed, although among some women the concentrations increased at the end of pregnancy. Positive intra-individual correlations (r=0.66-0.99) between OH-PCB concentrations were observed during the first and second trimester, whereas correlations with third trimester concentrations were more diverging (r=-0.70-0.85). No decline in PCP concentrations was observed during pregnancy and no significant correlations were found between concentrations at different sampling periods. Our results suggest that for both OH-PCBs and PCP, sampling has to be more specifically timed depending on the time period during pregnancy that is of interest. The differences in patterns of intra- and inter-individual variability of the studied compounds may be due to a combination of factors, including lipid solubility, persistence of the compounds, distribution in blood, metabolic formation, and pregnancy-related changes in body composition and physiological processes.

Pentachlorobenzene, hexachlorobenzene, and pentachlorophenol in children's serum from industrial and rural populations after restricted use.

The study of a population of 4-year-old children born between 1997 and 1999 in an urban area under strong inputs of pentachlorobenzene (PeCB) and hexachlorobenzene (HCB) suggested that the measured concentrations of pentachlorophenol (PCP) in serum may essentially result from metabolism of these chlorinated hydrocarbons. In contrast, examination of a rural population of children where the same compounds were present at relatively low levels points to other inputs besides transformation of PeCB and HCB being responsible for the measured PCP concentrations. In both populations, the results showed that a major proportion of the organochlorine compounds present in these children's serum at 4 years of age was incorporated during the lactation period.

Factors related to dioxin and furan body levels among Michigan workers.

We evaluated serum concentrations of five selected dioxin, furan, and polychlorinated biphenyls (PCB) congeners among 412 workers at a Midland, Michigan plant that manufactured trichlorophenol and pentachlorophenol (PCP) and formulated chlorophenol-based products. We examined occupational indicators of exposure to these chlorophenols taking into account intrinsic factors such as age and body fat and potential environmental sources of exposure from consumption of local game and fish and other occupations. All five congeners were significantly associated with age and body fat. 2378-TCDD serum concentrations were associated with trichlorophenol operations, total years employed at the plant, as well as working as a hazardous waste worker. 123678-H(6)CDD serum concentrations were related to occupational PCP exposure, chloracne, recent weight loss, eating local game, and working as a hazardous waste worker. Serum concentrations of PCB126 were related to smoking (inversely), and eating local fish or local game. Other factors such as diet and jobs outside of the chlorophenol plant exposures had only a very minor impact on dioxin and furan concentrations in these workers.

Development of a solid phase microextraction-gas chromatography-mass spectrometry method for the determination of pentachlorophenol in human plasma using experimental design.

A new method, headspace solid-phase microextraction (HS-SPME) with in situ derivatization and gas chromatography-mass spectrometry (GC-MS), which was used for the determination of trace amount of pentachlorophenol (PCP) in human plasma was presented. The acetylation derivatization reaction was firstly optimized using a Doehlert design. Then a series of parameters relevant to the headspace SPME procedure, including fiber coating, extraction temperature, extraction time and salt addition, were optimized using a two-level full factorial design expanded further to a central composite design. The validation of method showed that the optimized method had good linearity (R(2)=0.999) within the concentration ranges 0.1-50.0ngml(-1), and was sensitive with the limit of detection of 0.02ngml(-1). Intra- and inter-day precision for pentachlorophenol in human plasma samples were not greater than 11.9% and 12.6%, respectively. The proposed method, to our knowledge, describes the first application of HS-SPME with GC-MS for analysis of PCP in blood plasma sample. Application of the method to real human plasma samples, PCP was successfully detected in some cases at concentration levels 1.2-6.3ngml(-1).

Twenty years of the German Environmental Survey (GerES): human biomonitoring--temporal and spatial (West Germany/East Germany) differences in population exposure.

