Agata Witczak

DISTRIBUTION OF ENDOCRINE-DISRUPTING PESTICIDES IN WATER AND FISH FROM THE ODER RIVER, POLAND

ide. Mean concentrations of OCPs in the gonads ranged from 0.385 to 0.544 ng · g –1 wet weight (w.w.) for α-HCH, 0.745 to 0.832 ng · g –1 w.w. for γ-HCH, 0.479 to 0.576 ng · g –1 w.w. for dieldrin, and 0.381 to 0.684 ng · g –1 w.w. for endrin. Concentrations of the studied compounds in the water taken from the Oder River followed the order: endrin > γ-HCH > α-HCH > dieldrin > β-HCH > heptachlor ≈ aldrin > heptachlor epoxide. The highest log BCF was obtained for fish gonads and ranged from 1.5 (endrin) t o 3.4 (heptachlor epoxide). Estimated daily intakes (EDI) varied from 0.0014% to 0.097% of the acceptable daily intake (ADI). Conclusion. This study revealed no direct risk linked to the consumption of fish captured from the study area. However, from the ecological aspect, the accumulation of organochlorine residues in fish gonads has been considered a dangerous phenomenon, as this may result in decreased reproduction of fish and other aquatic organisms, potentially l eading to their extinction.

Comparison of organochlorine pesticides and polychlorinated biphenyls residues in vegetables, grain and soil from organic and conventional farming in Poland

Organic and conventional crops were studied by identifying the relationship between persistent organic pollutants in cereals, vegetables and soil. The residues of organochlorine pesticides and polychlorinated biphenyls (PCBs) were determined in grains (rye and wheat), vegetables (carrots and beets) and soil collected from the fields. PCB residues recorded in the beets from organic farming were as high as 3.71 ppb dry weight (dry wt.), while in the soil from conventional farming of beets 0.53 ppb dry wt. Among vegetables, higher concentrations of pesticides were detected in organically grown beets (190.63 ppb dry wt.). Soil samples from the organic farming contained lower levels of organochlorine pesticide residues compared to the conventional farming. Taking into account toxicity equivalent (TEQ), the conventionally grown carrots accumulated the most toxic PCBs. Non-ortho and mono-ortho PCBs were also noted in the grain of conventionally grown rye and amounted to 3.05 pg-TEQ/g wet wt.

Assessment of honey contamination with polycyclic aromatic hydrocarbons.

The aim of this study was to assess honey contamination by polycyclic aromatic hydrocarbons. Six species of honey were examined, as well as rape blossom and soil from villages Pęczerzyno and Przybysław in West Pomerania, Poland. The instrumental analysis was performed using a HP 6890 gas chromatograph coupled to a HP 5973 mass spectrometer with selected ion monitoring (SIM). Quantification was done by gas chromatography-mass spectrometry (GC-MS) using perdeuterated internal standards. Both soil samples showed high levels of all 23 PAHs, whereas honey contained mostly non-carcinogenic PAHs of low molecular weight. The most contaminated honey from Pęczerzyno contained 0.24 μg kg-1 benzo[a]pyrene. Moreover, despite low contamination of honey, a positive correlation was found between PAH content in honey, blossom and soil.

Polychlorinated biphenyl (PCB) residues in European roe deer (Capreolus capreolus) and red deer (Cervus elaphus) from north-western Poland

The purpose of this study was to evaluate polychlorinated biphenyls (PCBs) contamination levels in roe and red deer from north-western Poland and to assess environmental pollution in this area. A quantitative analysis was conducted using a capillary gas chromatography/mass spectrometry method. The mean concentrations of ΣPCBs (sum of PCBs: 28, 52, 101, 138, 153, 180) in liver samples were 30.24±12.35 ng·g−1 of lipid weight (l.w.) in roe deer and 60.13±14.23 ng·g−1 l.w. in red deer, compared with 24.21±10.02 and 45.22±9.77 ng·g−1 in the lungs of roe and red deer, respectively. PCBs 138, 153 and 180 were the dominant congeners in the liver samples of the analysed animals, whereas PCB 138 and 153 in the lungs. TEQs levels calculated for only dioxin-like PCBs were low: 0.32 and 0.29 pg WHO-PCB-TEQ·g−1 fat in liver of red deer and roe deer, respectively. The mean PCB concentrations obtained in our study for organs of roe deer and red deer were several times lower than those reported elsewhere. These findings show that the investigated roe and red deer originated from an area with low levels of PCB contamination.

