Decabromodifenyl Ether (BDE-209) in Surface Soils from Warsaw and Surrounding Areas: Characterization of Non-Carcinogenic Risk Associated with Oral and Dermal Exposure.

Polybrominated diphenyl ethers (PBDEs) have been used for many years as flame retardants. Due to their physicochemical and toxicological properties, they are considered to be persistent organic pollutants (POPs). BDE-209 is the main component of deca-BDE, the one PBDE commercial mixture currently approved for use in the European Union. The aim of this study was to analyse BDE-209 in surface soil samples from Warsaw and surrounding areas (Poland) as an indicator of environmental pollution with PBDEs, and to characterise the associated health risk. A total of 40 samples were analysed using gas chromatography with electron capture detection (GC-µECD). Concentrations of BDE-209 in soil ranged from 0.4 ng g-1 d.w. (limit of quantification) to 158 ng g-1 d.w. Overall, 52.5% of results were above the method's limit of quantification. The highest levels were found at several locations with heavy traffic and in the vicinity of a CHP plant in the city. The lowest concentrations were observed in most of the samples collected from low industrialized or green areas (<0.4 to 1.68 ng g-1 d.w.). Exposure to BDE-209 was estimated for one of the most sensitive populations, i.e., young children. The following exposure routes were selected: oral and dermal. No risk was found to young children's health.

Validation of a Modified QuEChERS Method for the Determination of Selected Organochlorine Compounds in Honey.

Honey is considered to be a health-promoting food product. Therefore, it is assumed that it should be free of contaminants. Although the use of organochlorine pesticides (OCPs) was banned a few decades ago in developed countries, persistent organic pollutants (POPs) are still detected in various environmental and biological matrices, including food. These contaminants exhibit toxic properties and bioaccumulate in some food chains. The validation of a modified QuEChERS extraction method was successfully performed for o,p'-DDT, o,p'-DDE, o,p'-DDD, p,p'-DDT, p,p'-DDE, p,p'-DDD, heptachlor and dieldrin. 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153) was used as an internal standard. The modification involved changing the solvent from acetonitrile to n-hexane after extraction. Quantitation was carried out using gas chromatography with an electron capture detector (µECD). The mean recovery values for o,p'-DDT, o,p'-DDE, o,p'-DDD, p,p'-DDT, p,p'-DDE, p,p'-DDD and dieldrin, spiked at 2.9 ng/g and 20 ng/g, ranged from 64.7% to 129.3%, and, for heptachlor spiked at 5.6 ng/g and 20 ng/g, ranged from 68.0% to 88.3%. The relative standard deviation (RSD) for these concentrations did not exceed 20%, and the within-laboratory reproducibility was below 20%, except o,p'-DDE and p,p'-DDT, which were 25.2% and 20.7%, respectively. This modified QuEChERS extraction method for selected organochlorine compounds was demonstrated as effective for routine testing in honey.

Hypomethylation of the c-myc promoter region induced by phenobarbital in rat liver

Background: The changes in DNA methylation are considered as one of the early events in hepatocarcinogenesis. Objective: We evaluated the ability of phenobarbital (PB) ­ the most widely used anticonvulsant worldwide and classical rodent liver carcinogen ­ to cause the promoter region of the c-myc protooncogene hypomethylation as well as changes of mRNA level of this gene. Moreover, the expression of Dnmt1 protein in rat treated with this compound was analyzed. Material and Methods: Male Wistar rats received PB in daily oral doses of 92.8 mg kg-1 b.w. day-1 (at 24-h intervals; for one, three and fourteen days). Methylation of the c-myc promoter region was measured by PCR-based methylationsensitive restriction enzyme analysis (MSRA). Levels of mRNA for c-myc and protein Dnmt1 were assayed using Real-Time PCR and Western Blot, respectively. Results: The study showed that phenobarbital stimulated persistent changes in DNA methylation, i.e. loss of methylation in the promoter region of the c-myc gene and up-regulated its mRNA level. In addition, a significant increase in protein level of Dnmt1 in the c-myc over-expressing liver cells was observed. Conclusion: The oppose relationship between Dnmt1 activity and methylation status of c-myc gene was demonstrated. The c-myc over-expression by demethylation might represent an important, early events in the mechanism of action (MOA) of phenobarbital.

