Christiane Fürst

Levels of PCDDs and PCDFs in food-stuffs from the Federal Republic of Germany

Abstract 107 food samples collected in the Federal Republic of Germany have been analyzed for residues of polychlorinated dibenzodioxins (PCDDs) and dibenzofurans (PCDFs). The results indicate that there is a remarkable difference between PCDD and PCDF levels in samples of animal and plant origin, respectively. While specimens of plant origin only contain very low levels near the detection limit all samples of animal origin show typical patterns of PCDDs and PCDFs. Common characteristic of all congeners identified is 2,3,7,8-chlorine substitution. When calculating toxic equivalents and taking consumption habits into account the average daily intake amounts to 85 pg TCDD-equivalents/person/day or 1.2 pg/kg body weight/day. From this it becomes evident that food-stuffs, especially of animal origin contribute to a considerable amount to the body burden of man.

Human milk as a bioindicator for body burden of PCDDs, PCDFs, organochlorine pesticides, and PCBs.

In the State Laboratory of North Rhine-Westphalia for Food, Pharmaceutical and Environmental Chemistry (Chemisches Landesuntersuchungsamt), more than 600 individual human milk samples have been analyzed for polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), and more than 1400 individual milk samples have been analyzed for organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs) since 1984. All samples were collected on a voluntary basis from nursing mothers mostly living in North Rhine Westphalia, a federal state in Germany. The samples analyzed so far show a typical pattern of PCDDs and PCDFs. Out of the 210 possible congeners, only those with 2,3,7,8-chlorine substitution were found. While OCDD normally shows the highest concentration, the levels of the other dioxin congeners decrease with decreasing number of chlorine atoms. A different pattern was found for PCDFs. Within this group 2,3,4,7,8-P5CDF is the most abundant congener, followed by the hexachlorodibenzofurans. The mean level of tetrachlorodibenzodioxin (TCDD) was found to be of 3.2 pg/g on a fat basis and for total PCDDs and PCDFs, calculated as I-TEq (NATO/CMMS), 29.3 pg/g on a fat basis. The investigations of the past 2 years have revealed somewhat lower levels compared to former years. This might be an indication that the efforts undertaken to minimize dioxin emissions and to shut down known sources have already had an effect on the body burden of humans. Although mostly banned for a considerable period of time now, some lipophilic persistent pesticides such as DDT, dieldrin, hexachlorobenzene (HCB), and hexachlorocyclohexanes (HCH) can still be found in human milk.(ABSTRACT TRUNCATED AT 250 WORDS)

Dioxins, dibenzofurans and selected chlorinated organic compounds in human milk and blood from Cambodia, Germany, Thailand, the U.S.A., the U.S.S.R., and Vietnam

Abstract This paper reports general population blood polychlorinated dioxin and dibenzofuran (PCDD/F) levels for various geographical regions in the north and south of Vietnam in pooled samples from 112 persons, the results of 85 individual analyses of blood from Germany, and levels from a pool of whole blood from 100 U.S. residents. This paper also presents selected population data for PCDD/Fs and certain other chlorinated chemicals such as PCBs and other chlorinated xenobiotics in human milk from locations in Vietnam, Cambodia, and Thailand. These represent new samples from seventy persons from the general population from three less industrialized Asian countries; these are compared with our previous findings from several hundred persons from Germany, the Soviet Union, and the United States.

Comparison of dibenzodioxin levels in blood and milk in agricultural workers and others following pentachlorophenol exposure in China.

Substantial amounts of sodium pentachlorophenol (Na-PCP) salts have been sprayed in certain areas in central China since the 1960s for control of snail-borne schistosomiasis. A sample of Na-PCP used in the area of concern was analyzed and showed 2,3,7,8-substituted dibenzodioxin (PCDD) and dibenzofuran (PCDF) congeners as well as some non-2,3,7,8-substituted congeners. Dibenzodioxin analysis of two pooled blood samples from 100 persons living in sprayed areas and a pooled sample from 26 individuals who had direct contact with the Na-PCP showed elevations of PCDD/F congeners found in the Na-PCP. Total PCDD/Fs ranged from 631 to 1252 parts per trillion (ppt) lipid in the blood of those exposed to Na-PCP, while two general population age-matched pooled blood samples from 50 persons each had total PCDD/Fs of 147 and 178 ppt. Toxic equivalents calculated with International Toxic Equivalency Factors (I-TEqs) ranged from 9 to 16.3 ppt in the blood samples from exposed persons while the general population blood I-TEqs were 4.8 and 6.4 ppt. A pooled breast milk sample from 50 women living in the sprayed areas was compared with a pooled sample from 50 women living in unsprayed areas. Total PCDD/Fs was low in both exposed and general population samples (134 and 42 ppt lipid, respectively), however, the women living in sprayed areas had considerably higher PCDDs, 129 ppt versus 34 ppt. The mothers exposed to Na-PCP had a I-TEq of 5.4, which was about double that of the mothers from the general population, 2.6 ppt, lipid. Although human PCDD and PCDF tissue levels in China are low compared with those in more industrialized countries, the higher levels in exposed persons are cause for concern.