The German Environmental Surveys (GerESs) are nationwide population studies, which have repeatedly been carried out in Germany since the mid-1980s. The subjects were representatively selected from the regional registration offices with regard to age, gender and community size. The first survey for adults (GerES I) was carried out in 1985/1986 (West Germany) followed by GerES IIa in 1990/1991 (West Germany) and GerES IIb in 1991/1992 (East Germany). In GerES II children were also included to some extent. In 1998, the third GerES for adults was conducted in both parts of Germany (GerES III). The current survey 2003/2006 (GerES IV) is focussing exclusively on children. A 1-year pilot study was conducted in 2001-2002 to collect information on parameters influencing the response rate and to test the suitability of the different instruments intended to be used for the main study. The main goal of the surveys is to analyse and document the extent, distribution and determinants of exposure to environmental pollutants of the German general population. Three main instruments of investigation were comprised in GerES: human biomonitoring (HBM), monitoring of the domestic environment, and collecting information on exposure pathways and living conditions via questionnaires. This paper is focussed on the general design of the GerESs, the trend over time and spatial differences (West Germany and East Germany) for HBM data on arsenic, cadmium, lead, mercury, pentachlorophenol (PCP), and polycyclic aromatic hydrocarbons (PAH). These substances have been determined in blood and/or morning urine of adults and children. All GerESs have been conducted in close connection with the National Health Interview and Examination Surveys performed by the Robert Koch-Institute, Berlin.

Polychlorinated biphenyls and their hydroxylated metabolites (OH-PCBS) in pregnant women from eastern Slovakia.

OBJECTIVE: Our aim in the present study was to characterize and quantify the levels of polychlorinated biphenyls (PCBs) and specific polychlorobiphenylol (OH-PCB) metabolites in maternal sera from women delivering in eastern Slovakia. DESIGN: During 2002-2004, blood samples were collected from women delivering in two Slovak locations: Michalovce district, where PCBs were formerly manufactured, and Svidnik and Stropkov districts, about 70 km north. PARTICIPANTS: A total of 762 and 341 pregnant women were sampled from Michalovce and Svidnik/Stropkov, respectively, and OH-PCBs were measured in 131 and 31. EVALUATION/MEASUREMENTS: We analyzed PCBs using gas chromatography (GC)/electron capture detection. OH-PCBs and pentachlorophenol (PCP) were determined as methyl derivatives using GC-electron capture negative ionization/mass spectrometry. We characterized distributions in the full cohort using inverse sampling weights. RESULTS: The concentrations of both PCBs and OH-PCB metabolites of Michalovce mothers were about two times higher than those of the Svidnik/Stropkov mothers (p < 0.001). The median weighted maternal serum levels of the sum of PCBs (sigmaPCBs) were 5.73 ng/g wet weight (Michalovce) and 2.82 ng/g wet weight (Svidnik/Stropkov). The median sum of OH-PCBs (ZOH-PCBs) was 0.55 ng/g wet weight in Michalovce mothers and 0.32 ng/g wet weight in Svidnik/Stropkov mothers. 4-OH-2,2',3,4',5,5',6-Heptachlorobiphenyl (4-OH-CB187) was a primary metabolite, followed by 4-OH-2,2',3,4',5,5'-hexachlorobiphenyl (4-OH-CB146). Only four PCB congeners-CBs 153, 138, 180, and 170--had higher concentrations than 4-OH-CB187 and 4-OH-CB146 (p < 0.001). The median ratio of the sigmaOH-PCBs to the sigmaPCBs was 0.10. CONCLUSIONS: Mothers residing in eastern Slovakia are still highly exposed to PCBs, and their body burdens of these pollutants and OH-PCB metabolites may pose a risk for adverse effects on health for themselves and their children.

Residential and biological exposure assessment of chemicals from a wood treatment plant.

