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.     

Status of the PCDD and PCDF contamination of commercial milk caused by milk cartons

Within the scope of this study, possible migration of polychlorinated dibenzodioxins and -furans (PCDDs/PCDFs) from cartons (produced using bleached cardboard) into cow's milk was investigated. Three different types of carton were examined. The milk samples were taken at different times of storage and analysed for PCDDs/PCDFs. In contrast to a similar study carried out in 1990, the I-TEQ-results of all cartons analysed may be considered very low. No significant migration of toxic (2,3,7,8-chlorine-substituted) PCDDs/PCDFs could be observed. This is due to the very low PCDD/PCDF concentrations in modern cardboards as a result of the elemental chlorine-free (ECF) bleaching processes used. As far as the milk samples are concerned, no influence of the cardboards (according to the I-TEQ data) could be ascertained. I-TEQ concentrations in milk did not noticeably change during storage times of three, six and eight days. The I-TEQ-data obtained for all milk samples was found to be in the range typical of background concentrations in cow's milk in Germany. Although 1,2,7,8-TCDF is not included in the calculation of the TEQ (no 2,3,7,8-chlorine-substitution), analysis of this congener in cardboard samples was also carried out as a matter of general interest for cardboard investigations and an indicator of pulp bleaching with free chlorine.     

A survey of PCDD and PCDF in French long-life half-skimmed drinking milk

A national survey was carried out in order to assess the concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) in long-life half-skimmed drinking milk produced and consumed in France. 151 Samples were collected from 33 dairy establishments selected for their production amounts following a random sampling scheme. 148 of the 151 results were finally used for statistical assessment. The mean concentration of 2,3,7,8-TCDD toxicity equivalent found is 0.65 pg/g of milk fat. This result is far below the threshold recommended by the European Union.     

Levels and possible sources of PCDD/PCDF in sediment and pike samples from Swedish lakes and rivers. (Part one)

One goal of the Swedish survey project is to discover possible sources of PCDD/F. Bottom sediment and pike were sampled at various sites near different types of industries along the coast line of two lakes and one river. The results show background levels of PCDD/F in some lakes which can only be explained by atmospheric input. In some lakes paper mill emissions of chlorinated PCDD/F give high levels of local contamination (≈1 ng/g IG) within short distances (<1 km) from the source. PCDD/F from paper mill effluents are transported long distances and traces can be detected over the entire lake area. The PCDD/F levels in pike are correlated with levels in the underlying sediment.     

PCDD/PCDF congener profiles in soil and herbage samples collected in the vicinity of a municipal waste incinerator before and after pronounced reductions of PCDD/PCDF emissions from the facility

Congener profiles are the fractional distribution of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) congeners in an environmental release, or in an environmental or biological sample. In 1999, an adaptation to the EU legislation on pollutant emissions from the stack was carried out in an old municipal solid waste incinerator (MSWI) from Montcada (Barcelona, Spain). The main goal of the present study was to determine if the environmental PCDD/F levels in the area under direct influence of the facility were mainly due to PCDD/F emissions from the plant. For this purpose, soil and herbage samples were collected near the MSWI before (1998) and after (2000) the technical improvements were performed. PCDD/F congener profiles were determined and compared with those from samples collected in a suburban area of Constantí (Tarragona, Spain) outside of direct emissions from any MSWI. The results of the present study suggest that the MSWI here assessed is not the main responsible for the environmental PCDD/F concentrations in the area under evaluation. Other PCDD/F emission sources in the same area seem also to have a notable impact on the atmospheric levels of these pollutants.     

Dioxins and furans in emissions from medical waste incinerators

Dioxins and furans were detected in emissions from eight medical waste incinerators tested in California. Total uncontrolled emissions ranged from 363 to 11, 811 nanograms per dry standard cubic meter. The most effective of three wet scrubbers achieved an emissions control efficiency of 95 percent for total PCDD and PCDF. A baghouse was less than 30 percent efficient in removing PCDD and PCDF from the incinerator emissions.     

Comparison of PCDD/PCDF levels in soil, grass, cow''s milk, human blood and spruce needles in an area of PCDD/PCDF contamination through emissions from a metal reclamation plant

When in the vicinity of a metal reclamation plant in Tyrol, Austria, increased PCDD/PCDF levels were found in soil and spruce needles, the extent of grass contamination as well as the PCDD/PCDF content in milk of cows fed with hay from this area was determined. The milk samples showed a significant increase in PCDD/PCDF levels compared to control samples. In a blood sample of a farmer a significant increase in PCDD/PCDF levels was found. Correlations in PCDD/PCDF levels between soil, spruce needles, grass, cow's milk and human blood will be presented.     

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.     

