Occurrence of organotin compounds in house dust in Berlin (Germany)
Introduction
Organotins are a large class of compounds which differ markedly in their properties and have been used for a variety of purposes since their discovery and initial use in the 1920s. They are organic derivatives of tetravalent tin and characterized by the presence of at least one covalent carbon–tin bond. They have the general structurewhere R is an alkyl or aryl group, Sn the central tin atom in the oxidation state +4 and X a singly charged anion or an anionic organic group. Most importantly, methyl, butyl, octyl and phenyl moieties are contained in the organic substituents of all compounds of any practical relevance, whereas the anionic moiety usually comprises chloride, fluoride, oxide, hydroxide, carboxylate or thiolate. Under normal conditions their physicochemical properties appear as only slightly volatile, insoluble in water and with a strong tendency to absorb particulate matter (KEMI, 2000).
Of the various organotins, the mono-, di- and tri-substituted compounds are the most widely employed, the first two (notably mono- and di-methyltin, butyltin and octyltin compounds) being used extensively as heat and light stabilizers in the manufacture of polyvinyl chloride (PVC) polymers and as industrial catalysts for polyurethane and silicone elastomers. Thus they are present in water pipes, food packing materials (e.g., dioctyltin), glass coatings (e.g., butyltin trichloride), polyurethane foams and many other consumer products. Another less extensive use of organotins is in industrial and agricultural biocides (fungicides, bactericides, miticides, insecticides), surface disinfectants and preservatives for wood, paper, textiles, paints and some electrical equipment. On a world wide basis tri-substituted organotins (notably tributyltin oxide and tributyltin methacrylate) are used as antifouling agents in paints for boats and ships, thereby accessing the aquatic environment (WHO, 1990, US EPA, 2002). It can be estimated that their most frequent uses are as PVC stabilizers (approximately 16 000 ton annually in Europe) and as catalysts (1300–1650 ton), thus accounting in each case for approximately 67% and 8% of total organotin consumption. About 2–4% of PVC production is ascribable to this type of stabilizer. Biocidal uses account for nearly 20% of the market and all other uses (including latex paint preservatives, anthelminthics and coccidiostats) for 5% (US EPA, 2002).
The prominent toxicological feature of the organotins is their immunotoxicity, an effect produced by di- and trialkyltins as well as triphenyltins. The acute toxicity after dermal or oral application of most organotins is low to moderate (depending on routes and species, for DBT 58–5480 mg kg−1 bw), though local effects possibly occurring are eye and skin irritation or sensitization at the site of contact (WHO, 1990, ATSDR, 1992, WHO, 1999a, WHO, 1999b, KEMI, 2000). The focus of ecotoxicology is on risks from the use of organotin compounds (especially butyltins) as biocides in antifouling paints. TBT acts as an endocrine disrupter in animals and induces masculinization (imposex) by increasing testosterone levels in different species of female gastropods (Fent, 1996). In experimental animals TBT produced endocrine tumors, although no evidence of any TBT mutagenicity is known (Wester et al., 1990). In vitro studies found that butyltins inhibit human cytochrome P450 aromatase and 5α-reductase activity and might therefore have a distinct impact on human hormone metabolism (Doering et al., 2002).
Section snippets
Material and methods
The present study was conducted for the identification of hazardous chemicals in the indoor environment of apartments in a particular urban area as part of a wider investigation (Fromme et al., 2004a, Fromme et al., 2004b). The aim was to measure the most significant organotins produced in industrial processes and present in house dust. That is, monobutyltin (MBT), dibutyltin (DBT), tributyltin (TBT), monooctyltin (MOT), dioctyltin (DOT), and triphenyltin (TPT). It is well known that house dust
Sampling procedure and analysis
The house dust was taken from the bags of the vacuum cleaners in regular use for cleaning the apartments. Inhomogeneity was avoided by only taking the fine dust from the space between the inner and outer paper layers of the bags. Any larger dust particles, fibres and debris, which might otherwise have distorted the results, were thus excluded. The dust was put directly to clean aluminium foil and then transferred to glass bottles for storage. Information reported in the literature indicates
Results and discussion
Table 2 shows the statistical parameters of organotin measurements in house dust. MBT and DBT were found in 86% and 82% of the samples above the detection limit, TBT and MOT only in 50% and DOT only in 43%. The concentrations of MBT and DBT determined ranged, respectively from 0.01 to 1.5 mg kg−1 (median: 0.045 mg kg−1) and 0.01 mg kg−1 to 5.6 mg kg−1 (median: 0.03 mg kg−1). Median levels of TBT and MOT were only 0.01 mg kg−1. The maximum value of the total organotins (using only values above the detection
Acknowledgements
The authors would like to thank Dr. Richard Flower for his help in preparing this manuscript. The study was funded by the Gesellschaft für Umweltmedizin und Toxikologie e.V.
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