This paper evaluates the results of contamination of residents and residential homes located in close proximity to a Wood Treatment Plant. The plant has produced treated wood products continuously since 1904. The principle chemicals used to treat the wood, which is primarily used for railroad ties (oblong objects laid perpendicular to the rails to act as a base for the tracks), are creosote and pentachlorophenol. For a number of years, the plant burned treated waste wood products containing creosote and pentachlorophenol. First the plant pressure impregnates the wood with creosote and pentachlorophenol, and then the wood is stacked on open ground to allow it to air dry. Chemicals from recently treated wood ties are allowed to evaporate into the air or drip onto the ground surrounding the stacked wood. Small drainage ditches carry the liquid wastes into larger water channels where eventually the waste streams are discharged into a river adjacent to the plant. The river serves as a source of drinking water for the nearby community. Prevailing wind patterns favor a drift of air emissions from the plant's boiler stack over the nearby community and its residents. Over the past few years, the town's residents have become increasingly concerned about their health status and have voiced concerns regarding multiple health problems (including cancer), possibly associated with plant discharges. The intention of this study is to examine a representative sample of the potentially affected residents and to evaluate their residential environment for the presence of dioxin and/or its congeners. Data obtained from EPA's Toxic Release Information (TRI) database revealed the plant routinely discharged creosote, pentachlorophenol, dioxin and dioxin-like compounds into the ambient air via fugitive air emissions and surface waste waters. Sampling of household dust and water sediment within and outside of residences within a 2-mile radius of the plant revealed the presence of significantly elevated levels of dioxins, principally octachlorodibenzo-p-dioxin (OCDD) and 1,2,3,4,6,7,8-hepta-CDD. Biomonitoring of 29 subjects identified the presence of significantly elevated chlorinated dioxins and furan levels (OCDD=1049 ppt for exposed and 374 ppt for controls and 1,2,3,4,6,7,8-hepta CDD=132 ppt for exposed and 45.1 ppt for controls). These levels are consistent with exposures to pentachlorophenol in this group of subjects. And they confirm the presence of unsafe levels of chlorinated dioxins in these persons.

Determination of hydroxylated polychlorinated biphenyls (HO-PCBs) in blood plasma by high-performance liquid chromatography-electrospray ionization-tandem quadrupole mass spectrometry.

Hydroxylated metabolites of polychlorinated biphenyls (HO-PCBs) and pentachlorophenol (PCP) are halogenated phenolic compounds, and they are increasingly common as environmental contaminants mainly in the blood of wildlife and humans. A methodology based on high-performance liquid chromatography (reversed-phase)-electrospray (negative) ionization-tandem quadrupole mass spectrometry (LC-ESI(-)-MS-MS) in the select ion monitoring or multiple reaction monitoring modes was developed for HO-PCB and PCP determination in blood plasma and serum. Among 11 environmentally relevant HO-PCB congeners and PCP spiked to fetal calf serum, quantitative assessments, including matrix effects on ESI(-) suppression/ enhancement, showed process (recovery) efficiencies of 73% to 89% without internal standard (IS) correction, and 88% to 103% with IS correction, and method limits of quantification ranging from 1 to 50 pg/g (wet weight). Using the developed LC-ESI(-)-MS methodology in comparison with GC-MS and GC-ECD based approaches, similar results were found for HO-PCB identification and quantification in the plasma of polar bear (Ursus maritimus) from the Canadian arctic. LC-ESI(-)-MS identified four HO-PCB congeners [4'-HO-2,2',4,6,6'-pentachlorobiphenyl (4'-HO-CB104), 4-HO-2,3,3',4',5-pentachlorobiphenyl (4-HO-CB107), 4-HO-2,3,3',5,5',6-hexachlorobiphenyl (4-HO-CB165) and 3'-HO-2,2',3,4,4',5,5'-heptachlorobiphenyl (3'-HO-CB180)], and 14 additional tetra- to hepta-chlorinated HO-PCBs isomers in the polar bear plasma.

Concentrations of polybrominated diphenyl ethers, polychlonnated biphenyls, and polychlorobiphenylols in serum from pregnant Faroese women and their children 7 years later.

