GERMAN ENVIRONMENTAL SURVEY 1998 (GERES III): PESTICIDES AND OTHER POLLUTANTS IN HOUSE DUST

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1 GERMAN ENVIRONMENTAL SURVEY 1998 (GERES III): PESTICIDES AND OTHER POLLUTANTS IN HOUSE DUST K Becker *, M Seiwert, S Kaus, C Krause, C Schulz and B Seifert Federal Environmental Agency (Umweltbundesamt), Berlin, Germany ABSTRACT The German Environmental Survey (GerES) is a large-scale population study which has repeatedly been carried out in Germany. GerES I was conducted in 1985/86 followed by GerES II in 1990/92 and GerES III in In GerES III about 750 samples of house dust collected in homes of the study participants were analysed for their content of PCP, lindane, DDT, propoxur, methoxychlor, chlorpyrifos, polychlorinated sulfonamide diphenyl ethers, pyrethroids and PCB. Flame proofing agents (e.g., TCEP, PBDE) and plasticisers (e.g., phthalates) were analysed in 200 samples. The analytical results are given and discussed. Looking at trends over time, it can be stated that the concentrations of PCP and lindane in house dust have decreased between 1990/92 and 1998 while the concentration of permethrin remained about the same. INDEX TERMS GerES, Pesticides, House dust, Flame proofing agents, Plasticisers. INTRODUCTION The German Environmental Survey (GerES) is a nationwide representative population study conducted to assess the exposure of the German population to various pollutants. The first German Environmental Survey was carried out in 1985/86 in West-Germany (GerES I). In 1990/92 the survey was repeated (GerES II), extending it at the same time to the former German Democratic Republic (GDR). GerES III was conducted in As dust in the indoor environment contributes to human total exposure, analysis of house dust samples has been included in GerES, the general emphasis of which being on human biomonitoring. In GerES III these samples were analysed inter alia for their content of pesticides (PCP, lindane, DDT, propoxur, methoxychlor, chlorpyrifos, polychlorinated sulfonamide diphenyl ethers), pyrethroids, flame proofing agents and plasticisers (phthalates and organo-phosphates). METHODS As in previous surveys, the study population of GerES III was selected from the subject reservoir of the German National Health Survey (Hoffmeister et al. 1996) and was representative with regard to age (18 to 69 years), gender, community size and place of residence (West- or East-Germany). A total of 4822 persons from 120 localities participated in GerES III. The sampling procedures, the study design and the field work in GerES III were generally identical to those of GerES II (Seifert et al. 2000a). Like its predecessors, GerES III comprised human biomonitoring, collection of information on exposure conditions via questionnaires, and the determination of exposure conditions in the home by analysis of drinking water and house dust. However, in comparison to GerES II the age limit was lowered * Contact author kerstin.becker@uba.de 883

