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This study describes the synthesis of a novel polymer (polypyrrole-polythiophene) coated magnetic porous carbon (MPC) composite derived from magnetic metal-organic framework (MOF) and its utilization in multi-target environmental pollutants preconcentration. In this regards, Fe 3 O 4 nanoparticles (NPs) was used as magnetic core and Co-MOF-71 was coated on the surface of the NPs. Afterwards, magnetic MOF (MMOF) was carbonized under nitrogen atmosphere and finally MNC was coated with a polymer layer of the type polypyrrole-polythiophene to obtain the nanocomposite (MPC@PPy-PTh). Magnetic property, structure and morphology of MPC@PPy-PTh were explored via various characterization techniques. Applicability of MPC@PPy-PTh nanoadsorbent was investigated in multi-target environmental pollutants preconcentration using 4-chlorophenol 2-naphtol, 1-amino-2-naphthol, 2,4-dichloroaniline, 3,4-dichloroaniline, benzothiophene and naphthalene as the model analytes. Effect of experimental factors on the preconcentration of target pollutants was explored and optimized systematically. Under the optimized condition, LODs were obtained in the range of 0.06-0.18 µg L -1 . The proposed method exhibited linearity within the range of 0.25-500 µg L -1 . Repeatability of the new method based on the relative standard deviations (n = 5) was in the range of 3.4-9.0%. Finally, the analytical applicability of the optimized method was investigated in seawater and wastewater samples and satisfactory results were achieved., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Plastic pollution is a defining environmental contaminant and is considered to be one of the greatest environmental threats of the Anthropocene, with its presence documented across aquatic and terrestrial ecosystems. The majority of this plastic debris falls into the micro (1 μm-5 mm) or nano (1-1000 nm) size range and comes from primary and secondary sources. Its small size makes it cumbersome to isolate and analyze reproducibly, and its ubiquitous distribution creates numerous challenges when controlling for background contamination across matrices (e.g., sediment, tissue, water, air). Although research on microplastics represents a relatively nascent subfield, burgeoning interest in questions surrounding the fate and effects of these debris items creates a pressing need for harmonized sampling protocols and quality control approaches. For results across laboratories to be reproducible and comparable, it is imperative that guidelines based on vetted protocols be readily available to research groups, many of which are either new to plastics research or, as with any new subfield, have arrived at current approaches through a process of trial-and-error rather than in consultation with the greater scientific community. The goals of this manuscript are to (i) outline the steps necessary to conduct general as well as matrix-specific quality assurance and quality control based on sample type and associated constraints, (ii) briefly review current findings across matrices, and (iii) provide guidance for the design of sampling regimes. Specific attention is paid to the source of microplastic pollution as well as the pathway by which contamination occurs, with details provided regarding each step in the process from generating appropriate questions to sampling design and collection.

Marine pollution and monitoring have received more and more concern in recent years. Herein, a fully automatic whole-algae biosensor was designed for low-cost and fast detection of toxic contaminants in seawater. It consists of a digital microfluidic (DMF) diluter chip, an actuation element, a detector element, and a microalgae bioreporter. A feedback-control protocol based on charging-time compensation was introduced. It ensures precise actuation of the droplet with diverse salty concentrations and contents in the marine environment. The two-mixer cross-split dilution engine increases the accuracy of droplet dispensing and concentration diluting. By selecting motility of P. subcordiformis as the sensor signal, the developed biosensor showed good sensitivity and robustness for a wide range of salinity (10-37‰), temperature (0-25 °C), light levels (0-325 μmol photons m -2 s -1 ), and cell density factor (1.0-4.0). The biosensor responses were examined in the presence of copper, lead, phenol, and nonylphenol (NP). In all cases, toxic responses (i.e. dose-related inhibition of algal motion) were detected with the detection limits of 0.65  μmol.L -1 , 1.90  μmol.L -1 , 2.85 mmol.L -1 , and 5.22  μmol.L -1 respectively. These results were obtained in a much shorter time (2 h for our biosensor vs. 24 h-10 d for growth inhibition test) and the data are consistent with previous classical studies. We thus developed a simple, rapid, and adaptable system for marine routine monitoring and early-warning detection for lab and on-site applications., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In the present work, a structure-based design approach was used for the generation of a novel variant of synthetic glutathione transferase (PvGmGSTU) with higher sensitivity towards pesticides. Molecular modelling studies revealed Phe117 as a key residue that contributes to the formation of the hydrophobic binding site (H-site) and modulates the affinity of the enzyme towards xenobiotic compounds. Site-saturation mutagenesis of position Phe117 created a library of PvGmGSTU variants with altered kinetic and binding properties. Screening of the library against twenty-five different pesticides, showed that the mutant enzyme Phe117Ile displays 3-fold higher catalytic efficiency and exhibits increased affinity towards α-endosulfan, compared to the wild-type enzyme. Based on these catalytic features the mutant enzyme Phe117Ile was explored for the development of an optical biosensor for α-endosulfan. The enzyme was entrapped in alkosixylane sol-gel system in the presence of two pH indicators (bromocresol purple and phenol red). The sensing signal was based on the inhibition of the sol-gel entrapped GST, with subsequent decrease of released [H + ] by the catalytic reaction, measured by sol-gel entrapped indicators. The assay response at 562 nm was linear in the range pH = 4-7. Linear calibration curves were obtained for α-endosulfan in the range of 0-30 μΜ. The reproducibility of the assay response, expressed by relative standard deviation, was in the order of 4.1% (N = 28). The method was successfully applied to the determination of α-endosulfan in real water samples without sample preparation steps., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Persistent organic pollutants (POPs) are dangerous and toxic pollutants that may cause adverse effects on human and animal health, including death. POPs such as polychlorinated biphenyls (PCBs) and pesticides are subtly released into the environment from industrial and agricultural use. Global circulation is due to their trans-boundary transport capacity, contingent on aerodynamic and hydrological properties. Plants have capacity to take-up POPs, and these bio-magnify along heterotrophic transfer pathways. In this study, levels of selected 6-PCB congeners and 3- DDTs in some leaf and root vegetables were investigated. Leaf and root vegetables were collected from different horticultural farms areas in Cape Town. The 6-PCBs and 3-DDTs were recovered from the samples using solid phase extraction(SPE), followed by GC-MS analysis. The ΣPCBs and ΣDDT (on-whole basis), were ranged: 90.9-234 ng/g and 38.9-66.1 ng/g respectively. The 3-PCBs and 6-DDTs levels were slightly higher in leaf vegetables compared to root vegetables. The detection of PCBs and DDTs in the vegetables suggest the probable use of PCBs containing pesticides. Although the observed concentrations were below the WHO maximum residue limits, consumption of such contaminated leaf and root vegetables portend a health risk.