The objective of this study was to assess blood concentrations of polybrominated diphenyl ethers (PBDEs) and polychlorinated biphenyls (PCBs), and their polychlorobiphenylol (OH-PCB) metabolites in humans with a high seafood intake. Samples were obtained from pregnant women in the Faroe Islands in 1994-1995 and from their children at 7 years of age to examine maternal transfer of the compounds to their child, age-dependent metabolism, and temporal changes. Maternal serum was dominated by 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), while 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153) prevailed in the children's serum seven years later. DecaBDE was present in both mothers and children up to 3 and 6 ng/g lipid weight, respectively. The sigmaPCB concentration in the children averaged about 60% of the concentrations in their mothers, with median levels for both above 1 microg/g lipid weight and .with similar PCB congener patterns. sigmaOH-PCB serum concentrations from the mothers and their children showed ranges of 1.8-36 ng/g wet weight (ww) and 0.49-22 ng/g ww, respectively, with all OH-PCB congener concentrations being lower in the children, except for 2,3,3',4',5-pentachloro-4-biphenylol (4-OH-CB107). Children at 7 years of age are exposed to PCBs at levels only slightly below those of their mothers, and the increased 4-OH-CB107 concentrations in children could be due to age-related differences in PCB metabolism. The PBDE concentrations were similar in both mothers and their children. The main persistent organic pollutant concentrations in the children are most probably due to other environmental exposure than maternal transfer.

Current internal exposure to pesticides in children and adolescents in Germany: blood plasma levels of pentachlorophenol (PCP), lindane (gamma-HCH), and dichloro(diphenyl)ethylene (DDE), a biostable metabolite of dichloro(diphenyl)trichloroethane (DDT).

Pesticides are widely used throughout the world in agriculture to protect crops, and in public health to control diseases transmitted by animal vectors or intermediate hosts. After the prohibition of organochlorines such as DDT internal exposure of the general population to the organochlorines has been reduced markedly. Herein, current internal exposure of children and adolescents in an urban area in Germany to PCP, lindane, and DDT/E is reported. One hundred and thirty children and adolescents took part in this voluntary investigation. All of them stated they had never used pesticides in their homes or for medical reasons. Blood plasma was analysed for pentachlorophenol (PCP), lindane (gamma-HCH), and dichloro(diphenyl)ethylene (DDE), a biostable metabolite of dichloro(diphenyl)trichloroethane (DDT), using gas chromatography/electron capture detection according to well established methods approved by the Deutsche Forschungsgemeinschaft. Median (and 95th percentiles) in the age groups < 6, 6- < 12, and 12- < 18 years of age were (microgram/l): DDE: 0.75 (4.45), 0.95 (5.04), 0.89 (8.77); DDT: < 0.1 (0.22), < 0.1 (0.25), < 0.1 (0.30); PCP: 2.48 (17.32), 2.69 (5.85), 2.08 (8.04); lindane: < 0.1 (0.12, < 0.1 (0.08), < 0.1 (0.09). High levels of internal exposure to DDT in two girls were probably obtained during a holiday stay in India; high PCP-levels in two other girls were caused by a leather jacket impregnated with PCP, and a holiday abroad, respectively. Current background levels of internal exposure to organochlorine insecticides in children and adolescents in Germany are quantified. Exposure to these substances in the general population is thought to occur mainly via residues in food, which are low in general, today. In special cases, however, individual exposures may be dominated by other sources, i.e. impregnated leather clothes.

Exposure assessment of residents living near a wood treatment plant.

