FEB – Fresenius Environmental Bulletin founded jointly by F. Korte and F. Coulston Copyright © by PSP – Parlar Scientific Publications, Angerstr. 12, 85354 Freising, Germany. Production by MASELL Agency for Public Relations, Angerstr. 12, 85354 Freising, Germany All rights are reserved, especially the right to translate into foreign language. No part of the journal may be reproduced in any form- through photocopying, microfilming or other processes- or converted to a machine language, especially for data processing equipment- without the written permission of the publisher. The rights of reproduction by lecture, radio and television transmission, magnetic sound recording or similar means are also reserved. Printed in GERMANY – ISSN 1018-4619 © by PSP Volume 10 – No 4. 2001 Fresenius Enviromental Bulletin CONTENTS ORIGINAL PAPERS POLYCHLORINATED BIPHENYLS IN HUMAN MILK 342 FROM SLOVAK MOTHERS J. Petrík, B. Drobná, A. Kocan, J. Chovancová and M. Pavúk ORGANOCHLORINE PESTICIDE RESIDUES IN BREAST MILK 349 FROM WOMEN LIVING IN TRIPOLI, LIBYA A. Elafi, M.Rahmani and El H. Abdennebi DETERMINATION OF THE PHOTOCHEMICAL LIFE TIME OF 353 PESTICIDES IN AQUEOUS MEDIUM WITH SOLAR LIGHT S. Guittonneau, I. Konstantinou, C. Emmelin, T. Albanis and P. Meallier PHOTOSTIMULATED DECOMPOSITION OF SOME SELECTED PESTICIDES 357 IN AQUEOUS PHASE IN THE PRESENCE OF AEROSOL CONSTITUENTS P.N. Moza, K. Hustert, E.A Feicht and A. Kettrup BIOSORPTION OF COPPER (II) BY POLLENS OF THYPHA LATIFOLIA L. 363 Ü. Danis, Y. Kaya and Ö.F. Algur EFFECT OF RESIDUAL ASHES ON CPMAS-13C-NMR SPECTRA OF 368 HUMIC SUBSTANCES FROM VOLCANIC SOILS P. Conte, A. Piccolo, B. van Lagen, P. Buurman and M. A. Hemminga POLYCHLORINATED BIPHENYLS IN SEDIMENTS 375 IN EASTERN SLOVAKIA J. Petrík, A. Kocan, S. Jursa, B. Drobná, J. Chovancová and M. Pavúk A NEW METHOD OF MEASURING 381 GASEOUS SEMI-VOLATILE ORGANIC COMPOUNDS (PAHS) BY SOLID PHASE MICRO EXTRACTION (SPME) L. Lassagne, V. Jacob, P. Desuzinges, F. Tripoli, P. Kaluzny, P. Baussand and P. Foster OXIDATION OF MANGANESE (II) WITH AIR IN WATER TREATMENT 386 S. Aydin, N. Tüfekçi and S. Arayici IMPROVEMENT OF LOW HYDRAULIC PERFORMANCE OF 392 SEA OUTFALLS USING BELL MOUTHEDPORTS IN THE BLACK SEA EXAMPLE S. Nemlioglu DENITRIFICATION OF WASTEWATER IN A FIXED FILM REACTOR 396 H. Timur PESTICIDE RESIDUES IN GROUND AND SURFACE WATER IN BULGARIA 401 Z. Bratanova and K. Vassilev 340 © by PSP Volume 10 – No 4. 2001 Fresenius Enviromental Bulletin SHORT COMMUNICATIONS INVESTIGATION OF HEAVY METAL POLLUTION OF 405 TRAFFIC IN KEMALPASA-TURKEY H. Arslan SERUM COPPER AND ZINC CONCENTRATIONS OF PATIENTS 409 WITH RHEUMATOID ARTHRITIS FROM KAYSERI-TURKEY M. Soylak and M. Kirnap MEASUREMENT OF RADON CONCENTRATION IN 411 NORTHERN GREECE GROUND WATER A. Savidou and N. Zouridakis GUIDE FOR AUTHORS 416 INDEX 419 341 © by PSP Volume 10 – No 4. 2001 Fresenius Enviromental Bulletin POLYCHLORINATED BIPHENYLS IN HUMAN MILK FROM SLOVAK MOTHERS Ján Petrík1, Beáta Drobná1, Anton Kocan1, Jana Chovancová1 and Marián Pavúk2 1Institute of Preventive and Clinical Medicine, Bratislava, Slovak Republic 2Department of Epidemiology, University of Iowa College of Public Health, Iowa City, IA, USA SUMMARY Polychlorinated biphenyls (PCBs) were analyzed in The experimental data support opinion that developing 67 breast milk samples of primiparae from six districts of embryos and infants are more sensitive to harmful effects the Slovak Republic. Dietary habits, demographic and of these compounds than adults [20,21]. The period of other relevant data on mothers and their children were breast-feeding is considered as the most important one collected by self-administered questionnaires. The highest with respect to amount of PCBs transferred to a human -1 levels (mean = 1318 ng.g lipid basis, n = 12) of PCBs were body [16,22]. Determination of these contaminants in found in the Michalovce district where these chemicals mother milk is an appropriate non-invasive method of risk were produced. They were statistically significantly assessment of breast-fed children [4,23]. higher than levels in other districts (P = 8.8 E-6). The mean PCB daily intake of breast-fed infants was PCBs were manufactured from 1959 to 1984 in -1 -1 assessed to be 5.5 mg.kg b.w.d (S.D. = 3.1). Chemko Co., Strážske in the Slovak republic. Technical formulations under trademarks DELOR, HYDELOR and KEYWORDS: DELOTHERM were intensively used as heat exchange PCBs; polychlorinated biphenyls; human milk; daily intake fluids, but also as paint additives [24]. The presence of PCBs was confirmed in considerable amounts almost in all environmental compartments in Slovakia, including food INTRODUCTION and human biological matrices [20,25,26]. Although the limits [21] are not exceeded today [27], PCB levels in the PCBs are a group of 209 individual congeners with Slovak general population are still rather high [20,28-32]. different chlorine substitution patterns [1]. The higher chlorinated PCB congeners are predominantly present in the most of biological