Comparative study of methodologies for the analysis of PCDDs and PDCFs in powdered full-fat milk. PCB, PCDD and PCDF levels in commercial samples from Spain

Feasibility of two different extraction methods involving solid-liquid extraction and Soxhlet extraction, previously used for the determination of lipid contents and PCB levels on powdered full-fat milk, are now examined for simultaneous PCDD/F analysis. The results of this study are consistent with those found for PCBs. The solid-liquid procedure provides the most efficient extraction of both labelled spiked and endogenous PCDD/Fs with the lowest variability. The average recoveries were 101% (R.S.D. = 6.9%) for 13C12-2,3,7,8-TCDD and 95% (R.S.D. = 11%) for 13C12-1,2,3,4,7,8-HxCDD. The R.S.D.s for endogenous 2,3,7,8-PCDD/Fs were in the 9.3-25% range. In addition, this methodology simplified the subsequent clean-up step as it allowed a semi-selective extraction of the apolar lipids from the milk. The proposed method was applied to simultaneous PCB and PCDD/F analyses in different brands of powdered full-fat milks commercially available in Spain. In all cases, very similar PCB and PCDD/F levels were found. Differences among batches from the same manufacturer were even lower. The total i-TEQ average for PCDDs and PCDFs in the 22 powdered full-fat milk samples analysed was 1.87 pg/g fat basis. This value was similar to those found in cow's milk from other European countries.     

Dioxins in human milk and smoking of mothers

BACKGROUND: The relation between the levels of dioxins in human breast milk and the smoking habits of the mothers is controversial. To clarify this relationship, we analyzed data from the human milk survey in Japan. METHODS: The human milk survey has been conducted in Japan since 1997. Healthy pregnant women aged 20-39 years were recruited and 50 ml of breast milk was collected from them at 30 days after delivery. PCDDs, PCDFs, and dioxin-like PCBs were measured by using GC/MS. The smoking habits of the mothers were established by interviewing them soon after delivery and were classified into four categories: current smokers, ever smokers who quit smoking at the pregnancy, ever smokers who quit smoking before the pregnancy, and never smokers. The levels of dioxins in breast milk were compared in the four categories of smoking among 853 primiparas. In addition, we analyzed the association between dioxin levels and passive smoking among never smokers. The geometric means of the dioxin concentrations were calculated in order to compare the differences between dioxins. RESULTS: The geometric means of dioxin-like PCBs in milk of never smokers was the highest (9.2 pg TEQ/g fat); followed by ever smokers who quit smoking before the pregnancy, ever smokers who quit smoking at the pregnancy, and current smokers (7.5, 7.2, and 6.6 pg TEQ/g fat, respectively). The differences between these levels were statistically significant (ANOVA, p<0.001). No significant difference was observed between the level of dioxins in milk from never smokers subjected to passive smoking status and those who had not experienced passive smoking. CONCLUSION: The levels of dioxin-like PCBs in human milk were negatively related to the smoking habits of mothers.     

Preliminary report: Dioxins and furans in prescribed burns

The Ontario Ministry of Environment (MOE) recently participated in a joint Canadian/U.S. program to monitor the behavior and environmental impact of prescribed fires. Air, soil and ash samples were collected at the burn sites and analyzed for chlorinated dibenzo-p-dioxins (CDD) and dibenzofurans (CDF). Preliminary results indicated that larger air sample volumes were required.     

Levels of dioxins, furans and PCBs in human serum and milk of people living in Greece

In an attempt to evaluate the background levels of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), non-ortho, mono-ortho and indicator polychlorinated biphenyls (PCBs) in people living in an urban (Athens) and a rural (Kozani) area of Greece, blood serum and mother milk samples were analyzed. Analytical results are reported in this study. Statistically significantly differences were observed between regions, sexes and ages. Contamination levels in blood and human milk from Greece reported here are low compared to the previously reported dioxin data from other European countries and give no indication of particular health risk.     

Database of PCDD/PCDF levels in ambient air and in samples related to the pulp and paper industry

A literature and questionnaire survey has been carried out in order that a database be developed for PCDD/PCDF levels in ambient air. The data received to date and entered into the database indicates that standardization in methodologies and reporting is required. The overall response to the survey, even with reminders, was disappointing.     

Emission and chlorination pattern of PCDD/PCDF predicted from indicator parameters

The emission and chlorination pattern of polychlorinated dioxins and dibenzofurans from waste combustion shows a close covariation with that of chlorinated benzenes and phenols. This covariation can be utilized to predict the emission levels of specific isomers as well as the pattern of congeners.     

Thermal behavior of PCDD/PCDF in fly ash from municipal incinerators

The effect of thermal treatment of fly ash on the behaviour of PCDD/PCDF was studied in the range between 120 and 600° C. Annealing at 300° C (2 hrs) resulted in an increase of PCDD/PCDF concentration by a factor of 10 to 15. At 600° C degradation to concentrations below 0.1 ng/g is observed.     

