PCDD/F and dioxin-like PCB in human blood and milk from German mothers

Blood samples of pregnant women aged between 19 and 42 years at the time they gave birth and milk samples from the same women following delivery were collected between September 2000 and January 2003 from 169 participants living in an industrialized area of Germany (Duisburg birth cohort study). All samples were analyzed for their content of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) as well as dioxin-like and indicator polychlorinated biphenyls (PCB). Levels of WHO-TEq were in the range of 4.34-97.3 pg/g(lipid base) (median: 26.37, arithmetic mean: 28.36) for blood, or 3.01-78.7 pg/g(lipid base) (median: 26.40, arithmetic mean: 27.27) for milk, respectively. The four congeners 12378-PeCDD, 23478-PeCDF, 33'44'5-PeCB (# 126) and 233'44'5-HxCB (# 156) contribute the main share to total WHO-TEq. The contribution of PCDD/F in relation to PCB to total WHO-TEq was 60:40% in blood and 52:48% in milk. Good correlations of the contaminant levels in lipid base between both matrices were found. The distribution between blood and milk depends on the molecular weight of the substances. Higher chlorinated PCDD/F- and PCB-congeners were found in 2-4-fold higher concentrations in blood in relation to milk and the concentrations of lower chlorinated PCB-congeners were up to 2-fold higher in milk in relation to blood. The body burden of PCDD/F and PCB increases with age and decreases over the total nursing period. Women who had lived outside highly industrialized countries showed lower concentrations of PCDD/F and PCB. In some cases, elevated levels of PCB were observed when the women had previously lived in Eastern Europe for a long time. In comparison with recent data, the decline in human PCDD/F and PCB levels observed during the nineties seems to have stopped. The individual exposures of the infants due to breastfeeding within the first 18 months were calculated to be from 4.4 to 318 ng WHO-TEq (median: 106, arithmetic mean: 118). The actual mean daily exposure of a breastfed infant can be estimated to 131 pg WHO-TEq/kg(body weight).     

Relationship of PCDD/F and Co-PCB concentrations in breast milk with infant birthweights in Tokyo, Japan

OBJECTIVE: To observe how PCDD/F and Co-PCB concentrations in breast milk relate to infant birthweights in Tokyo, Japan. STUDY DESIGN: Breast milk samples were collected from 240 mothers (aged 25-34years old) residing in Tokyo to measure the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs; 14 congeners), polychlorinated dibenzofurans (PCDFs; 15 congeners), and coplanar polychlorinated biphenyls (Co-PCBs; 12 congeners) in the breast milk fat. Individual milk samples (about 50ml) were obtained 30days after delivery, between the months of June and September in 1999 and 2000. The relationship of the infant birthweights with the PCDD/F and Co-PCB concentrations was observed. RESULTS: The birthweights were negatively correlated the concentrations of many of the PCDD/F and Co-PCB congeners, with the mean toxic equivalent quantities (TEQs) of the Co-PCBs, and with the sum of the PCDD, PCDF and Co-PCBs, although their correlation coefficients were less than 0.200. Multiple regression analysis showed octachlorodioxin was statistically significant explanatory variate. CONCLUSIONS: There were slight relationship between the dioxins levels of breast milk and the birthweights of the infants.     

PCDD/PCDF, dl-PCB and PBDE serum levels of Slovak general population

Blood serum specimens from 81 non-occupationally exposed adults residing in four areas close to municipal and waste incinerators as well as metallurgical industry plant and 44 adult subjects coming from control area of Slovakia were analysed for polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs). The concentration of total WHO(98)TEQ PCDD/F/dl-PCBs in whole group of donors from areas where known sources causing dioxin contamination are present was significantly higher than in control group of donors (p<0.001). Correlation between the age of donors and PCDD/F and dl-PCB levels was confirmed (Spearman's r(PCDD/Fs)=0.543, r(dl-PCBs)=0.521, p<0.001). Furthermore, this study presents first results concerning the PBDE congeners in human serum of Slovak general population. The total concentration (congeners 28, 47, 99, 100, 153, 154, 183) in control group was approximately 1.5-times higher in comparison to that of residents coming from areas with supposed environmental pollution. The most abundant congeners in all samples were BDE-47 and BDE-153 with median values of 0.24 ng g(-1) lipid and 0.23ngg(-1) lipid, respectively. The positive association between PBDE values and age of donors was not found.     