2 from 25 years in GerES II to 18 years in GerES III. In the caomparison of the results of both surveys only the age group 25 to 69years of GerES III has been used. House dust was analysed using the content of the study participant s vacuum cleaner bag as available at the time of the visit to the household. The bags were stored deep frozen until analysis. A subset of 750 randomized selected vacuum cleaner dust samples was analysed for pesticides and pyrethroids and a subset of 200 samples was analysed for the other substances. The samples were sieved and all analyses were carried out on the 2-mm size fraction. Lindane, DDT, propoxur, methoxychlor, chorpyrifos and polychlorinated sulfonamide diphenylether, the phthalates, the organo-phosphates and the PCBs were analysed after extraction with toluene with GC/MS. In the case of methoxychlor and DDT GC-analysis was carried out after reaction with KOH and extraction with hexane. PCP was analysed with GC/ECD (Butte et al. 2001). The phthalates analysed were DEP (diethylphthalate), DEHP (di- (2-ethylhexyl)-phthalate), DMP (dimethylphthalate), DiBP (diisobutylphthalate), DnBP (di-nbutylphthalate), BBP (butylbenzylphthalate), DnOP (di-n-octylphthalate). The organophosphates analysed were TBEP (tris-(2-butoxyethyl)-phosphate), TCEP (tris-(2-chlorethyl)- phosphate), TEHP (tris-(2-ethylhexyl)-phosphate), TCP (tricresylphosphate), TPP (triphenylphosphate). The pyrethroides (permethrin, cyfluthrin, cypermethrin, deltamethrin, d-phenothrin, empenthrin, λ-cyhalothrin) and PBO were analysed after extraction with toluene using high resolution gas chromatography and high resolution mass spectrometry (HRGC/HRMS) (Ball et al. 1996). Internal standards were run together with the samples on a periodical basis for internal quality control. Since no reference material is available for the analysis of the substances selfprepared pooled dust material was used. Concentrations below the limit of quantification (LOQ) were set to LOQ/2 for calculation purposes. Data on pesticides and pyrethroides were adjusted by weighting according to age, gender and community size. RESULTS Table 1 gives an overview of the results of the content of the various pollutants in house dust. PCP was the most frequently encountered pesticide (in 70 % of the samples) with a median of 0.23 µg/l followed by methoxychlor which could be determined in 47 % of the samples. Lindane, DDT, propoxur, chlorpyrifos and polychlorinated sulfonamide diphenyl ethers (PSDE) were found in 26 %, 38 %, 7 %, 16 %, 29 % of the samples, respectively. Of the pyrethroides analysed only permethrine was found in the majority of the samples with a mean concentration of 0.17 mg/kg. Cyfluthrin and cypermethrin were found in 3 %, deltamethrin, d- phenothrin and λ-cyhalothrin in 1 % of the samples (LOQ=0,1 mg/kg). Empenthrin (LOQ=1 mg/kg) was not found in any sample. Detectable amounts of PCB were found in between 2 % (PCB-28) and 51 % (PCB-138) of the samples. The flame proofing agents and plasticisers, which were analysed showed a median concentration over a wide range. As PCP and lindane were determined in house dust in both GerES II and GerES III, time trends from 1990/92 to 1998 can be described for the 25 to 69 years old population (Table 2). The geometric mean (GM) of the PCP content decreased from 0.33 mg/kg to 0.25 mg/kg and that of the lindane content from 0.21 mg/kg to < 0.09 mg/kg, which had been the limit of quantification of GerES II. In GerES II PCP-GM had been significantly higher in West- Germany (0.40 mg/kg vs mg/kg) whereas the oposite was found for lindane-gm 884

3 (0.15 mg/kg vs mg/kg) (Schulz et al., 1999; Seifert et al., 2000b). In GerES III the differences between the contents in West- and East-Germany were less marked (PCP: 0.27 mg/kg vs mg/kg; lindane < 0.09 mg/kg in both parts of the country). Table 1. Pesticides in house dust (mg/kg) of homes of the German population (18 to 69 years) Substance LOQ N %>LOQ 10P 50P 90P P95 Max Pesticides PCP < Lindane <0.05 < DDT <0.05 < Propoxur <0.1 <0.1 < Methoxychlor <0.05 < Chlorpyrifos <0.05 < PSDE <0.5 < PBO and permethrine PBO < Permethrine PCB PCB <0.02 <0.02 <0.02 < PCB <0.02 <0.02 < PCB <0.01 < PCB < PCB <0.02 < PCB <0.02 < Σ PCB ( ) Σ PCB ( ) Flame proofing agents. plasticisers DEP DEHP DMP < DiBP DnBP BBP DnOP TBEP TCEP <0.1 < TEHP <0.1 < TCP <0.1 <0.1 < TPP < Notes: 1 : polychlorinated sulfonamide diphenylether; LOQ = limit of quantification; N = sample size, %>LOQ = percentage of values above LOQ 10P, 50P, 90P, 95P = percentiles, Max = maximum value 885