Validation of the analytical method for the simultaneous determination of selected polybrominated diphenyl ethers, polychlorinated biphenyls and organochlorine pesticides in human blood serum by gas chromatography with microelectron capture detector.

BACKGROUND: Polybrominated diphenyl ethers (PBDEs) as other persistent organic pollutants like polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) pose a significant hazard to human health, mainly due to interference with the endocrine system and carcinogenetic effects. Humans are exposed to these substances mainly through a food of animal origin. These pollutants are globally detected in human matrices which requires to dispose reliable and simple analytical method that would enable further studies to assess the exposure of specific human populations to these compounds. OBJECTIVE: The purpose of this study was to modify and validate of the analytical procedure for the simultaneous determination of selected PBDEs, PCBs and OCPs in human blood serum samples. MATERIAL AND METHODS: The analytical measurement was performed by GC-µECD following preparation of serum samples (denaturation, multiple extraction, lipid removal). Identity of the compounds was confirmed by GC-MS. RESULTS: The method was characterised by the appropriate linearity, good repeatability (CV below 20%). The recoveries ranged from 52.9 to 125.0% depending on compound and level of fortification. The limit of quantification was set at 0.03 ng mL(-1) of serum. CONCLUSIONS: The modified analytical method proved to be suitable for the simultaneous determination of selected PBDEs, PCBs and OCPs in human blood serum by GC-µECD with good precision.

Risk assessment for pesticides' MRL non-compliances in Poland in the years 2011-2015.

BACKGROUND: Human exposure to trace levels of pesticide residues present in food of plant origin is inevitable as long as pesticides continue to be applied in agriculture. Since Maximum Residue Levels (MRL) are not toxicological endpoint values, their violation is not by default equivalent to health risk for consumers. However, its essential to provide a health- based risk assessment for each case of MRL non-compliance reported during monitoring and official control of foodstuffs. OBJECTIVE: To assess the potential short-term risk associated with consumption of food products of plant origin containing pesticide residues above MRL values based on notifications forwarded by the National Contact Point for RASFF in Poland during 2011-2015. MATERIAL AND METHODS: 115 notifications including 127 analytical results non-compliant with respective MRL values were forwarded to provide risk assessment. An internationally accepted deterministic approach based on conservative model assumptions for short-term exposure assessment was applied. The risk was characterized by comparing an estimated dietary intake with respective acute reference dose (ARfD). RESULTS: Black currant, tea, lettuce, Chinese cabbage and carrot were among the most frequently notified products in years 2011-2015. Among pesticides exceeding respective MRL values, over 90% belonged to fungicides and insecticides/acaricides such as acetamiprid, chlorpyrifos, dimethoate, imidacloprid, dithiocarbamates and procymidone. For 15 and 6 results noncompliant with respective MRL value, a predicted short-term intake exceeded ARfD for children and adults, respectively. CONCLUSIONS: Residue levels that could potentially pose a health threat are found incidentally. The science-based and transparent risk assessment process with regard to the data, methods and assumptions that are applied is essential to risk management authorities. KEY WORDS: risk assessment, pesticide residues, MRL, dietary intake, RASFF, food safety.

Development and validation of a method for determination of selected polybrominated diphenyl ether congeners in household dust.

BACKGROUND: Polybrominated diphenyl ethers (PBDEs) belong to group of so-called persistent organic pollutants (POPs). These compounds occur in nearly all elements of the environment, including household dust which constitutes one of a major route for human exposure. Their main adverse effects on human health are associated mainly with endocrine disruption--they interfere with thyroid function exhibit anti-androgenic action. OBJECTIVES: To develop and validate analytical method for determination of BDE-47, BDE-99, BDE-153, and BDE-209 congeners in household dust. MATERIAL AND METHODS: Household dust was sampled in residences from Warsaw and the surrounding areas. An automated Soxhlet extraction of samples was then performed and PBDE congeners were subsequently measured in cleaned-up extracts by GC-microECD. The identity of quantified compounds was confirmed by GC/MS. RESULTS: Household dust samples were fortified at levels of 2.88, and 28.8 ng g(-1) for BDE-47, BDE-999, and BDE-153, and for BDE-209 at levels of 101.2, and 540 ng g(-1). Recoveries ranged between 72 - 106%. The relative standard deviations (RSD) were less than 16% for all PBDE congeners analysed. The relative error determined on the basis of multiple analyses of certified reference material ranged from 1.07 - 20.41%. The method's relative expanded uncertainty varied between 16 - 21%. CONCLUSION: The presented method was successfully validated and can be used to measure concentrations of BDE-47, BDE-99, BDE-153 and BDE-209 congeners in household dust.