We report the results of environmental sampling and modeling in a neighborhood adjacent to a wood processing plant. This plant used creosote and pentachlorophenol (PCP) to treat wood for over 70 years. Between 1999 and 2001, environmental samples were obtained to quantify the level of environmental contamination from the wood processing plant. Blood from 10 residents was measured for chlorinated dioxins and dibenzofurans. Soil sediment samples from drainage ditches and attic/dust samples from nearby residents' homes were tested for polychlorinated dioxins, furans, and polycyclic aromatic hydrocarbons (PAH). The dioxin congeners analysis of the 10 residents revealed elevated valued for octachlorodibenzo-p-dioxin and heptachlorodibenzo-p-dioxin compatible with PCP as the source. The levels of carcinogenic PAHs were higher than background levels and were similar to soil contamination on wood preserving sites. Wipe sampling in the kitchens of 11 homes revealed that 20 of the 33 samples were positive for octachlorinated dioxins with a mean value of 10.27 ng/m2. The soil, ditch samples, and positive wipe samples from the homes indicate a possible ongoing route of exposure to the contaminants in the homes of these residents. Modeled air exposure estimated for the wood processing waste chemicals indicate some air exposure to combustion products. The estimated air levels for benzo(a)pyrene and tetrachlorodibenzodiozin in this neighborhood exceeded the recommended levels for these compounds in some states. The quantitative data presented suggest a significant contamination of a neighborhood by wood processing waste chemicals. These findings suggest the need for more stringent regulations on waste discharges from wood treatment plants.

Human prenatal and postnatal exposure to polybrominated diphenyl ethers, polychlorinated biphenyls, polychlorobiphenylols, and pentachlorophenol.

The aim of this study was to determine human prenatal and postnatal exposures to polybrominated diphenyl ethers (PBDEs), polychlorinated biphenyls (PCBs), hydroxylated metabolites of PCBs (polychlorobiphenylols; OH-PCBs), and pentachlorophenol (PCP). The median PBDE fresh-weight concentrations in maternal and cord blood plasma and in breast milk were 24, 4.3, and 75 pg/g, respectively. The PCB concentrations were approximately 60 times higher in each compartment (1,560, 277, and 4,310 pg/g, respectively). Calculated on a lipid weight basis, the levels were comparable in maternal blood plasma and breast milk. In contrast to PCBs, differences were found between PBDE congener distribution in maternal and cord blood plasma. The OH-PCBs constituted up to 26% of the PCB levels in maternal blood plasma and 53% in cord blood plasma, with levels of 120 and 88 pg/g fresh weight, respectively, and in breast milk 3 pg/g. The corresponding concentrations for PCP were 2,830, 1,960, and 20 pg/g. The ratios of PCB to OH-PCB were 13, 3, and 1,400 in maternal, cord plasma, and breast milk, respectively. It is evident that prenatal exposures occur for all the analytes. Moreover, the exposure continues after birth via breast milk. However, levels of OH-PCBs and PCP in breast milk are low compared with levels in blood plasma. Exposures to both PCBs and PBDEs, and in particular to the endocrine-active halogenated phenolic compounds, are of concern and implicate a potential risk for developmental disturbances.

Predictive value of human biomonitoring in environmental medicine: experiences at the outpatient unit of environmental medicine (UEM) of the University Hospital Aachen, Germany.

There is little data on the distribution of biomonitoring parameters in patients at outpatient Units of Environmental Medicine (UEM). We evaluated the biomonitoring parameters of 646 UEM outpatients from our University Hospital 1988-1998. Few patients were exposed to specific substances. Data of patients who were not obviously exposed was analysed statistically (geometric mean, standard deviation, median, 95th percentile). Results were compared with reference values in literature. Normal distribution of biomonitoring parameters was rare. 95th percentiles for arsenic, chromium, selenium, zinc, phenol and toluene were below standard, 95th percentiles for copper and mercury above, and 95th percentiles for lead, cadmium, pentachlorophenol, lindane, and beta-hexachlorocyclohexane were within the published range of reference values. Thallium as well as most volatile organic compounds analyzed were below detection levels. Aluminum and fluorine exposure was rarely analysed. In view of these results, it is concluded that the indication for biomonitoring needs to be stringent as levels of biomonitoring parameters are generally not risen in patients of the UEM.