Temporal and local trends of PCDD/F levels in cow's milk in Switzerland

Levels of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) were determined in 30 Swiss cow's milk samples collected at dairy farms in the vicinity to point sources, in rural/alpine areas distant to known sources, and from tanks in large industrial milk processing plants. The contaminant concentrations in samples collected in 2001 were compared to data from analyses conducted in 1984 and 1990/1991 at the same sites. In 2001, the PCDD/F levels in milk from farms near point sources (0.63+/-0.26 ng I-TEQ/kg milk fat) are slightly but significantly higher in than milk from remote areas (0.36+/-0.09 ng I-TEQ/kg milk fat). Consumer milk collected at the processing plants had intermediary levels (0.51+/-0.19 ng I-TEQ/kg milk fat). However, milk in 2001 was significantly less contaminated than the samples collected in 1990/1991 and 1984. This trend is particularly pronounced near point sources but is also apparent in consumer milk and milk from remote areas. No geographical gradient in the atmospheric input of PCDD/F in Switzerland was found. The reduction in PCDD/F levels in dairy milk is paralleled by and correlated to the remediation of known PCDD/F emitting industries, as enforced by federal authorities.     

A study of the influence of sewage sludge fertilization on the concentrations of PCDD/F and PCB in soil and milk

The influence of the agricultural use of sewage sludge on the concentrations of PCBs and PCDD/Fs in soil, feed and milk was investigated on four dairy farms. Evidence of contaminant accumulation in the soil was found on both farms that fertilized with sewage sludge. The concentrations in feed and milk from one of these farms were similar to the concentrations in the matched control, while the concentrations in the samples from the second sludge user were elevated. The study demonstrates that the agricultural use of sewage sludge does under some conditions lead to higher levels of PCBs and PCDD/Fs in food products.     

PCDD, PCDF, AND PCB concentrations in human milk from two areas in Finland

Concentrations of 17 toxic 2,3,7,8-chlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) and of 36 polychlorinated biphenyl congeners (PCBs) were analyzed from 167 randomly sampled human milk samples from Southern (77 samples) and Eastern (90) Finland. The level of PCDD/Fs and PCBs in human milk in Southern Finland was about 25% higher than those from Eastern Finland. The level of PCDD/Fs in human milk in Finland was the same as in Sweden, 30–50 % lower than in milk from Central Europe but about 45% higher than values from Norway or Russia. The PCB concentrations in Southern Finland were at the same level as in the Netherlands, and in Eastern Finland at the same level as in Norway. The levels of PCDD/Fs and PCBs decreased with increasing number of children: the third child was exposed to about 70% of the amount of PCDD/Fs and PCBs as compared with the first child, and the eighth to tenth child to about 20%. The congener patterns of PCDD/Fs and PCBs in Finnish human milk were similar to the countries of Central Europe, however, the levels of penta- and heptachlorinated furans were slightly higher than in milk from other countries.     

Using PCDD/F congener patterns to determine the source of elevated TEQ concentrations in cows milk: a case study

PCDD/F congener profiles have been used to determine the source of elevated TEQ concentrations in cows' milk collected in the vicinity of several industrial sites. Principal components analysis and modelling of the air-to-milk transfer of individual PCDD/F congeners have shown that the milk fingerprint was related to that of sediment taken from the River Rother adjacent to the farm where the cows had grazed. It is suggested that sediment from the river had been washed onto the grazing land during periods of flooding, and this had been ingested by the grazing cows. This pathway could represent an important route of contaminant intake for livestock grazing on the regularly inundated floodplains of rivers containing contaminated sediments.     