Assessment of Furan and Its Derivatives Intake with Home Prepared Meals and Characterization of Associated Risk for Polish Infants and Toddlers.

Furan and its derivatives are found in various heat-treated foods. Furan is classified as a possible human carcinogen. The European Union authorities recommend collecting data on the occurrence of these compounds, estimating consumer exposure, and taking measures to protect human health based on a scientific risk assessment. The aim of this study was to estimate the exposure of infants and toddlers to furan and its methyl derivatives-2-methylfuran, 3-methylfuran, and ∑2,5-dimethylfuran/2-ethylfuran-present in home-prepared foods and to characterize the associated health risks. The compounds of interest were determined using the HS-GC/MS. The risk was characterized by the calculation of the margin of exposure (MoE). Levels of furan and its derivatives in analyzed samples were in the range of

[Indoor dust as a pathway of human exposure to polybrominated diphenyl ethers (PBDEs)]. / Kurz zródlem narazenia czlowieka na polibromowane difenyloetery (PBDE).

The brominated diphenyl ethers (PBDEs) belong to a class of synthetic, additive brominated flame retardants (BFRs). PBDEs are used to reduce the flammability of commercial and household products such as textiles, various plastic polymers, furnishing foam, and electronic equipment. People spend a large percentage of their life-time indoors at home, in offices and cars, etc, providing many opportunities for lengthy exposure to PBDEs from residential settings and commercial products in an indoor environment. In recent time, the foodstuffs, mainly food of animal origin, have been indicated as the main pathway of human exposure to PBDEs. However, many studies have shown that the indoor environment, mainly indoor dust, can be also a significant source of exposure to PBDEs, especially for younger children (toddlers) because of their behavioral patterns, eg. putting fingers, toys, and other items in their mouth. Numerous studies show that the median intakes of PBDEs via dust for adult range from 1.41 to 277 ng x day(-1) is lower than that via food which range from 135 to 333 ng x day-', while the median intake of these compounds via indoor dust for children range from 101 to 404 ng x day(-1) is much higher than via food: 77-190 ng x day(-1). The congener pattern observed in the indoor dust is different to that found in food. The indoor dust is dominated by the congener BDE-209 vs. food where the most dominated congeners are BDE-47 and BDE-99. Human exposure to PBDEs and other brominated flame retardants (BFRs) is widely widespread throughout the world and it depends on a country range of usage, production and legislation concerning these chemicals as well as a citizen's behavior. Generally, human exposure has been found higher in North America than in Europe and Asia. Within European countries the significant highest concentrations in dust have been found in the United Kingdom. It should be noted that many uncertainty factors such as personal habits, dietary preferences, and time spent in various rooms, cars and outdoors could affect the exposure assessment. In some cases the occupational exposure is the most important source of PBDEs for adults, for example air crews, car sale employees and disposal/recycling of electronic waste workers.

Risk assessment for infants exposed to furan from ready-to-eat thermally processed food products in Poland.

