Enantiomer ratios,patterns and levels of toxaphene congeners in human milk from Germany

High resolution gas chromatography (HRGC) coupled to quadrupole negative ion chemical ionization (NICI) mass spectrometry (MS) was used to investigate congener patterns, levels and enantiomer distribution of selected toxaphene congeners (#26, #41, #44, #50, #63, B7-1453) in human milk from Germany. #50 and #26 were the most abundant congeners. Furthermore, the identification of B7-1453, B8-1412, #41, #42, #44 and #63 was possible. Levels for the sum of #26, #41, #44 and #50 ranged from 7 to 24 microg kg(-1) milk fat and contributed between 2 and 9% to the total burden of investigated organochlorines such as selected compounds of the chlordane group, HCH, DDT and polychlorinated biphenyls (PCB). Capillaries coated with heptakis-(2,3,6-O-tert-butyldimethylsilyl)-beta-cyclodextrin (TBDMS-CD) or octakis-(2,3,6-tri-O-ethyl)-gamma-cyclodextrin (TEG-CD) were used for the enantioselective separations. Enantiomer ratios (ER) and enantiomer fractions (EF) of the abundant toxaphene congeners #26 and #50 as well as of B7-1453, #41 and #63 were determined. Greatest deviations from a racemic composition in individual human milk samples were found for #41 (1.54-2.37), #50 (1.37-1.72) and #63 (0.53-0.71) whereas ERs for #26 were close to 1. Compared to wildlife biota such as fish and raptors ER changes were more pronounced in human milk but comparable to human adipose tissue.     

ESF Workshop

Dioxin and PCB monitoring programs for food and feeding stuff in most countries of the world, including many European Countries are currently inadequate. Better control of food production lines and food processing procedures is needed to minimize entry of dioxin to the food chain and will help to avoid dioxin contamination accidents. This would also improve the ability to trace back a possible contamination to its source. European guidelines for monitoring programs should be established to ensure comparable and meaningful results. These guidelines should define the minimum requirements for the design of monitoring programs, analytical methods, and quality assurance. Though data from Northern Europe shows that the general population exposure to dioxin and PCB has decreased during the last ten years these compounds continue to be a risk of accidental contamination of the food chain. The most prominent recent example is the Belgian dioxin contamination of feeding stuff in 1999. The Belgian dioxin contamination was not detected due to dioxin monitoring programs but by their direct biological effects seen in animals. Four other cases of dioxin contamination have been detected in Europe since 1997 due to local monitoring programs. One of them (citrus pulp pellets 1998) was in a much larger scale than the Belgian dioxin contamination. The general population's exposure to dioxins and PCBs is still in the same range (1-4 pg WHO-TEQ/kg body weight and day) as the recently revised WHO tolerable daily intake (TDI). There is concern that short-term high level exposure to dioxins, furans, and PCB may cause biological effects on the human fetal development and further research is required. Further actions to control sources building on considerable advances already made in many countries may need to be supplemented by measures to prevent direct contamination of feeding stuff or food to reduce general population exposure further.     

Teil 1: PCDD/F in Böden,Vegetation und Kuhmilch

Soil samples were taken from residential gardens, grasslands and forests at 22 locations in Marsberg, North Rhine-Westphalia, and analyzed for PCDD/F. Sampling was concentrated on the vicinity of a former copper smelter where copper waste material (calledKieselrot) was deposited and emissions from former stacks contaminated a large land area. Maximum PCDD/F-concentrations were 407 ng TE GBA/kg dm in garden soil (0–30 cm depth), 98 ng TE BGA/kg dm in agricultural grassland (0–10 cm depth), 227 ng TE BGA/kg dm in wasteland, and up to 8073 ng TE BGA/kg dm in forest soils. PCDD/F-levels in soil decreased with increasing distance from the former sources providing a large historic emission problem, apart from the still existing kieselrot waste site. Ash residues from former flue gas duct showed up to 2,4 mg TE BGA/kg dm. PCDD/F-concentrations in vegetable samples from highly contaminated garden soils and grass from agricultural grassland were found to be relatively low in relation to soil values. PCDD/F-levels in salad showed a mean of 2,2 ng TE BGA/kg dm while grass concentrations were <6 ng TE BGA/kg dm. Thus, no correlation was found between soil and vegetation values with the exception for carrot roots where obviously a small transfer of PCDD/F between the two media took place. PCDD/F-content in grass taken over the vegetation period showed a tendency to increase toward the end of the growing season, which is probably related to changes in the dry matter yield over the season. No correlation was found in general between soil, grass and milk PCDD/F contents when all samples were taken from the same grassland. PCDD/F-concentrations in milk ranged between 0,6 and 1,1 pg TE BGA/g milkfat and were thus in the same range as consumer milk in the Federal Republic of Germany. PCDD/F in needles from conifers showed a clear relationship with respect to distance from the former waste site. The relatively high levels in conifer needles [36 ng TE BGA/kg dm] were obviously due to sporting activities (i.e. motocross racing where contaminated material was resuspended and deposited on surrounding trees).     