The PCDD/F and PBDD/F pollution in the ambient atmosphere of Shanghai, China

Rapid economic growth in the last two decades in Shanghai has had a great adverse influence on its air quality. Therefore, the atmospheric pollutants of Shanghai have received much concern. In this study, concentrations of 2,3,7,8-substituted PCDD/Fs and PBDD/Fs congeners were measured in the ambient air of four districts in Shanghai. The mean atmospheric concentrations (TEQs) of total 2,3,7,8-PCDD/Fs and 2,3,7,8-PBDD/Fs were 8031 fg m(-3) (497.1 fg I-TEQ m(-3)) and 1358 fg m(-3) (304.1 fg I-TEQ m(-3)) for Jiading District, 5308 fg m(-3) (289.0 fg I-TEQ m(-3)) and 709 fg m(-3) (146.9 fg I-TEQ m(-3)) for Zhabei District, 4014 fg m(-3) (144.4 fg I-TEQ m(-3)) and 1239 fg m(-3) (256.9 fg I-TEQ m(-3)) for Pudong District, 3348 fg m(-3) (143.2 fg I-TEQ m(-3)) and 699 fg m(-3) (148.4 fg I-TEQ m(-3)) for Huangpu District, respectively. Our results showed that almost all the PCDD/Fs and PBDD/Fs congeners were partitioned into the particulate phase except the lower chlorinated or brominated ones. The logarithm of the gas/particle partitioning coefficient K(p) has good linear correlation with that of the sub-cooled vapor pressure p(L). Concentrations of PCDD/Fs and PBDD/Fs were both positively correlated to elemental carbon in all districts except Pudong District, suggesting elemental carbon could be a good indicator for dioxins' air pollution. It is intensively suggested that more detailed and deeper studies about PBDD/Fs should be carried out due to their relatively high atmospheric concentrations in Shanghai.     

Levels and trends of PCDD/Fs and PCBs in human milk in Finland

Word Health Organization, WHO/EURO, has coordinated two rounds of follow-up studies on levels of PCDDs, PCDFs, and PCBs in human milk which were analyzed as two pooled samples from each participating country, one from urban and the other one from rural area. Finland has taken part to both of those studies and we are now reporting results of all the second round randomly sampled human milk samples (84 samples) from Southern (20) and Eastern (64) Finland. The levels of PCDD/Fs and PCBs in human milk in Southern Finland were considerably higher than in Eastern Finland. The level of PCDD/Fs in human milk in Southern Finland was the same as in the Central Europe but the level in Eastern Finland was similar to levels in Norway and eastern parts of Europe. The concentrations of PCDD/Fs and PCBs showed a significant decrease from 1987 to 1994. Declining of PCDD/Fs and PCBs was 36 and 49% in primiparae mothers' milk, respectively. This decrease in concentrations of PCDD/F and PCB was slightly greater in Eastern than in Southern Finland.     

Trends of PCDD/F and PCB concentrations and depositions in ambient air in Northwestern Germany

Time series of polychlorinated dioxins and furans (PCDD/F) and polychlorinated biphenyls (PCB) in ambient air of a large conurbation in North-Western Germany are presented and analyzed. The trend of PCDD/F concentrations, starting from as early as 1988, shows a pronounced decrease by at least one order of magnitude, demonstrating that the emission reductions were effective. The PCDD/F depositions also have decreased by a factor of 5 since 1992. However, both trends have leveled out since 2005. Time series of PCB concentrations and depositions starting in 1994 show only slight decreases for the concentrations and almost no decrease for the depositions. From the decay rates following first order kinetics, half-lives in the order of 5-15 years for the PCDD/F and 15-31 years for the sum of the six indicator PCB could be calculated, which are much longer than the half-lives estimated from their reactivity towards the OH radical. Apparently, small fresh emissions (PCDD/F), considerable secondary emissions and evaporation from contaminated soils slow down their decay in the atmosphere of big conurbations. Analyzing the decay rates of individual PCB congeners shows that the lower chlorinated and more volatile ones are removed faster than the higher chlorinated congeners, probably via gas phase reactions with the OH radical. It can be concluded from the present study that the input of PCDD/F and PCB into the food chain via the air path will continue for another one or two decades in big conurbations.     

Effect of urea on fly ash PCDD/F concentrations in different particle sizes

The effect of urea as an inhibitor for reducing polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) concentrations in flue gases was studied in a pilot scale plant, together with the effect on the particle size distribution of these compounds. Total PCDD/F concentrations decreased by a maximum of 74%, the decrease being greatest for the most highly (octa-) chlorinated isomers. The PCDD/F reduction affected all the particle size classes when an adequate amount of urea was used (1% of the fuel input), which indicates that inhibition, unlike formation, is independent of the fly ash particle size distribution.     

