PCDD/PCDF-Kontaminationen aus Kieselrot von Sport- und Spielanlagen

Surfaces of many sports fields, playgrounds and paths in Germany are covered with red slag ?Kieselrot”. Kieselrot is extremely high contaminated by polychlorinated dibenzodioxines and dibenzofurans. Mean PCDD/F-concentration in surface layers of 35 locations in Hessen is 45 500 ng I-TE/kg. PCDD/F-contents range from 1 000 to 250 ng I-TE/kg within 10 cm under surface layers and from 6 000 to 600 ng I-TE/kg in top soils of three metres wide peripheral areas. Concentration in subsoils is a function of depth (n=18, r=?0,741), concentration in topsoils of peripheral areas is a function of distance from large sports fields (n=14, r=?0,881) or small sportsfields (n=23, r=?0,742), respectively. A 15 metres wide and 10 centimetres deep peripheral area contains 0,8 g I-TE PCDD/F. The pollution of surroundings and further observations indicate that ?Kieselrot-areas” must be regarded as important dioxin sources.     

Teil 3: PCDD/F im Blutfett ausgewählter Personen

This study was designed to assess the degree of exposure to PCDD/F in 56 selected persons living in the vicinity of a former copper smelter located in Marsberg, Germany. The copper smelter was in operation until 1945. In 1991, high levels of PCDD/F were found particularly in materials from the slag dumps (10 000 – 100 000 ng TE/kg). The levels of PCDD/F in blood fat were used as parameters for individual PCDD/F exposure. Since only limited reference data for PCDD/F in human blood were available, blood samples of a reference group were analyzed in the same way. The criteria were collected from a group matched for sex, age (±3 years) and body mass. The median NATO/CCMS-Toxicity equivalency values (NATO/CCMS-TE-values) of the Marsberg group (43,2 pg NATO/CCMS-TE/g blood fat) and the reference group (43,0 pg NATO/CCMS-TE/g blood fat) were similar, whereas the arithmetic mean of the Marsberg group (52,7 pg NATO/CCMS-TE/g blood fat) was higher than that of the reference group (44,4 pg NATO/CCMS-TE/g blood fat). The frequency distribution of the individual TE-values of the Marsberg group was slightly shifted toward higher values. The individuals of the Marsberg group had significantly higher levels of PentaCDF, HexaCDF and HeptaCDF on average than the individuals of the reference group. On the basis of TE-values, the majority of the individuals from Marsberg did not have an increased body burden of PCDD/F. However, some individuals could be identified with TE-values exceeding background levels ranging up to 231 pg NATO/CCMS-TE/g blood fat. Although it must be assumed that the unusual congener pattern found in many of the test subjects is a result of ingestion of contaminated slag material or soil, the findings of this study could not verify this fact.     

Verhalten von PAK im system boden/Pflanze

The results of lysimeter experiments conducted since 1991 dealing with the behavior of PAH in soil/plant systems demonstrate that the PAH pollution to cultivated plants may be caused by both atmospheric deposition and by the soil-to-plant transfer observed in contaminated sites. In the latter, a “direct contamination” of plant surfaces with PAH-loaded soil particles and the subsequent PAH turnover by desorption/adsorption processes is seen to dominate—at least for the most relevant PAHs toxic to humans, benzo(a)pyrene and dibenz(a,h)anthracene. Leafy vegetables growing close to the soil surface are therefore endangered most by a PAH contamination of the soil. The soil-to-plant transfer via “direct contamination” can be reduced to a high degree by covering the contaminated soil with different mulch materials. Systematic PAH transfer via root uptake could not generally be observed. From the reported results, a trigger value in the soil of 1 mg·kg^?1 for benzo(a)pyrene is proposed to make a judgement on PAH contaminated soils with regard to the soil-to-plant transfer pathways. Soils with excessive concentrations of benzo(a)pyrene demand special attention when considering the recommendations for the growth and consumption of cultivated vegetables. The “soil”as well as the “deposition pathways” must be integrated into a complete risk assessment of locations with food plant production, especially in urban areas.     

Bestimmung und Bewertung der Emissionen von PCDD/PCDF,PAK und kurzkettigen Aldehyden in den Brandgasen von Kerzen

Exhaust fumes of paraffin, beeswax and stearin candles without any further paint or decorative element were analysed for the toxicological important substance classes of PCDD/PCDF, PAH and short chain aldehydes. The candle waxes and wicks were investigated for chlorinated dioxins, furans and some known precursors. Toxicological risk assessment shows that emissions of the investigated candles are much lower than all administrative limitation values — even under “worst case conditions”. Thus, they do not produce a toxicological risk for human health.     

