Seven polybrominated diphenyl ether (PBDE) congeners were measured in the particulate fraction (<2 mm) of household dust samples (n = 40), collected in four different countries (Australia, Germany, Great Britain, and United States). Dust samples from Germany contained the lowest concentrations of total PBDEs (median: 74 ng/g, range: 17–550 ng/g dust). Australian dust contained the second lowest concentration (median: 1200 ng/g, range: 500–13,000 ng/g dust). The dust from the United States and Great Britain contained the highest measured amounts of total PBDEs (US median: 4200 ng/g dust, range: 520–29,000 ng/g; Great Britain median: 10,000 ng/g, range: 950–54,000 ng/g). Daily intake of PBDEs has been estimated from published reference values on daily dust intake rates. The highest daily intake of 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47) found was in the United States (<1–330 ng/day) and the lowest was in Germany (<1–2 ng/day). The PBDE congeners present in commercially available pentabromodiphenyl ether were the highest in concentration in the United States, and the congener distribution was similar to that of the technical preparation (i.e., 2,2′,4,4′,5-pentabromodiphenyl ether [BDE-99] was similar in concentration to that of BDE-47). We conclude that further studies are required to investigate human indoor exposure to PBDEs across countries and to determine the risk factors related to indoor design factors.

In a long-term program polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) as well as dioxin-like polychlorinated biphenyls (DL-PCBs) were analyzed in the muscle tissue of eels (Anguilla anguilla), bream (Abramis brama), European chub (Leuciscus cephalus) and ide (Leuciscus idus) from the river Elbe and its tributaries Mulde and Saale. The variation of the PCDD/F and DL-PCB concentrations in all fish samples is very large, whereby the DL-PCBs predominate in comparison to the PCDD/Fs. In the eels, the concentrations (pg WHO-TEQ/g ww) for the PCDD/Fs lie in the range of 0.48–22 and for the DL-PCBs between 8.5 and 59. In the whitefish, the concentration range is 0.48–12 for the PCDD/Fs and 1.2–14 for the DL-PCBs. Statistical analysis using relative congener patterns for PCDD/Fs allow spatial correlations to be examined for sub-populations of eels and whitefish. The results are compared to the maximum levels laid down in the European Commission Regulation (EC) No. 466/2001 and the action levels of the European Commission Recommendation 2006/88/EC. Eels caught directly after the major flood in August 2002 as well as eels near Hamburg (years 1996 and 1998) show high concentration peaks. Compared to the eels whitefish is less contaminated with PCDD/Fs and DL-PCBs.

This study was designed to determine the body burden of polybrominated diphenyl ethers (PBDEs) among first-time mothers in the Greater Boston, Massachusetts area and to explore key routes of exposure. We collected breast milk samples from 46 first-time mothers, 2-8 weeks after birth. We also sampled house dust from the homes of a subset of participants by vacuuming commonly used areas. Data on personal characteristics, diet, home furniture, and electrical devices were gathered from each participant using a questionnaire. Breast milk and dust samples were analyzed for PBDEs using gas chromatography/mass spectrometry. PBDE concentrations were log-normally distributed in breast milk and dust. We found statistically significant, positive associations between PBDE concentrations in breast milk and house dust (r = 0.76, p = 0.003, not including BDE-209), as well as with reported dietary habits, particularly the consumption of dairy products (r = 0.41, p = 0.005) and meat (r = 0.37, p = 0.01). Due to low detection rates, it was not possible to draw conclusions about the association between BDE-209 in milk and dust. Our results support the hypothesis that the indoor environment and diet both play prominent roles in adult human exposure to PBDEs.

The levels of selected polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) were measured in human milk samples from the areas of Venice and Rome, primarily in order to characterize the current levels of infant exposure to PCBs and PBDEs due to breast feeding in Italy. Sixteen non-dioxin-like PCBs, including the traditional indicator congeners, and 11 PBDEs, comprising the relevant PBDE-47, PBDE-99, and PBDE-153, were determined. Congeners were selected for analysis according to their relative abundance in human tissues, toxicological relevance, and diffusion in the environment. Dietary habits of the milk donors were recorded by questionnaires; mothers of the Venice area were classified into three groups according to their consumption of local fish, molluscs, and other fishery products. Σ16(PCBs) and Σ11(PBDEs) (ngg−1 fat) for the areas of Venice and Rome were respectively, 250–390 and 240, and 1.6–2.8 and 4.1. An increase of fish and fishery product consumption could not be associated with an increase of PCB and PBDE levels in milk.