BACKGROUND: Thermal processes and long storage of food lead to reactions between reducing sugars and amino acids, or with ascorbic acid, carbohydrates or polyunsaturated fatty acids. As a result of these reactions, new compounds are created. One of these compounds having an adverse effect on human health is furan. OBJECTIVE: The aim of this paper was to estimate the infants exposure to furan found in thermally processed jarred food products, as well as characterizing the risk by comparing the exposure to the reference dose (RfD) and calculating margins of exposure. MATERIALS AND METHODS: The material consisted of 301 samples of thermally processed food for infants taken from the Polish market in years 2008 - 2010. The samples included vegetable-meat, vegetables and fruit jarred meals for infants and young children in which the furan levels were analyzed by GC/MS technique. The exposure to furan has been assessed for the 3, 4, 6, 9,12 months old infants using different consumption scenarios. RESULTS: The levels of furan ranged from <1 microg/kg (LOQ) to 166.9 microg/kg. The average furan concentration in all samples was 40.2 microg/kg. The estimated exposures, calculated with different nutrition scenarios, were in the range from 0.03 to 3.56 microg/kg bw/day and exceeded in some cases RfD set at level of 1 microg/kg bw/day. Margins of exposure (MOE) achieved values even below 300 for scenarios assuming higher consumption of vegetable and vegetable-meat products. CONCLUSIONS: The magnitude of exposure to furan present in ready-to-eat meals among Polish infants is similar to data reported previously in other European countries but slightly higher than indicated in the recent EFSA report. As for some cases the estimated intake exceeds the RfD, and MOE) values are much lower than 10000 indicating a potential health concern, it is necessary to continue monitoring of furan in jarred food and estimate of its intake by infants.

[Dioxins and food safety]. / Dioksyny a bezpieczenstwo zywnosci.

Among numerous potential chemical food contaminants, polychlorinated dibenzo-p-dioxins, dibenzofurans and dioxin-like polychlorinated biphenyls, collectively referred as dioxins, are commonly considered as bearing substantial risk for human health due to their toxicological properties, persistency and ability to bioaccumulate in food chains. The results of epidemiological studies suggest that environmental exposure to these compounds may affect multiple physiological processes in humans, mainly by the mechanism of endocrine disruption. Adverse health effects linked to the long-term exposure to dioxins include the increase of cancer risk, reproductive and developmental impairment as well as effects on immune functions. Exposure through food (mainly of animal origin) is the major source of dioxin exposure for humans, estimated to account for about 95% of the total intake for non-occupationally exposed persons. Recent studies showed that a consistent part of the European population has an intake exceeding internationally agreed "safe" doses as the Tolerable Daily or Weekly Intake (TDI, TWI). It is worthy to note that percentage of persons with estimated dioxin intake above tolerable limits is much higher among children than in adults. Since the "Belgian dioxin crisis" that occurred in 1999, the estimation of human exposure to these compounds and related consumer risk assessment has been recognized in the European Union as one of the priority activities in the field of food safety. Among activities undertaken by the European Commission during implementation of the Community Strategy for dioxins, furans and polychlorinated biphenyls the maximum and action levels have been established with random monitoring by Member States. The legislation on the requirements for sampling and methods of analysis used in the official control laboratories has been set up as well. Member States are obliged to measure background levels of dioxins and dioxin-like PCBs in defined food categories for the EU monitoring program on a yearly basis and to forward the results to the European Commission (since 2008 to the European Food Safety Authority). The monitoring results, covering samples collected from 1999 to 2008, evaluated and reported recently by EFSA, became the basis for updating maximum levels of dioxins and dl-PCBs as set up in Commission Regulation (EC) 1881/2006. The legislation will also be changed by replacing the current toxicity equivalency factors (TEFs) system from 1998 (WHO,1998-TEFs) by a new TEFs proposed by the WHO in 2005 (WHO 2005-TEFs). It is expected that new limits for dioxins and dl-PCBs in food will come into force not later than in the beginning of 2012.

[Ubiquitous perfluorinated compounds]. / Wszechobecne zwiazki perfluorowane.

Perfluorinated compounds are derivatives of hydrocarbons, in which all or most of hydrogen atoms are substitiuted by fluorine atoms. These compounds are commonly used in many branches of industry. Perfluorinated compounds are in the limelight because of numerous reports concerning their toxicity and negative effects on human health as well as contradictory information about their cancerogenic effect. The above compounds are used in production of many commonly used products including such brand names as Gore-Tex, Teflon, Stainmaster. The most common ways of penetrating these compounds into a human organism are: via food, inhalation and skin contact. Perfluorooctanesulfonate (PFOS) has been added to the list of persistent organic pollutants (POPs).

[Application of the quechers method coupled with gas chromatography with electron capture detection (GC-ECD) in analysis of pesticide residues in food]. / Zastosowanie metody QuEChERS w polaczeniu z chromatografia gazowa z detektorem wychwytu elektronów (GC-ECD) w analizie pozostalosci pestycydów w zywnosci.

