Marek Biziuk

Environmental Fate and Global Distribution of Polychlorinated Biphenyls

In recent decades, regulators, academia, and industry have all paid increasing attention to the crucial task of determining how xenobiotic exposures affect biota populations, communities, or entire ecosystems. For decades, PCBs have been recognized as important and potentially harmful environmental contaminants. The intrinsic properties of PCBs, such as high environmental persistence, resistance to metabolism in organisms, and tendency to accumulate in lipids have contributed to their ubiquity in environmental media and have induced concern for their toxic effects after prolonged exposure. PCBs are bioaccumulated mainly by aquatic and terrestrial organisms and thus enter the food web. Humans and wildlife that consume contaminated organisms can also accumulate PCBs in their tissues. Such accumulation is of concern, because it may lead to body burdens of PCBs that could have adverse health effects in humans and wildlife. PCBs may affect not only individual organisms but ultimately whole ecosystems. Moreover, PCBs are slower to biodegrade in the environment than are many other organic chemicals. The low water solubility and the low vapor pressure of PCBs, coupled with air, water, and sediment transport processes, means that they are readily transported from local or regional sites of contamination to remote areas. PCBs are transformed mainly through microbial degradation and particularly reductive dechlorination via organisms that take them up. Metabolism by microorganisms and other animals can cause relative proportions of some congeners to increase while others decrease. Because the susceptibility of PCBs to degradation and bioaccumulation is congener-specific, the composition of PCB congener mixtures that occur in the environment differs substantially from that of the original industrial mixtures released into the environment. Generally, the less-chlorinated congeners are more water soluble, more volatile, and more likely to biodegrade. On the other hand, high-chlorinated PCBs are often more resistant to degradation and volatilization and sorb more strongly to particulate matter. Some more-chlorinated PCBs tend to bioaccumulate to greater concentrations in tissues of animals than do low-molecular-weight ones. The more-heavily chlorinated PCBs can also biomagnify in food webs. Other high-molecular-weight congeners have specific structures that render them susceptible to metabolism by such species as fish, crustacea, birds, and mammals. In recent years, there has been substantial progress made in understanding the human health and ecological effects of PCBs and their environmental dynamics. However, risk assessments based only on the original PCB mixture that entered the environment are not sufficient to determine either (1) the persistence or toxicity of the weathered PCB mixture actually present in the environment, or (2) the risks to humans and the ecosystem posed by the weathered mixture. In this paper, we have reviewed the status of current knowledge on PCBs with regard to environmental inputs, global distribution, and environmental fate. We conclude that to know and understand the critical environmental fate pathways for PCBs, both a combination of field studies in real ecosystems and more controlled laboratory investigations are needed. For the future, both revised and new models on how PCBs behave in the environment are needed. Finally, more information on ow PCBs affect relevant physiological and behavioral characteristics of organisms tha are susceptible to contamination are needed.

Applications of sample preparation techniques in the analysis of pesticides and PCBs in food.

Pesticides and polychlorinated biphenyls (PCBs) are found in various parts of the environment in quite small concentrations, but they accumulate and thus become a threat to human health and life. A review is focused on the application of some popular techniques for sample preparation in analysis of these compounds in food. Even with the emergence of advanced techniques of final analysis, complex matrices, such as food, require extensive sample extraction and purification. Traditional sample preparation techniques are time consuming and require large amount of solvents, which are expensive, generate considerable waste, contaminate the sample and can enrich it for analytes. There have been many sample preparation techniques proposed to meet the requirements connected with the multiplicity of food. Optimal sample preparation can reduce analysis time, sources of error, enhance sensitivity and enable unequivocal identification and quantification. Sample extraction and purification techniques are discussed and their most recent applications in food analysis are provided. This review pointed out that sample preparation is the critical step.