Assessment of daily intake of organochlorine pesticides from milk in different regions of Poland.

The common occurrence of organochlorine compounds in the environment, food and human tissues may constitute a serious threat to human health. The method of gas chromatography-mass spectroscopy was used to determine the content of pesticides in 15 samples of raw cows milk from different regions of Poland. The results revealed high levels of p,p′-DDE, p,p′-DDT, heptachlor and aldrin. The studied milk contained lindane in average concentrations within the maximum limits. Although in 20% of all samples tested, the concentration of lindane exceeded permissible limits, while in 15% of samples the content of Σ DDT was too high. But the average daily consumption of milk containing organochlorine pesticides poses no direct threat to human health, because daily intake (DI) for all compounds were below the acceptable daily intake (ADI). Attention should be paid to the exposure of consumers to pesticide residues from other dairy foods.

Assessment of health risk from organochlorine pesticides residues in high-fat spreadable foods produced in Poland

Currently, butter and margarine are food products attracting wide customer interest. Every day, consumers around the world buy these products for human consumption. Butter is obtained from milk fat, while margarine is derived from vegetable oils. The content of organochlorine pesticide (OCP) residues was examined in both types of these high fatty products. A gas chromatograph with MSD (HP 5973) detector was used for the determination of pesticides such as α-HCH, β-HCH, γ-HCH, DDT, DDD, DDE, aldrin, dieldrin, endrin, heptachlor and heptachlor epoxide. The examined products had diverse concentrations of the analyzed compounds. Visible was the division based on the origin of the product, which might be composed of animal or vegetable fats. The research has revealed the presence of OCP residues in all examined spreads. Quantities of organochlorine compounds did not pose an immediate danger to the consumers’ health. Human and environmental health risk assessment was carried out by the estimation of lifetime average daily dose (LADD) and non-carcinogenic health hazard quotient (HQ). Total estimated LADD ranged between 1.3 × 10−5 and 3.1 × 10−5 mg kg−1 d−1 for butter, and 1.9 × 10−6 and 4.6 × 10−6 mg kg−1 d−1 for margarine and mix spread. The HQ ranged between 1.1 × 10−4 and 3.7 × 10−4 for butter, and 1.4 × 10−5 and 9.0 × 10−6 for margarine and mix spread for adults. These estimated HQs were within the safe acceptable limits, indicating a negligible risk to the residents of the study area.

Influence of smoking on indicatory PCB congeners residues levels in fish slices.

Influence of Smoking on Indicatory PCB Congeners Residues Levels in Fish Slices The aim of this study was do determine changes in concentrations of indicatory PCB congeners (IUPAC numbers: 28, 52, 101, 118, 153, 138, 180) during industrial hot smoking of mackerel (Scomber scombrus L.) and herring (Clupea harengus L.) slices and cold smoking of mackerel slices. PCB content in raw mackerel slices averaged from 1.32±0.29 ng/g wet w. for PCB 52 to 4.66±0.72 ng/g wet w. for PCB 153. In herring slices, PCB content ranged from 1.36±0.25 ng/g wet w. for PCB 28 to 16.50±1.94 ng/g wet w. for PCB 153. During hot smoking, losses of the examined compounds were observed - in herring slices by 15% (PCB 153) to 32% (PCB 52), while in mackerel slices by 3.7% (PCB 80) to 38% (PCB 28). Simultaneously, a slight increase in the content of PCB 180, PCB 118, PCB 153, PCB 138 and PCB 101 occurred during the proper smoking, between 1.5th and 2.5th hour of the smoking process. During cold smoking (26°C, 8 h), PCB concentrations increased significantly (p<0.05) by 26% (PCB 28, PCB 138) to 43% (PCB 180). In the final stage of smoking, PCB content in the alder sawdust and in the smoke had a significant effect on the levels of the analysed PCB congeners in the smoked slices. The main parameter determining the change of these compounds contents was their decrease in co-distillation with steam. In the final phase of the hot smoking a little increase of PCB compounds contents was a consequence of their penetration with smoke to the fish meat tissue.