In 2003 Anastassiades and Lehotay described the "quick, easy, cheap, effective, rugged and safe" (QuEChERS) method for the multi-class, multiresidue analysis of pesticides in fruit and vegetables. The QuEChERS method allows to obtain high quality results with a minimum number of steps and a low solvent and glassware consumption. The QuEChERS method based on liquid-liquid partitioning with acetonitrile followed by a cleanup step with dispersive-SPE (Solid Phase Extraction). The aim of this study was to check the usefulness of the QuEChERS method coupled with gas chromatography with electron capture detection (GC-ECD) in analysis of pesticide residues in food. Ready-to-use QuEChERS reagents kits and own-weighed reagents have been applied. In recovery experiment for 15 selected pesticides, three matrices belonging to different groups--carrots (high carotenoids content), raspberry (highly acidic matrix) and tomatoes (high water content)--have been used, according to the SANC0/10684/2009 guideline and PN-EN 15662:2008 requirements. Fourteen compounds showed a recovery in the range of 70-120% and only one compound (trifluralin in raspberry) presented a recovery lower than 70% at the 0.5 mg/kg fortification level. The repeatability was satisfying with a RSD lower than 20% apart from trifluralin in raspberry (27.16%).

[Organohalogen compounds--new and old hazards for people]. / Zwiazki halogenorganiczne --stare i nowe zagrozenia]

The organohalogen compounds (OCs, PCBs, PBDEs) are persistent organic pollutants (POPs) that have a widespread distribution in the environment. Their chemico-physical stability and lipophylic properties are responsible for their accumulation in the human body. The general human population is exposed to PCBs and OCs through foodstuffs, mainly food of animal origin. However the main source of the human exposure to PBDEs are also food and inhalation of dust or respirable phase of the indoor air The POPs from this group are present on different levels in human tissues (fat tissue, liver; placenta), and even in human blood and breast milk. The organohalogen compounds may cause endocrine disrupting (ED) effects as they have been shown to interact as antagonists or agonists with androgen, progesterone, and estrogen receptors. Most of them shows antiandrogenic, estrogenic and antiestrogenic activity.

[The role and tasks of the National Reference Laboratory in the scope of pesticide residues in food]. / Rola i zadania krajowego laboratorium referencyjnego w zakresie pozostalossci pestycydów w zywnosci.

The Member States are obliged to establish the specific programmes and the control systems ensuring that food products placed on the market are safe for the consumer In Poland, the official food control laboratories of the State Sanitary Inspection carry out the analysis of food contaminants, including pesticide residues. Those laboratories closely cooperate with the National Reference Laboratories (NRLs). They are also receiving necessary technical assistance from NRLs.

Alternative toxicological methods for establishing residue definitions applied for dietary risk assessment of pesticides in the European Union.

Consumers are constantly exposed to trace levels of residues present in food commodities, arising from the use of pesticides. For this reason, assessing the risk caused by pesticide residues present in food requires not only identification and toxicological properties assessment of the active substance, but also of its metabolites, isomers, and degradates. This requires the use of many laboratory animals. On the other hand, currently there is an emphasis on minimizing the use of animals in toxicological research. This review article presents current activities of the European Food Safety Authority (EFSA) and the European Commission's Joint Research Centre (JRC) aiming to replace at least a part of toxicological tests on substances of unknown toxicity with the alternative methods. Quantitative Structure-Activity Relationship (QSAR) and Threshold of Toxicological Concern (TTC) can be used for this purpose in procedure of establishing residue definitions applied for dietary risk assessment.

A novel method for rapid and quantitative detection of bisphenol A in urine.

Bisphenol A (BPA) is classified as an endocrine disruptor (ED) and it can interact with variety of hormone receptors leading to hormonal disruption and increased risk of various adverse health effects. Reducing human exposure to BPA is one of the main challenges of public health, as it is constantly present in daily life. A low-cost and commonly applied method to enable determination of BPA in the patient's body has yet to be developed. Currently available techniques are expensive, time-consuming, and require access to highly equipped analytical chemistry laboratories. Here we describe a fast and cheap engineered lateral flow assay of our design, to detect of BPA in urine samples. The technology not only provides an opportunity to perform rapid medical diagnostics without the need for an access to the central laboratory but also a means for self-diagnosis by the patient. The addition of ß-glucuronidase improves the sensitivity of detection as it releases the free BPA from glucuronide complexes in urine. This invention may become a demonstrated analytical means for lowering human exposure to BPA and probably also to other EDs and consequently, may be useful in decrease of the risk for several lifestyle diseases.