Isolation and preconcentration of volatile organic compounds from water

Abstract Methods for the isolation and/or concentration of volatile organic compounds from water samples for trace organic analysis by gas chromatography are reviewed. The following basic groups of methods are discussed: liquid-liquid extraction, adsorption on solid sorbents, extraction with gas (gas stripping and static and dynamic headspace techniques) and membrane processes. The theoretical bases of these methods are discussed. Experimental arrangements for the isolation and/or concentration of volatile compounds from water are presented and discussed with respect to their efficiency. The applicability of the described methods to the isolation and/or concentration of various organic compounds from waters of various origins is discussed.

Solid-phase extraction clean-up of soil and sediment extracts for the determination of various types of pollutants in a single run

A new sample clean-up procedure based on solid-phase extraction (SPE) sorbents was proposed for the determination of pesticides, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in soils and sediments. The main purpose of the research was to find a combination of sorbents for the SPE method that would permit the determination of many types of analytes (polycyclic aromatic hydrocarbons, polychlorinated biphenyls, N-, P- and Cl-containing pesticides) in a single run. Elution profiles for both the analytes and the interfering components were determined for several types of SPE sorbents (alumina, silica and surface-modified silica) and combinations of them. The efficiency of the clean-up method developed was evaluated using real soil samples.

Occurrence and determination of organic pollutants in tap and surface waters of the Gdańsk district

The results of the determination of different classes of organic pollutants (trihalomethanes, polycyclic aromatic hydrocarbons (PAHs), pesticides, volatile hydrocarbons and phenols) in ground water and drinking water sampled at different sites in the Gdańsk District are presented. Different methods were used to determine organic compounds in water: direct aqueous injection or sorption on solid sorbent (XAD-4) and extraction with pentane followed by a gas chromatography-electron capture detection (GC-ECD) for determination of volatile organohalogen compounds: purge and trap with a gas chromatography-flame ionization detection for determination of volatile hydrocarbons; sorption on solid sorbent XAD-4 or C18, elution with organic solvent and GC-ECD for determination of pesticides; sorption on solid sorbent C18, elution with organic solvent and a gas chromatography-mass spectrometry for determination of PAHs and sorption on solid sorbent C18, elution with organic solvent and high performance liquid chromatography-ultraviolet determination of phenols. The proposed methods have been used successfully for the determination of organic compounds in samples of tap, swimming pool, river and sea waters. The content of analysed organic compounds in the water delivered to the water supply system for Gdańsk from the surface water intake in Straszyn and from other selected intakes satisfies Polish, EC and WHO standards. The surface water bodies, i.e., rivers, sea and lakes in the Gdańsk District are not very polluted by anthropogenic compounds originating from municipal and industrial sewages and from agriculture.

Some aspects of the analysis of environmental pollutants in sediments using pressurized liquid extraction and gas chromatography-mass spectrometry.

Pressurized liquid extraction (PLE) is a fully automated extraction technique for isolation of analytes from solid samples. This technique combines elevated temperature and pressure of liquid solvents during the extraction process. In this study the efficiency of a PLE system for the isolation of wide range of analytes (polychlorinated biphenyls and organic pesticides from sediments under different pressure and temperature conditions) was investigated. The temperature 100 degrees C and pressure 6.9 MPa (1000 p.s.i.; 1 p.s.i.=6894.76 Pa) were found to be the most efficient from all investigated conditions. Using these PLE parameters, the average recoveries for most of the analytes were in the range 80-105% and relative standard deviation was usually under 15%. The conditions of determination of analytes in the extracts using GC-MS were established. Some problems occurring during the analysis of real samples, such as coelution of analytes, were established. The influence of internal standard addition on the final analysis results was determined.

Multi-residue method for the determination of 16 recently used pesticides from various chemical groups in aqueous samples by using DI-SPME coupled with GC-MS.