Levels of dioxins, dibenzofurans and other chlorinated xenobiotics in human milk from the Soviet Union

Abstract This paper documents, for the first time, levels of PCDD/Fs in human tissue from the Soviet Union. Levels of dioxins and PCBs are lower than in some heavily industrialized countries such as West Germany (FRG). Dibenzofurans, in contrast to dioxins, are usually similar, in milk from most FRG, the United States (U.S.), and Soviet Union (USSR) locations. Only PCB congener number 28 is higher than in the FRG. Levels of DDT and alpha and beta HCH are higher in the USSR samples than in FRG or U.S. samples. Regional differences are noted within and between countries. Dioxin equivalents usually average slightly higher in West Germany, followed by the U.S., with the USSR slightly lower.

Levels of chlorinated dioxins, dibenzofurans and other chlorinated xenobiotics in food from the Soviet Union and the south of Vietnam

Abstract Although levels of dioxins and dibenzofurans in humans from a small number of countries have recently been reported, very few publications exist on the levels of these contaminants in food. Food, especially milk products, meat, and fish, are believed to be the route of entry of most of the dioxins found in humans. There have been only three published studies of dioxins in food from Vietnam; the remaining worldwide dioxin food data comes from a relatively small number of Canadian and German reports. In an attempt to correct this lack of information concerning these highly toxic xenobiotics we report here for the first time PCDD/F levels in food from the Soviet Union and compare these with levels we found in Vietnamese food, reported on a whole weight or lipid basis, and with some newly reported German food data, presented in detail in a separate paper in this volume.

Polychlorinated dioxin and dibenzofuran levels from human milk from several locations in the United states, Germany and Vietnam

Abstract This work extends our previous work on levels of PCDD/Fs in human milk. In this paper, three countries are presented, the Federal Republic of Germany for reference purposes, pooled specimens from Los Angeles California and Binghamton, New York, widely separate cities in the United States, and various locations in the north and south of Vietnam, from 1980s specimens. Milk from the 2 US cities contain almost identical levels of the detectible PCDD/Fs, whereas in the north of Vietnam, a less industrial area, markedly lower PCDD/Fs levels were found. 2,3,4,7,8-PnCDF was markedly higher in Germany than the USA, although other values were similar. German specimens had higher PCDD/Fs levels than the USA, however, and higher toxic equivalents. Vietnamese milk specimens from the south have lower TCDD values now than they did in the 1970s when Agent Orange spraying occurred, when TCDD levels were, in some cases, markedly elevated.

Analysenverfahren zur Bestimmung von polychlorierten Dibenzodioxinen und Dibenzofuranen in Frauenmilch