[Nanotechnology--possibilities and hazards]. / Nanotechnologia--mozliwosci i zagrozenia.

Nanoparticles are the objects with at least one demension smaller than 100 nm. Nanoparticles exist in nature or can be produced by human activities, intentionally or unintentionally. Nanotechnology is an emerging science involving manipulation of matter at nanometer scale. Nanoparticles find numerous applications in many fields, starting with electronics, throught medicine, cosmetology, and ending with automotive industry and construction industry. Depending on the use of nanoparticles, the routes of exposure may be inhalation, dermal, oral or parenteral. Nanoparticles have a greater active surface area per unit mass than larger particles. Together with an increase of surface area, toxicity and potential health effects may also increase. Toxicity of nanoparticles depend on many factors, for example: size, shape, chemical composition, solubility, surface area and surface charge. Risk assessment related to human health, should be integrated at all stages of the life cycle of the nanotechnology, starting at the point of conception and including research and development, manufacturing, distribution, use and disposal or recycling.

[The survey of pesticide residues in food of plant origin in Poland, 2004-2007]. / Badania pozostalosci pestycydów w zywnosci pochodzenia roslinnego w Polsce w latach 2004-2007.

The Member States of the European Union are obliged to provide the official food control. For the pesticides, each country develops the monitoring and official control of pesticide residues in food on the market. In Poland, as in the other Member States, the monitoring of pesticide residues in food and official control are performed in order to check compliance with the Maximum Residue Levels (MRLs). In 2004-2007 the total number of samples analyzed in monitoring and official control of pesticide residues in foodstuffs of plant origin in Poland was 5340. Those were 1419 samples of fruit, 2383 samples of vegetables, 561 samples of cereal crops, 371 samples of processed products, and 509 samples of baby food During those four years residues above the MRLs were detected in 116 samples. The number of exceedances of MRLs was higher in domestic food products, which equaled 90% of analyzed samples.

[Analysis of scientific background of establishing definitions for Maximum Residue Levels (MRLs)]. / Analiza podstaw naukowych ustalania definicji Najwyzszych Dopuszczalnych Poziomów Pozostalosci pestycydow (NDP).

For each pesticide used in food or feed productions, the legislative authorities have to establish the residue definitions, that mean compounds which need to be taken into account in risk assessment in process of authorization of plant protection products as well as in establishing and enforcing Maximum Residue Levels (MRLs). The residue definition for a given pesticide can be different depending on the aim for which they are used. Inclusion of a compound in such definition results in consequence in its later analysis in different matrices during monitoring and official control. Inclusion of compounds in the definition depends on a number of factors, and the decisions on whether they should be included have to be made for every case separately. The definition should include toxicologically important compounds, and those which contribute into the residue in 10 or more percent of TRR, or those that have been detected in livestock and plants as metabolites different than those found in rats.

[The application of statistical methods in chemical experiments]. / Zastosowanie metod statystycznych w badaniach chemicznych.

Quality of the analyzed data has a major impact on reliability of the results. Application of statistical methods allows to reduce some stages of chemist's work, for example classification of the numerous data sets. The statistical methods are applied for preliminary evaluation of the data quality. In this case it is necessary to verify that the raw data base does not include large errors or outliers, which could influence the result of experiment. Data analysis, which is performed by chemometric techniques, rely on finding the most correlated attributes. Chemometry is used towards creation of the mathematical model of relation between analyzed property and numerous sets of described variables (parameters which affect measure). Modeling requires calculations towards model identification, checking its relevance, evaluation of the adequacy and determination of model's prognostic ability. The obtained model of relation could be used for the system optimization in the technological process, forecasting the values subsidiary conditioned upon known values described, also for control of the analytical system. The statistical methods are applied in chemical studies for data collection and analysis of chemical compounds for more efficient management of flow of the information. They allow to foreseen physical and biological properties of chemical compounds. The statistical methods are also applied for quality management in chemical analysis of contaminants including pesticide residues in foodstuff.