A design of two simple models to predict PCDD/F concentrations in vegetation and soils

The vegetation and soil levels of the 17 polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/F) toxic congeners were calculated by means of a vegetation and a soil model, respectively. Both models predicted the levels of the 17 PCDD/F congeners in quite good agreement with the observed results although the soil model was more accurate than the vegetation model. Four different pathways of contribution to the vegetation concentrations were taken into account: vapour-phase absorption, dry particle deposition, wet particle deposition and uptake by root. The most important pathway was the vapour-phase absorption and the less was the uptake by root. In the soils model four pathways were considered: background soil concentration, dry particle deposition, wet particle deposition and uptake by root. After the background concentration, the most important pathway was the wet deposition.     

Atmospheric concentrations of PCDD/Fs, dl-PCBs and some pesticides in northern Algeria using passive air sampling

Perfluorooctanesulfonate (PFOS) is the terminal degradation product of many commercially used perfluorinated compounds, and most of the toxicity testing to date has focused on its potential biological effects. While PFOS has been extensively studied, other PFCs including replacement chemicals such as perfluorobutanesulfonate (PFBS) and perfluorobutyric acid (PFBA), have not been well characterized. Despite the relative lack of data available on these other PFCs it has been assumed that they will cause similar or lesser effects than PFOS. This study compared the effects of 10 PFCs routinely found in the environment on mRNA abundance of 7 genes related to processes known to be affected by PFOS, such as fatty acid and cholesterol synthesis, and thyroid development. Rat H4IIE hepatoma cells were exposed and changes in mRNA abundance were quantified by real-time PCR. Significant changes in mRNA abundance were observed. The effects caused by the shorter chain replacement chemicals differed significantly from those caused by PFOS or PFOA. Furthermore, not all of the PFCs caused the same effects, and changes could not simply be attributed to chain-length or functional group. These differences could mean that these replacement chemicals do not act through the same mechanisms as the more studied PFOS and PFOA.     

Quantification of PCDD/F concentrations in animal manure and comparison of the effects of the application of cattle manure and sewage sludge to agricultural land on human exposure to PCDD/Fs

PCDD/Fs were quantified in samples of cattle, pig, sheep and chicken manure. TEQs ranged from 0.19 ng TEQ/kg dw for the pig manure to 20 ng TEQ/kg dw for one cattle manure sample. Exposure assessments were carried out to compare the effect of various sewage sludge and cattle manure land application scenarios on human PCDD/F exposure. Background exposure was estimated at 4.9 pg TEQ/kg bw/day and it was found that land application of sewage sludge and cattle manure at contemporary rates did not increase PCDD/F TEQ background exposure. It was concluded that the application of sewage sludge, under the new UK guidelines, and cattle manure to agricultural land, do not make a significant contribution to human exposure to PCDD/Fs.     

PCDD/F and metal concentrations in soil and herbage samples collected in the vicinity of a cement plant

Juvenoids are biologically active compounds, of relatively low toxicity to humans, that efficiently inhibit the fertility of insects. However, little attention has been paid to the stability and toxicity of products that may be generated by their biodegradation in the ecosystem. This study describes a simple comparison of the toxicity of the active compound and its degradation products generated by aerobic soil microbial isolates. Surprisingly we have found that toxicity of a biologically active carbamate juvenoid N-[2-[4-(2,2-ethylenedioxy-1-cyclohexylmethyl)-phenoxylethyl]carbamate (W328) was comparable with that of 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT). The toxic effect was evaluated using the determination of the ATP/ADP content and viability of HeLa S3 cells exposed to various concentrations of the chemicals tested for various durations. DDT was used as a reference compound. Its toxicity was compared with two juvenile hormone analogs. The original compound, W328, was found to be the most toxic. The major product (W329) generated both by yeast isolates and the mixture of moulds lost its activity on reproduction of the tested insect. Its toxicity towards human cells was also decreased. Another two W328 degradation HPLC fractions exhibited significantly reduced toxicity compared to W328.     