Workers at an electronics recycling plant have previously been shown to have elevated serum levels of polybrominated diphenyl ethers (PBDEs) compared to referents without occupational PBDE exposure. Subsequent structural changes and industrial hygiene measures at the plant were applied to improve the work environment. The present study aims to assess the impact of these work environment changes on the occupational exposure to PBDEs. Blood were drawn from the workers and analyzed at two different laboratories, and serum concentrations of several PBDE congeners were determined by GC/MS or GC/HRMS. Cross-sectional studies were performed prior to (in 1997; N = 19) and after (in 2000; N = 27) workplace improvements. Longitudinal studies were performed on twelve of the workers that were sampled at both occasions. Even though the amount of processed goods had doubled in 2000 as compared to 1997, there was a significant decrease in the serum levels of BDE-183 and BDE-209. For BDE-209 the levels observed in year 2000 were even lower than in referents with no occupational exposure. In contrast to the decrease of higher brominated diphenyl ethers, the concentrations of BDE-47 did not significantly change. For BDE-153, the cross-sectional study indicated no change, whereas the longitudinal follow up indicated a significant increase. This study shows that the industrial hygiene improvements clearly reduced the occupational exposure to BDE-183 and BDE-209 at the plant. Still, the levels of hexa- to nonaBDEs but not BDE-209 were elevated, compared to referents with no occupational exposure.

Meadow soils, feeding-stuffs and foodstuffs from the alluvial plain of the river Elbe were analyzed in respect of PCDD/Fs, DL-PCBs and mercury with a view to assessing the consequences of the extreme flood of August 2002. The PCDD/F concentrations in the soils range from 3 to 2100 ng WHO-TEQ/kg dm, and for the DL-PCBs the range was 0.32 to 28 ng WHO-TEQ/kg dm. On the basis of established threshold values >40% of the areas are only fit for restricted usage. Mercury concentrations range from 0.11 to 17 mg/kg dm, whereby the action value of 2 mg/kg dm is exceeded in about 50% of the soil samples. A cumulative memory effect from past floods rather than a recent contamination from August 2002 is documented. Soils taken from behind broken dykes showed significantly lower concentrations. Grass, hay and grass silage originating from pasture land in Lower Saxony were taken before and immediately after the flooding. PCDD/Fs range from 0.29 to 16 ng WHO-TEQ/kg, the maximum permitted value of 0.75 ng WHO-TEQ/kg was exceeded in about 50% of the samples. Muscle-tissue from cattle, sheep, lamb and a roe deer as well as untreated milk from individual cows returned values ranging from 0.76 to 5.9 pg WHO-PCDD/F-TEQ/g fat, and 10% of the samples returned values higher than the permitted maximum of 3 pg WHO-PCDD/F-TEQ/g fat. The action value of 2 pg WHO-PCDD/F-TEQ/g fat was exceeded in 33% of the samples. No direct connection between these results and the effects of the flood could be established. A major input path for PCDD/Fs is the tributary Mulde, which discharges contaminated sediments from its catchment area into the Elbe.

Concentrations of polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other organic micropollutants were determined in dated sediment/soil cores collected from the flood-plain of the river Elbe near Pevestorf (PT), approximately 125km upstream of Hamburg, and Heuckenlock (HL) in southeast of Hamburg. Concentrations of PCDD/Fs peaked sharply at PT in the 1950s and at HL at the end of the 1940s. Cluster analyses provide evidence that the region of Bitterfeld-Wolfen (about 350–400km upstream of Hamburg) could be the source of the PCDD/F contamination existing in the cores PT and HL since the 1940s. Obviously it is caused by sediments of the river Elbe of a similar composition. Whereas the PCDD/Fs, HCHs (hexacyclohexane isomers), DDX (DDT, DDD, DDE), and tetrachlorinated ethers in PT and HL presumably originated predominantly from the Bitterfeld-Wolfen region, organotin compounds in HL and dichlorinated haloethers in HL during the 1940s and 1950s can probably largely be attributed to emissions from the Hamburg region.Although they are separated by a large distance, in both sediment cores PT and HL concentrations and composition patterns of most organic micropollutants analyzed widely match. Inductively it can be concluded that similar contaminations will be found in many of the river bank soils between the Bitterfeld-Wolfen region and Hamburg. Excavation of top soils may uncover highly contaminated materials. Since the dated sediment cores show the variation in contaminants in the Elbe sediments over a defined time period, it is possible to make an approximate assessment of the actual degree of contamination to be expected in areas where in previous decades contaminated dredged sediments from the Elbe and from the Port of Hamburg have been deposited on land and used for building plots or for agricultural purposes.