Bestimmung von Mineralölkohlenwasserstoffen im Boden

The infra-red (IR) and the gas Chromatographic (GC) methods for the determination of mineral oil hydrocarbons in soils were examined in collaborative trials with regard to their accuracy and reproducibility. Natural, homogenized soils and soils spiked with mineral oil were used as standards. The soil matrix was composed relatively simply. The repeatability and reproducibility values obtained were about 5 % und 23 %, respectively. In contrast, the GC method revealed a considerably higher error range, especially by using the split/splitless technique. The degradation of mineral oil hydrocarbons in soils under different temperatures was investigated by IR throughout one year. The degradation rate at room temperature was about 25 %; at lower temperatures no degradation was detected. Thus, the spiked soils may be used as calibration standards for the mineral oil analysis.     

PCDD/PCDF in Papierprodukten und Kartontüten

Various paper products and cardboard containers produced from bleached or unbleached cellulose and from recycled paper were investigated. In coffee filters and milk cartons manufactured from chlorine-bleached cellulose, the amount of tetrachlorinated dibenzodioxins and dibenzofurans of the sum of the to xicity equivalents (TEQ) exceeds 90%. The use of unbleached or not chlorinebleached cellulose leads to products with significantly lower concentrations of PCDD/F congeners. However, the contents of higher chlorinated dibenzodioxins are higher in these products. In products from recycled paper, both the more toxic lower chlorinated PCDD/F with the pattern typical for chlorine bleached cellulose and high contents of higher chlorinated PCDD/F can be detected. The use of recycled paper for manufacturing kitchen tissues, paper serviettes, and paper handkerchiefs should be critically re-examined. *** DIRECT SUPPORT *** A00HP015 00003     

Polychlorierte Dibenzo-p-dioxine und Dibenzofurane (PCDD/F)

Distillation residues of dry cleaning machines contain small quantities of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F), independent of the type of solvent employed. PCDD/F were not only detectable in distillation residues using perchloroethylene as dry cleaning solvent, but also similar quantities and congeneric patterns of PCDD/F were found in residues from machines operated with stoddart solvent or CFC 113. Current results suggest that PCDD/F occurrence is linked to the dirt adhering to the textiles. Dirty textiles were a prerequisite for finding PCDD/F in the distillation residues. The congeneric patterns of the identified PCDD/F in the distillation residues were found to be similar as those from household dust, sewage sludge, as well as those from soil, sediments, and street dust. The investigations clearly show that perchloroethylene is not linked to PCDD/F formation. The freshly produced, commercial perchloroethylene as well as laboratory-distilled perchloroethylene did not contain any detectable quantities of PCDD/F. Also, the possibility of PCDD/F formation through decomposition reactions of the solvents during the dry cleaning process can be excluded on the basis of existing data.     

Bestimmung der resorptionsverfügbaren PCDD/PCDF aus Kieselrot

For the estimation of intestinal absorption of polychlorianted dibenzodioxins/dibenzofurans (PCDD/F), ain-vitro model was developed in order to study PCDD/F mobilization by digestion of technogenic soils using ?Kieselrot” (red slag) as substrate and digestive juice model mixtures. Red slag samples were shaken successively with model mixtures of saliva, gastric juice, duodenal juice and bile. The solids were separated, the aqueous phase was extracted with hexane, the hexane extract analyzed for PCDD/F. Additionally, the PCDD/F-content of the red slag was determined. Extraction efficiency was tested with three different digestive juice model mixtures and also tap water for comparision. The percentage of PCDD/F transferred from the red slag sample into the digestive juice mixture was defined as absorption availability. In our experiments, a maximum absorption availability of 2 % was found.     

上海地区大气中二噁类分布特征的初步研究

为了研究上海地区大气中二噁英（PCDD/Fs）的污染水平、分布特征和相分配规律,分别选取了上海典型的工业区、居民区和郊区的采样点进行了大气样品的采集。通过对3个采样点的研究发现,上海地区的大气中二噁英的平均毒性当量浓度为0.201 pg/m^3,居民区最高,工业区其次,郊区最低。大气中二噁英排放的平均浓度属于典型的城市工业区水平。在常温下,大气中90%二噁英主要分布在颗粒物相中,从单体看,高氯代同系物主要分布在颗粒相中,而低氯代同系物则分布在气相当中。通过二噁英的气相/颗粒相分配系数Kp与蒸气压PL的关系式评价了污染物的气相/颗粒相分配行为。并应用Junge-Pankow模型预测了大气中的气相/颗粒相分配,通过与实测值的比较发现,上海地区大气中二噁英的气相/颗粒相分布十分接近于模型中的城市地区,郊区采样点和模型预测值最为吻合,工业区和居民区大气中的二噁英在颗粒物上的浓度则要高于模型预测值,对造成偏离的原因进行了分析,并对3个采样点周围的污染源进行了初步的探究。