Comparison of PCDD/F and coplanar PCB concentrations in Japanese human adipose tissue collected in 1970-1971, 1994-1996 and 2000

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), dibenzofurans (PCDFs) and coplanar biphenyls (Co-PCBs) were determined in Japanese human adipose tissues. Temporal trends were assessed by comparing data collected during 1970-1971, 1994-1996 and 2000. Mean TEQ levels of PCDD/Fs in human adipose tissue showed a significant decrease from 31.6 +/- 9.2 pg-TEQ/g fat wt in 1970-1971 to 11.9 +/- 7.4 pg-TEQ/g fat wt in 2000, and coplanar PCBs decreased from 35.4 +/- 21.9 pg-TEQ/g fat wt in 1970-1971 to 15.3 +/- 8.2 pg-TEQ/g fat wt in 2000. However, some PCB congener concentrations did not change during this time. A comparison of data using the latest PCB-TEQ showed no significant changes. Therefore, research on source characterization and monitoring of short-term temporal trends on these compounds should be carried out continuously.     

PCDD/F concentrations in soil and vegetation in the vicinity of a municipal waste incinerator after a pronounced decrease in the emissions of PCDD/Fs from the facility

Emission of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) by municipal solid waste incinerators (MSWI) is an issue of great concern. In 1997, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an MSWI from Tarragona (Catalonia, Spain). As a result, PCDD/F emissions were significantly reduced. The aim of this study was to determine the current levels of PCDD/Fs in soil and vegetation samples collected near the facility and to compare these levels with those obtained in previous surveys (1996 and 1997). In the period 1997-1999, PCDD/F concentrations in vegetation samples were significantly decreased (60%). By contrast, the levels of PCDD/Fs in soil samples increased slightly (14%, P > 0.05) during the same period. An exhaustive analysis of the present data indicates that other emission sources of PCDD/Fs have also a notable environmental impact on the area under direct influence of the MSWI.     

Myeloperoxidase-catalyzed formation of PCDD/F from chlorophenols

Chlorophenols (CP) are transformed in vitro to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) by a biochemical-catalyzed oxidation. This is shown for 2,4,5-tri-, 2,3,4,6-tetra-and pentachlorophenol with myeloperoxidase recovered from human leucocytes in the presence of hydrogen peroxide. The yield, the reaction, and the PCDD/F-pattern found depend on the CP. The formation rates are in the micromol-per-mol range for all substrates. The experiments confirm the suspicion that a biochemical formation of PCDD/F from precursors such as CPs can take place in the human body and that this metabolic pathway may lead to a higher inner exposure with PCDD/F than is now assumed.     

PCDD/Fs and dioxin-like PCBs in human milk and estimation of infants' daily intake: a review

This paper reviews the recent scientific literature on PCDDs, PCDFs and dioxin-like PCBs in human milk. All the papers reporting levels of these contaminants in human breast milk published from January 2000 to January 2009 and available on the www.sciencedirect.com web site were identified and included. The aim was (1) to study levels of PCDDs, PCDFs and PCBs in human milk in mothers from different geographical areas and assess infant exposure to these contaminants; (2) to study the effect of variables such as the mother’s age, number of deliveries, dietary and smoking habits and her own nutrition in infancy, and the environment, on levels of the contaminants in breast milk; (3) to study time patterns, and (4) to identify data gaps.     

PCDD/F and PCB in spruce forests of the Alps

PCDD/F and PCB concentrations in remote mountainous spruce stands of the Central European Alps show strong geographic variation. Independent of the matrix (0.5 year old needles, humus or mineral soil), the highest pollutant levels were always found at the lateral zones of the mountain range. High levels coincided with strong precipitation, particularly along the northern margin of the study region. The most volatile PCB congener propagated farther into the colder, drier central Alps than the heavier species. Matrices with different accumulation history (needles and humus) repeatedly reflected different spatial immission patterns. Consistent with its much longer exposure, pollutant levels in humus exceeded those of needles by up to two orders of magnitude. Needle contamination varied with altitude but the vertical trends were highly variable between transsects and changed between years, too.