samples because of their lipophilic- MATERIALS AND METHODS ity, chemical stability, and low biodegradation. The main exposure route to humans is food consumption, mostly Breast milk was obtained from volunteers - primiparas milk products, meat and fish [2-7]. PCBs are classified as (singleton infant) without any serious metabolic disorders, probable carcinogens - group 2A [8]. The toxicity of pregnancy and delivery complications - during 1992-94 in individual congeners is structure dependent. The most six model areas (districts) of Slovakia (Figure 1). Milk toxic ones are those with no or just one chlorine atom in samples were collected in accordance with the WHO ortho position of the biphenyl structure that may assume guidelines [9,33] and stored in sealed precleaned PTFE glass planar configuration [9-14] and elicit dioxin-like toxicity. vials at -35 oC till analysis. Informed consent documents The toxicity lessens with decreasing planarity between were obtained from all mothers. A questionnaire was phenyl rings [6]. distributed to the participating mothers after the delivery, including questions on maternal education, age, height and Exposure to PCBs by ingestion was connected with weight before pregnancy and after delivery, smoking, dietary adverse effects to cardiovascular system, liver, and also habits including use of dairy products and fish consumption, with hyperpigmentosis, chloracne [7-17], and early-life occupational history, use of medicines, as well as newborns’ exposure to PCBs can have long term consequences: sex, weight, and height. Data on the time of residence in the growth, cognitive and psychomotor development delay, district and possible sources of environmental contamination neurologic and immunologic anomalies, effects to thyroid (industrial production, location of waste-disposal sites, heavy hormone metabolism, etc. [16,18,19]. traffic etc.) were also collected. 342 © by PSP Volume 10 – No 4. 2001 Fresenius Enviromental Bulletin FIGURE 1 - A map of the Slovak Republic with the areas studied: Michalovce District (PCB production 1959-84), Trebišov District (possible influence of the former PCB production), Velký Krtíš District (PCB contamination of dairy products in 1989-92), town of Bratislava (industry, traffic), Nitra District (agriculture), Myjava Region (highland area, home-made food) - situation in y. 1992. Sample preparation for analysis of PCBs The known amount of milk sample (50-100 mL) was Operating conditions: injection mode, splitless for weighed into a separatory funnel, and 10 mL 10% natrium 1 min.; column temperature held at 110 oC for 1.5 min. oxalate solution, 50 mL ethanol and 20 mL diethyl ether and then raised to 200 oC at 30 oC.min-1, to 300 oC at were added. The mixture was shaken vigorously for 2.5 oC.min-1; carrier gas, He; head column pressure, -1 1 min. Then, 30 mL hexane was added, and the mixture 200 kPa; makeup gas, N2 at 50 mL.min. was shaken for 5 min. The organic phase was transferred into another separatory funnel. The aqueous phase was extracted twice with 30 mL hexane. The combined Each GC peak in sample chromatogram was identi- hexane phases were extracted twice with 20 mL distilled fied by accurate coincidence with retention time of an water, separated from aqueous phase, dried, concentrated, authentic standard. Identified peaks were checked by and weighed as lipid. HRGC/LRMS-SIM (GC HP 5890 in combination with MSD HP5790B) in problematic cases. A method of A small amount of lipid (ca 100-200 mg) was dis- external standard was applied for quantitation. In solved in 1 mL hexane and transferred onto a combined accordance with the internal QA/QC rules a solvent blank Florisil-Silica Gel column (0.5 g Florisil, 1 g 44% H2SO4 was run in every batch of samples (usually 10). This on Silica Gel, 0.5 g Florisil, 1 g anhydrous Na2SO4). blank was not allowed to overstep 1/20 of the level of Residues were eluted with 10 mL 10% (v/v) dichloro- compounds analyzed in the sample at the same dilution. methane in hexane. Eluate was collected into 50 mL flask, To confirm recovery of the analytical method a sample of rotary evaporated to a volume of ca 0.5 - 1 mL and blown pure olive oil with known amount of PCB congeners was up to dryness under a gentle N flow. Prior to injection to 2 used. The samples were diluted so that the peak area of the gas chromatograph the residues were redissolved in determined compound was in the middle of calibration known amount of heptane. curve. Individual congener was quantitated if retention Two micro liters of treated sample in heptane solution time fit the retention time in standard solution ± 6 s. was injected. Analyses were performed on HP5890 gas Arithmetic means were used to summarize the concentra- chromatograph equipped with 63Ni ECD. A DB-5 (J&W tions of PCBs in breast milk. The influence of different Scientific, USA) capillary column, 0.25 mm id × 60 m and covariates was examined by linear regression and analysis 0.25 mm film thickness was used for the separation.