Results of an "emergency quality control study" as confirmation of a PCDD/PCDF-contamination of milk and butter samples

Elevated PCDD/F levels in four butter samples and one milk sample had to be confirmed under considerable time pressure. These samples should demonstrate a raising dioxin contamination in different regions of Germany caused by the use of Brazilian citrus pulp as feedstuff. Above all, the increase of 2,3,7,8-TCDD and 1,2,3,7,8-PeCDD had to be confirmed. Thus, an "emergency quality control study" was performed including five laboratories from the official food control in Germany. The results had to be reported about two to three weeks after the first announcement of the samples (including time for shipment). The five laboratories applied different extraction and clean-up methods, used different GC-columns and GC/MS-equipment and different standard solutions. The results are in a good agreement. Slightly different results for most individual congeners were of minor importance. A difference was observed only in the 2,3,7,8-TCDF content of one laboratory which was not relevant for the evaluation of the increase of the dioxin contamination in milk and dairy products. The laboratory's individual methods proved to give correct results even under a very tight schedule.     

Monitoring the impact of sulphur with the Austrian Bioindicator Grid

In Austria, the impact of sulphur has been assessed since 1985 with the help of the Austrian Bioindicator Grid on 760 sample plots with Picea abies as the main tree species (90%). The annual sampling allows a precise evaluation of the temporal and regional development of the impact of sulphur on the basis of legal standards. Despite the reduction of SO2 emissions in Austria, the legal standard is still exceeded on 8% of the plots. These plots are mainly located near large Austrian emittors, but also in areas affected by transboundary sulphur emissions from neighbouring countries. The present paper describes how the Bioindicator Grid can be applied for the control of legal requirements to enact effective clean air measures in Austria and take supportive measures that reduce the impact of sulphur from emittors in neighbouring countries.     

Teil 2: PCDD/F,Biphenyle und Organochlorpestizide in Frauenmilch

After the discovery of high dioxin levels (>100 000 ng TE BGA/kg) in copper slag (Kieselrot) from a specific chlorinating roasting process performed in Marsberg, human milk samples from mothers living in Marsberg were analyzed for polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and other pollutants. PCDD/F levels in all samples were comparable with levels in human milk samples from other locations in the Federal Republic of Germany. An increase in congeners, especially of those predominating in ?Kieselrot“, could not be measured. Although several thousand tons of dioxin contaminated copper slag still lie on the slagheap, a higher burden in human milk from Marsberg could not be observed.     

Experimental evidence of chemokinesis in newly hatched cod larvae (Gadus morhua L.)

The swimming behaviour of laboratory-reared newly hatched cod larvae (Gadus morhua L.) was observed in a control solution of artificial seawater and in seven solutions, each with a different concentration of arginine (10⁹ to 10^-3 M). The behaviour of 20 larvae was analysed in each of the eight solutions; the individual observation time was 1 min. Individual movements were recorded on video and analyzed using a computer-assisted program. The larvae swam in straight lines (a trajectory), rested, moved and started swimming again. For the parameters analyzed, i.e., number of movements, angle between successive trajectories and straightness index, there was no significant difference between the behaviour of the larvae in the different solutions. However, for the larvae in 10^-5, 10^-4 and 10^-3 M arginine solutions, the analyzed parameters, i.e., time active, frequency of trajectories (number of movements exceeding body length), distance swum min^-1, length of individual trajectories and trajectory velocity, were all significantly lower than for the larvae in the control solution of artificial seawater and for larvae in the solutions of 10^-9, 10^-8, 10^-7 and 10^-6 M arginine. The results show that the mean distance swum by cod larvae min^-1 was two to five times longer in artificial seawater without arginine and in the four lower concentrations of arginine than in the three higher concentrations. Scanning micrographs show that newly hatched (pre-feeding) cod larvae possess olfactory organs. It seems reasonalbe to assume that the observed changes in swimming behaviour are mediated by the olfactory sense and are important in the feeding strategy of cod larvae. We suggest that the observed behaviour increases the probability of the larvae localizing patches of prey organisms and remaining in the patch once they have found it. The results show that chemokinesis is a mechanism by which the spatial distribution of fish larvae will be correlated with their prey.