4 Table2. PCP, lindane, permethrin and PBO in house dust of the German population in 1990/92 and 1998 (25 to 69 years) GerES II (1990/92) GerES III (1998) Substance N 50P GM CI GM N 50P GM CI GM PCP Lindane <0.09 <0.09 Permethrin PBO Notes: N = sample size, 50P = percentile, GM = geometric mean, CI GM = 95th confidence interval of the geometric mean The GM of permethrin did not change significantly: it was 0.22 mg/kg in GerES II and 0.24 mg/kg in GerES III. PBO-GM decreased significantly from 0.09 mg/kg in 1990/92 to 0.06 mg/kg in DISCUSSION Although in Germany like in other industrialised countries the production and use of PCP, lindane, DDT are regulated they still can be detected in 70 %, 26 % and 38 % of the house dust samples of the German population. However, it could be shown that regulation has had a positive effect: the mean concentrations of PCP and lindane in house dust decreased significantly from 1990/92 to Still, more than 10 years after unification different mean concentration of PCP in house dust can be found in East- and West-Germany. In 1989 the production, the application as well as the trade and commerce of PCP and products and formulations containing PCP was forbidden in West-Germany. In East-Germany PCP was used to a much lesser extent than in West- Germany which easily explaines the higher level in house dust in West-Germany. The higher concentrations of DDT in East-Germany might be caused by the use for special purposes (forestry, indoor wood protection), in high quantities until unification in 1989 (Horn et al. 1999). In former West-Germany DDT had been banned in the seventies. After the ban of PCP and PCP-containing insecticides, pyrethroids were used as substitutes. Among the pyrethroides, the most widespread single compound used seems to be permethrin; it was present in 91 % of the dust samples. However, the mean concentration in house dust did not increase between 1990/92 and Phthalates represent 90 % of the plasticisers used in Western Europe and are found, e.g., floor coverings, wallpapers, repellents, biocides and cosmetics. As they are suspected to act as endocrine disruptors, it was of interest to get data on the occurrence of these substances in house dust. Extraordinarily high concentrations were found for DEHP (50th percentile: 416 mg/kg). Phosphoric acid triesters, which serve e.g. as flame proofing agents and plasticisers in foam material as well as in paints, varnishes and wallpapers were found in 6 % - 92 % of the samples depending on the substance analysed. 886

5 CONCLUSION AND IMPLICATIONS The German Environmental Surveys (GerES) are an integral part of a surveillance system which includes measuring, analysing and documenting changes in the environment and in environmental health. House dust which is one of the matrices under study in these surveys, can be used to document trends over time in the occurrence of environmental hazards. In this study it could be shown for example that the concentrations of PCP and lindane in house dust have decreased between 1990/92 and 1998 while the concentration of permethrin remained about the same. Future surveys will permit to evaluate temporal trends for the concentration of other substances in house dust. ACKNOWLEDGEMENTS We are highly indebted to the study participants and to the many local health and environmental offices who supported our work. The financial support of the Federal Ministry for the Environment, Nature Conservation and Nuclear Safety is gratefully acknowledged. REFERENCES Ball M., Herrmann T, and Quast T A rapid method for determination of pyrethroids in house dust in sub-ppm concentrations, Proceedings of the 7 th International Conference on Indoor Air Quality and Climate - Indoor Air 96, Vol. 3. pp Nagoya: Indoor Air 96. Butte W, Hoffmann W, Hostrup O, et al Endokrin wirsame Substanzen im Hausstaub: Ergebnisse eines repräsentativen Monitorings. Gefahrstoffe - Reinhaltung der Luft. Vol. 61, 1/2, pp Seifert B, Becker K, Hoffmann K, et al. 2000a. The German Environmental Survey 1990/92 (GerES II): a representative population study. J. Exp. Anal. Environ. Epidemiology. Vol. 10, pp Seifert B, Becker K, Helm D, et al. 2000b. The German Environmental Survey 1990/92 (GerES II): reference concentrations of selected environmental pollutants in blood, urine, hair, house dust, drinking water, and indoor air. J. Exp. Anal. Environ. Epidemiology. Vol. 10, pp Schulz C, Becker K, Friedrich C, et al German Environmental Survey (GerES): pesticides in the house dust of the German residential population, Proceedings of the 8 th International Conference on Indoor Air Quality and Climate - Indoor Air 99, Vol. 2. pp Edinburgh: Indoor Air 99. Hoffmeister H, Mensink GBM, and Stolzenberg H Reduction of coronary heart disease in Germany. Prev. Med. Vol. 25, pp Horn W, Rosskamp E, Ullrich D, et al Indoor concentrations of DDT and lindane after extensive use of wood preservatives in the past, Proceedings of the 8 th International Conference on Indoor Air Quality and Climate - Indoor Air 99, Vol. 2. pp Edinburgh: Indoor Air