Comparison of two sample preparation methods for analysis of organochlorine pesticides residues in fish muscle

The aim of this study was to compare recoveries of organochlorine pesticides (heptachlor, α-HCH, β-HCH, γ-HCH, op′-DDD, pp′-DDD, pp′-DDE, op′-DDT, pp′-DDT) from fish muscle dried by two alternative methods: (i) grinding with anhydrous sodium sulphate and (ii) freeze drying. Pesticide residues content was determined by gas chromatography-mass spectrometry (GS-MS) method. For four pesticides (γ-HCH, α-HCH, heptachlor and pp;-DDD) in four of five fish species, higher recoveries were obtained from the freeze-dried samples. For five remaining pesticides, correlations between fish species and drying method were not found. The results of this study do not clearly indicate which drying method caused lower losses of analytes. Recoveries from the freeze-dried samples ranged from 69.9 to 117.6 %, while recoveries from the samples ground with sodium sulphate varied from 64.4 to 126.7 %. Either of the methods gave satisfactory recoveries and they both can be used interchangeably.

Residues of some organophosphorus pesticides on and in fruits and vegetables available in Poland, an assessment based on the European union regulations and health assessment for human populations

Abstract The use of organophosphorus pesticides is undeniably beneficial in agriculture and veterinary medicine, but their excessive use can pollute the environment, as well as contaminate foodstuffs. The objective of this study was to assess contamination of vegetables and fruits available in Poland by organophosphate pesticides (ethoprophos, diazinon, chlorpyrifos, chlorpyrifos-methyl, parathion-methyl, fenchlorphos, merfos,, as well as to assess a potential health risk posed to consumers. The pesticide content was determined by gas chromatography-mass spectrometry (GC-MS). The pesticides were detected in the peel and pulp of vegetables and fruits from Polish crops, as well as imported ones. Pesticide levels in most products were higher in the peel than in the pulp. Neither chlorpyrifos-methyl nor fenchlorphos were found in the material under study. Chlorpyrifos was the pesticide occurring in the highest levels in the peel of both vegetables (31 ng · g−1 w.w.) and fruit (9.3 ng · g−1 w.w.). The Maximum Residue Level (MRL) for parathion-methyl was exceeded in some samples of zucchini pulp of Spanish origin and in the peel of potato from Poland. But levels of other pesticides in the studied vegetables and fruits were significantly lower than the current MRLs. The assessment of consumer health risk showed a significantly lower Lifetime Average Daily Dose (LADD) of pesticides under this study comparing to the Acceptable Daily Intake (ADI). Moreover, the Hazard Quotient (HQ) was low with a maximum of 3.93 × 10−2 for vegetables and 4.26 × 10−3 for fruits. These estimated HQs were within the safe acceptable limits, indicating low risk to human populations from exposure to organophosphorus pesticides in the study area. Graphical Abstract

Tracking residual organochlorine pesticides (OCPs) in green, herbal, and black tea leaves and infusions of commercially available tea products marketed in Poland

ABSTRACT The content of residual organochlorine pesticides (OCPs) was examined in green, herbal, and black tea leaves as well as in their infusions prepared from tea products marketed in the main supermarkets in Poland. It was found that the detected mean levels of organochlorine residues in tea leaves ranged from <LOD to 16.36 ng g−1 dry weight. Among hexachlorocyclohexane isomers, γ-HCH in green tea occurred in the highest concentrations. Among dichlorodiphenyltrichloroethane (DDT) metabolites the highest level of p,p′DDT (1.96 ng g−1 dw) was in green tea samples. The transfer of OCPs from tea leaves to brew was investigated. The present study revealed that during the infusion process, a significant percentage of the residues, particularly pesticides with high water solubility, were transferred to the infusions. The obtained results show that the percentage transfer of each pesticides from tea to the tea infusions ranged from 6.74% (heptachlor) to 86.6% (endrin). The detected residues were below current MRLs for these pesticides.