A simple and solvent-free multi-residue method has been optimized to determine 16 currently used pesticides from different chemical groups in aqueous samples. The extraction of analytes was carried out with direct immersion solid-phase microextraction (DI-SPME) and for the identification and quantitative determination gas chromatography coupled with mass spectrometry (GC-MS) was applied. Two commonly used adsorbent coatings have been applied and compared: 100 μm of polydimethylsiloxane (PDMS) and 85 μm of polyacrylate (PA). The method development parameters of DI-SPME, analyte desorption and GC-MS analysis have been outlined along with the final experimental conditions. When the optimum extraction conditions were applied (extraction time 60 min, 10% (w/v) NaCl solution, 45°C) the limits of detection (LODs) were in the range of 0.015-0.13 μgL(-1) and the relative standard deviations (RSDs) were between 1.9 and 9.6%. The developed analytical method was successfully applied to the analysis of natural water samples from the following sources: river, sea, canal and rain.

Prenatal exposure to substance of abuse: a worldwide problem.

Substance abuse during pregnancy is an important public health issue affecting the mother and the growing infant. Preterm labor, miscarriage, abruption and postpartum hemorrhage are obstetric complications which have been associated with women who are dependent on abused substances. Moreover, women are also at an increased risk of medical problems such as poor nutrition, anemia, urinary tract infections as well as sexually transmitted infections, hepatitis, HIV and problems related to infection. Intrauterine growth restriction, prematurity, stillbirth, neonatal abstinence syndrome, and Sudden Infant Death Syndrome represent only some of fetal effects. Later on, during childhood, it has been shown that in utero exposure to substances of abuse is associated with increased rates of respiratory infections, asthma, ear and sinus infections. Moreover, these children are more irritable, have difficulty focusing their attention, and have more behavioral problems. Therefore, the assessment of in utero exposure to abused substance is extremely necessary and is relevant for the care of the mother and the offspring. In this sense, several approaches are possible; however, recently the evaluation of in utero exposure to abused drugs has been achieved by testing biological specimens coming from fetus or newborn, pregnant or nursing mother, or from both the fetus and the mother. Maternal and neonatal biological materials reflect exposure in a specific time period and each of them has different advantages and disadvantages in terms of accuracy, time window of exposure and cost/benefit ratio. The methodology for identification and determination of abused substances in biological materials are of great importance. Consequently, sensitive and specific bioanalytical methods are necessary to accurately measure biomarkers. Different immunoassays methods are used as screening methods for drug testing in the above reported specimens, however, the results from immunoassays should be carefully interpreted and confirmed by a more specific and sensitive chromatographic methods such as GC-MS or LC-MS. The interest in the development and optimization of analytical techniques to detect abused substances in different specimens is explained by the several possibilities and information that they can provide.

Methods of isolation and determination of volatile organohalogen compounds in natural and treated waters

Volatile organohalogen environmental pollutants and their sources and the routes of entry into various elements of the environment are described. Comprehensive literature data on the concentrations of these pollutants in natural and treated waters and in wastewaters in various countries are tabulated and discussed. A wide selection of the techniques for the isolation and preconcentration of the above pollutants are presented and discussed. Direct aqueous injection into a capillary column, liquid-liquid extraction, solid-phase extraction and headspace analysis are emphasized.

Green Aspects of Techniques for the Determination of Currently Used Pesticides in Environmental Samples

Pesticides are among the most dangerous environmental pollutants because of their stability, mobility and long-term effects on living organisms. Their presence in the environment is a particular danger. It is therefore crucial to monitor pesticide residues using all available analytical methods. The analysis of environmental samples for the presence of pesticides is very difficult: the processes involved in sample preparation are labor-intensive and time-consuming. To date, it has been standard practice to use large quantities of organic solvents in the sample preparation process; but as these solvents are themselves hazardous, solvent-less and solvent-minimized techniques are becoming popular. The application of Green Chemistry principles to sample preparation is primarily leading to the miniaturization of procedures and the use of solvent-less techniques, and these are discussed in the paper.