In the context of a monitoring program, persistent organic pollutants (POPs) were quantified in the blood of 10 year old children at four different demographic regions in Baden-Wuerttemberg, a highly industrialised federal state in South West Germany. DDE, HCB, PCB 138, PCB 153 and PCB 180 were measured in 1996/1997, 1998/1999, 2000/2001 and 2002/2003 in individual samples of about 400 children per year. PCDD/PCDFs and some relevant coplanar PCBs were determined in pooled samples from children in seven cycles from 1993 to 2003. Blood concentrations of the investigated compounds decreased in that time period by a factor of 2–4 with the exception of most PCDFs. The concentrations of POPs in the blood of the children were distinctly lower than the concentrations reported for adults. Breast feeding was associated with about 30% higher median concentrations of DDE, HCB, PCBs and a 30% increase for mean PCDD/PCDF concentrations. Concerning demographic differences, significant lower concentrations of HCB, PCBs and PCDD/PCDFs could be seen in children from Mannheim compared to the region of Aulendorf. About 10–20% higher concentrations were found in boys compared to girls for HCB, indicator PCBs and PCDD/PCDFs. The pattern of non-ortho and mono-ortho PCBs in the blood of children was similar to the pattern reported for mother’s milk, and PCB 126 and PCB 156 contributed about 70% to the toxicity of dioxin-like PCBs and about one-third to total TEQ including PCDD/PCDFs.

This paper gives an overview on the determination of PBDEs in biological tissues, such as human blood and milk, cow's milk and fish with special emphasis on quality control and assurance measures which are mandatory and a prerequisite for a reliable determination of environmental pollutants at trace levels. First experiences in the determination of PBDEs have been gained nearly 20 years ago. Due to great progress in the development of analytical instrumentation, the applied GC/MS methods resulted in very low detection limits. Furthermore, because of unexpected findings in biological tissues, the determination of PBDEs became of growing importance in the past few years. The analysis of hundreds of samples demonstrated the need for extensive quality control/quality assurance (QC/QA) measures which will be reported in detail in the following.

B. Stachel*, R. Götz**, T. Herrmann***, F. Krüger****, W. Knoth*****, O. Päpke***, U. Rauhut****** H. Reincke*, R. Schwartz*******, E. Steeg******** and S. Uhlig********* * Wassergütestelle Elbe der Arbeitsgemeinschaft für die Reinhaltung der Elbe, Nessdeich 120-121, D 21129 Hamburg, Germany (E-mail: burkhard.stachel@arge-elbe.de) ** Behörde für Umwelt und Gesundheit, Institut für Hygiene und Umwelt, Umweltuntersuchungen, Marckmannstraße 129 b, D 20539 Hamburg, Germany (E-mail: rainer.goetz@bug.hamburg.de) *** ERGO Forschungsgesellschaft, Geierstraße 1, D 22305 Hamburg, Germany (E-mail: thomas.herrmann@ergo-research.com) **** ELANA Boden-Wasser-Monitoring, Lysimeterstation, Dorfstraße 55, D 39615 Falkenberg, Germany (E-mail: krueger.zehren@freenet.de) ***** Umweltbundesamt, POP-Labor, Paul-Ehrlich-Straße 29, D 63225 Langen, Germany (E-mail: wilhelm.knoth@uba.de) ****** Landesamt für Umweltschutz Sachsen-Anhalt, Sternstraße 52 a, D 06886 Wittenberg, Germany (E-mail: dioxinlabor@lau.mu.lsa-net.de) ******* Leipniz-Institut für Gewässerökologie und Binnenfischerei, Müggelseedamm 301, D 12587 Berlin, Germany (E-mail: rene_schwartz@web.de) ******** Behörde für Umwelt und Gesundheit, Institut für Hygiene und Umwelt, Abt. für Rückstände und Kontaminanten, Marckmannstraße 129 a, D 20539 Hamburg, Germany (E-mail: elke.steeg@bug.hamburg.de) ********* quo data, Siedlerweg 20, D 01465 Dresden-Langebrück, Germany (E-mail: uhlig@quodata.de)

As a result of extreme precipitation in August 2002 major flooding occurred in the catchment area of the rivers Elbe, Vltava (Moldau) and Mulde. Pollutants from industrial sites and from municipal sewage treatment works (STW) entered the Elbe and led to a serious pollution problem in the river. PCDD/F concentrations (in pg WHO-TEQ/g dw) in SPM ranged from 7-150, in sediments from 3-140; the "safe sediment value" of 20 was exceeded in 46% of the samples. 24 eels showed a wide concentration variation for these contaminants. The WHO-PCDD/F+PCB-TEQ values lay in the range from 11-56 pg/g ww, whereby the WHO-PCB-TEQ values were several times higher than the WHO-PCDD/F-TEQ values. The maximum permitted value of 4 pg WHO-PCDD/F/g ww (EU Directive No. 2375/2001) was reached or exceeded in 54% of the individuals. A statistical analysis using data from SPM and sediment samples showed that in the Czech river section the flooding activated a contamination source in the vicinity of the Spolana works. The influence of the tributary Mulde could be clearly demonstrated. Only a major clean-up of the contaminated sites in Bitterfeld can lead to a mid to long term improvement in respect of PCDD/F and dioxin-like PCB input into the Elbe.