PCDD, PCDF, PCB and PBDE concentrations in breast milk of mothers residing in selected areas of Slovakia

The concentrations of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), dioxin-like polychlorinated biphenyls (dl-PCBs) and polybrominated diphenylethers (PBDEs) in 33 breast milk samples collected in 2006-2007 from primipara mothers close to four industrial areas of Slovak Republic were determined. The total PCDDs/PCDFs and dl-PCBs expressed as TEQ based on WHO TEFs 1998 in breast milk samples varied from 5.0 to 51.8 pg g⁻¹ fat (median: 13.1 pg g⁻¹ fat; mean: 18.0 pg g⁻¹ fat). The measurements of seven PBDE congeners (IUPAC No. 28, 47, 99, 100, 153, 154, and 183) were performed for the first time in human milk from Slovakia. PBDE levels ranged between 0.22 and 1.62 ng g⁻¹ fat, with median and mean value of 0.43 ng g⁻¹ fat and 0.57 ng g⁻¹ fat respectively. No statistically significant differences were observed between studied areas in total PBDE concentrations.Furthermore, this study presents first results concerning the daily intake (DI) of PCDDs/PCDFs and dioxin-like compounds for the most vulnerable breast-fed infant population in Slovakia. The total PCDD/PCDF and dl-PCB DI for an infant during the first 2 months of life was estimated in a range from 14.4 to 230 pg TEQ kg⁻¹ b.w., with a median value of 58.9 pg TEQ kg⁻¹ b.w.. The DI values substantially exceeded the tolerable daily intake (TDI) 1-4 pg TEQ kg⁻¹ b.w. recommended by WHO. The dietary infant intake concerning PBDEs was estimated to be between 0.69 and 7.1 ng kg⁻¹ b.w. d⁻¹, with median value of 1.7 ng kg⁻¹ b.w. d⁻¹.     

Environmental impact of a new hazardous waste incinerator in Catalonia,Spain: PCDD/PCDF levels in herbage samples

In April 1996 and 1998, the concentrations of polychlorinated dibenzo-p-dioxins (PCDD) and polychlorinated dibenzofurans (PCDF) were determined in 40 herbage samples collected in the neighborhood of a hazardous waste incinerator (HWI) under construction in Constanti (Catalonia, Spain). In April 2000, 20 months after the HWI began operating, herbage samples were again collected at the same sampling points in which samples had been taken in the previous surveys. PCDD/F concentrations ranged between 0.13 and 0.65 ng I-TEQ/kg (dry matter), with a median and mean values of 0.29 and 0.32 ng I-TEQ/kg (dry matter), respectively. The results were compared with those obtained in the 1996 (median, 0.53 ng I-TEQ/kg; mean, 0.61 ng I-TEQ/kg) and the 1998 (median, 0.23 ng I-TEQ/kg; mean, 0.31 ng I-TEQ/kg) surveys. While in the period 1996-1998 a significant decrease (49%, P < 0.001) in the mean PCDD/F levels was noted, in the period 1998-2000 an increase of 3% (P > 0.05) was found in the concentrations of PCDD/Fs. The analysis of the results suggests two potential hypotheses: either the emissions of PCDD/Fs from the HWI are not negligible, or the current PCDD/F emissions from other sources near the HWI remained at similar levels to those reached in 1998. Anyhow, an exhaustive evaluation of the present data shows an absence of notable PCDD/F contamination by the HWI in the area under its direct influence. It seems also probable that the decline in the atmospheric levels of PCDD/Fs due other emission sources of PCDD/Fs in this area is currently stopped.     

Thermally induced formation of PCDD and PCDF from tri- and tetrachlorobenzene in dielectric fluids

The thermal behavior of dilute (5000-50 ppm) solutions of tri- and tetrachlorobenzene in mineral oil, silicone oil, and tetrachloroethylene (TCE) has been investigated. Although pyrolyses or combustion of neat chlorobenzenes readily forms significant yields of PCDDs/PCDFs, corresponding treatment of dilute solutions was generally non-productive. This result is consistent with the proposition that, under the conditions studied, the rate-limiting step for PCDD/PCDF formation is bimolecular in chlorobenzene. In contrast, earlier studies of PCBs implied a rate-limiting step that was unimolecular in chloroaromatics. Combustion of dilute solutions of chlorobenzenes in tetrachloroethylene did produce detectable concentrations of PCDF; this result reflects combination of chlorobenzene and TCE- or TCE-derived species.     

Comparison of PCDD and PCDF in flyash collected from muncipal incinerators of different countries

Flyash samples were collected from the electrostatic precipitators of seven municipal refuse incinerators of four different countries. Analytical results of PCDD and PCDF in these samples shows a very similar iosmer distribution pattern for all PCDD/PCDF although concentrations of PCDD and PCDF vary. These results imply that PCDD/PCDF were formed through the same mechanism in those incinerators regardless of garbage composition or incinerator design.     

Atmospheric baseline levels of PCDD and PCDF in the region of Oporto

An external monitoring plan (EMP) is being implemented in the region of Oporto, Portugal, to follow the potential effects of a future incinerator of municipal solid waste. Polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/PCDF) were measured during 1998 and the first semester of 1999, prior to the working up of the incineration unit. The baseline levels obtained through this intensive monitoring work are presented and discussed in the present paper.