A method is described for the determination of polychlorinated dibenzodioxins and dibenzofurans in breast milk. After addition of potassium oxalate, the compounds are extracted, along with fat and other lipophilic compounds, using ethanol, ethyl ether and pentane. An aliquot of the fat is fortified with seven 13C-labelled dioxins and furans. Gel permeation chromatography on Bio-Beads S-X3 is used for removal of fat followed by column chromatography on florisil, charcoal and acid alumina. Except for 2,3,7,8-tetrachlorodibenzodioxin (2,3,7,8-TCDD), all other congeners are determined by combined capillary gas chromatography/mass spectrometry by use of negative chemical ionization employing methane as reagent gas. MS analysis is performed in the SIM mode (selected ion monitoring). For each isomer group two ions are monitored. Octachloronaphthalene is used as a syringe spike for the quantification based on a calibration run of standards. The calibration mixture, which contains the spike as well as all 2,3,7,8-chlorine substituted dioxins and furans and the 13C-labelled surrogates at a concentration level of 3-5 pg/microliters, is injected twice every day. For the determination of 2,3,7,8-TCDD a mass selective detector is used operating in electron impact mode. The MS analysis is also performed in SIM mode monitoring two ions for TCDDs and one ion for 13C-2,3,7,8-TCDD. Dependent on the level of each congener in breast milk, the coefficient of variation of the method varies between 3% for 2,3,4,7,8-pentachlorodibenzofuran and 40.9% for octachlorodibenzofuran. More than 200 human milk samples, mostly from nursing mothers living in North Rhine-Westphalia, have been analysed for residues of polychlorinated dibenzodioxins and polychlorodibenzofurans.(ABSTRACT TRUNCATED AT 250 WORDS)SummaryA method is described for the determination of polychlorinated dibenzodioxins and dibenzofurans in breast milk. After addition of potassium oxalate, the compounds are extracted, along with fat and other lipophilic compounds, using ethanol, ethyl ether and pentane. An aliquot of the fat is fortified with seven13C-labelled dioxins and furans. Gel permeation chromatography on Bio-Beads S-X3 is used for removal of fat followed by column chromatography on florisil, charcoal and acid alumina. Except for 2,3,7,8-tetrachlorodibenzodioxin (2,3,7,8-TCDD), all other congeners are determined by combined capillary gas chromatography/mass spectrometry by use of negative chemical ionization employing methane as reagent gas. MS analysis is performed in the SIM mode (selected ion monitoring). For each isomer group two ions are monitored. Octachloronaphthalene is used as a syringe spike for the quantification based on a calibration run of standards. The calibration mixture, which contains the spike as well as all 2,3,7,8-chlorine substituted dioxins and furans and the13C-labelled surrogates at a concentration level of 3–5 pg/μl, is injected twice every day. For the determination of 2,3,7,8-TCDD a mass selective detector is used operating in electron impact mode. The MS analysis is also performed in SIM mode monitoring two ions for TCDDs and one ion for13C-2,3,7,8-TCDD. Dependent on the level of each congener in breast milk, the coefficient of variation of the method varies between 3% for 2,3,4,7,8-pentachlorodibenzofuran and 40.9% for octachlorodibenzofuran. More than 200 human milk samples, mostly from nursing mothers living in North Rhine-Westphalia, have been analysed for residues of polychlorinated dibenzodioxins and polychlorodibenzofurans. The results of this investigation are also reported.ZusammenfassungEs wird eine Methode zur Bestimmung von polychlorierten Dibenzodioxinen (PCDD) und Dibenzofuranen (PCDF) in Frauenmilch beschrieben. Die PCDD und PCDF werden mit dem Fett und anderen lipophilen Verbindungen nach Zusatz von Kaliumoxalat mit Ethanol, Diethylether und Pentan extrahiert. Einem aliquoten Fettanteil werden sieben13C-markierte Dioxine und Furane zugesetzt. Nach gelchromatographischer Abtrennung des Fettes an Bio-Beads S-X3 erfolgt eine weitere Reinigung des Extraktes an einer Florisil-, Aktivkohle- und an einer Aluminiumoxidsäule. Mit Ausnahme von 2,3,7,8-TCDD werden alle anderen Verbindungen durch kombinierte Capillargaschromatographie/Massenspektrometrie mit Hilfe der negativen chemischen Ionisation (NCI) und Methan als Reaktantgas bestimmt. Für die Registrierung wird die SIM-Technik (selected ion monitoring) eingesetzt, wobei für jede Isomerengruppe zwei Fragmente gemessen werden. Zur Kompensation der Volumenungenauigkeit beim Injizieren wird Octachlornaphthalin (OCN) zugesetzt. Über diese Substanz erfolgt auch die quantitative Auswertung nach der für gaschromatographische Analysen üblichen Peakflächenmethode. Für die Ermittlung der Korrekturfaktoren wird eine Standardlösung, die OCN, alle 2,3,7,8-chlorsubstituierten PCDD und PCDF sowie die13C-markierten Verbindungen enthält, zweimal täglich eingespritzt. Die Bestimmung von 2,3,7,8-TCDD erfolgt mit Hilfe der Elektronenstoßionisation (EI) an einem massenselektiven Detektor, ebenfalls unter Verwendung der SIM-Technik. In Abhängigkeit von der Konzentration des jeweiligen Analyten in der Frauenmilch beträgt der Variationskoeffizient der Methode zwischen 3% für 2,3,4,7,8-Pentachlordibenzofuran und 40,9% für Octachlordibenzofuran. Insgesamt wurden bisher über 200 Frauenmilchproben, hauptsächlich von stillenden Müttern aus Nordrhein-Westfalen, isomerenspezifisch auf Rückstände von polychlorierten Dibenzodioxinen und Dibenzofuranen untersucht. Die dabei erhaltenen Ergebnisse werden ebenfalls mitgeteilt.

Levels of polychlorinated dibenzodioxins and dibenzofurans in cow's milk and in soy bean derived infant formulas sold in the United States and other countries

Abstract During the past few years, PCDD/F analysis of human milk from a number of more as well as less industrialized countries has documented contamination of milk with higher levels in the more industrialized countries, with lesser amounts in less industrialized countries. At a certain point, usually during the first year of life, the newborn infant changes from mothers milk to formula or cows milk. We extend previous findings to soy milk substitutes and cows milk with PCDD/F analyses of specimens from Thailand and the United States. We find quite low levels of chlorinated dioxins and dibenzofurans in soy preparations and in cows milk as compared to human milk.

Levels of dioxins, dibenzofurans and selected other chlorinated organic compounds in food from Russia

Abstract Food is considered to be the main source of dioxins (PCDDs) and dibenzofurans (PCDFs) for human intake, but there are relatively few publications reporting the levels of dioxins and furans in food samples. (1–4) Food samples from western to eastern Russia were collected during three recent trips by one of us (AS), and tested for dioxins and dibenzofurans to provide some indication of environmental contamination. The results show that in specific food samples there are more dioxins present than dibenzofurans, but in fish samples the opposite is true. We compare the levels found in Russian food with levels found in samples from other countries, on both wet weight and lipid basis. These Russian samples show ranges similar to but slightly lower than those seen in other industrial countries.