High throughput screening (HTS) projects like the U.S. Environmental Protection Agency's ToxCast program are required to address the large and rapidly increasing number of chemicals for which we have little to no toxicity measurements. Concentration-response parameters such as potency and efficacy are extracted from HTS data using nonlinear regression, and models and analyses built from these parameters are used to predict in vivo and in vitro toxicity of thousands of chemicals. How these predictions are impacted by uncertainties that stem from parameter estimation and propagated through the models and analyses has not been well explored. While data size and complexity makes uncertainty quantification computationally expensive for HTS datasets, continued advancements in computational resources have allowed these computational challenges to be met. This study uses nonparametric bootstrap resampling to calculate uncertainties in concentration-response parameters from a variety of HTS assays. Using the ToxCast estrogen receptor model for bioactivity as a case study, we highlight how these uncertainties can be propagated through models to quantify the uncertainty in model outputs. Uncertainty quantification in model outputs is used to identify potential false positives and false negatives and to determine the distribution of model values around semi-arbitrary activity cutoffs, increasing confidence in model predictions. At the individual chemical-assay level, curves with high variability are flagged for manual inspection or retesting, focusing subject-matter-expert time on results that need further input. This work improves the confidence of predictions made using HTS data, increasing the ability to use this data in risk assessment., Competing Interests: The authors have declared that no competing interests exist.

While reversed-phase (RP) liquid chromatography can separate a wide range of analytes, for strongly acidic compounds such as environmentally relevant dialkyl phosphates (DAPs), this remains a challenge because they have low affinity for standard RP columns or they exhibit inferior peak shapes. Mixed-mode chromatographic (MMC) columns, which contain both RP and ion-exchange functionalities, can address these resolution problems. However, using current MMC separation approaches, analyte peaks are relatively broad as compared to conventional RP chromatography. Herein we present an enhanced MMC-based UHPLC/ESI-MS method for the analysis of DAPs. In contrast to commonly available MMC-based methods, we applied the MMC Luna ® Omega PS C18 column that was conditioned by 0.1% formic acid and equilibrated with the initial mobile phase before sample injection. This conditioning step tremendously improved the retention and separation of the DAPs, especially for those with high water solubility and shorter carbon chain lengths. Using water/methanol (95 v/5 v) and ammonium acetate in methanol as the mobile phases, nine DAPs could be baseline resolved with very sharp peaks, including the shorter-chain dimethyl phosphate, diethyl phosphate and bis(2-chloroethyl) phosphate. Other columns were examined to facilitate method optimization, and to identify stationary phases with the ability to separate DAPs as well as to elucidate the retention and separation mechanisms. With this novel UHPLC and post-column dication ion-pairing ESI-MS/MS method, instrumental detection limits as low as 0.01 ng/mL level were achieved. Representing other strongly acidic analytes, the short-chain perfluoroalkyl acid, perfluorobutyl sulfonic acid could also be analyzed with this method., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Up to now, knowledge of enzymes capable of degrading various contaminants of emerging concern (CEC) is limited, which is especially due to the lack of rapid screening methods. Thus, a miniaturized high-throughput setup using a chip-based robotic nanoelectrospray ionization system coupled to mass spectrometry has been developed to rapidly screen enzymatic reactions with environmentally relevant CECs. Three laccases, two tyrosinases, and two peroxidases were studied for their ability to transform ten pharmaceuticals and benzotriazole. Acetaminophen was most susceptible to enzymatic conversion by horseradish peroxidase (HRP), laccase from Trametes versicolor (LccTV), and a tyrosinase from Agaricus bisporus (TyrAB). Diclofenac and mefenamic acid were converted by HRP and LccTV, whereas sotalol was solely amenable to HRP conversion. Benzotriazole, carbamazepine, gabapentin, metoprolol, primidone, sulfamethoxazole, and venlafaxine remained persistent in this study. The results obtained here emphasize that enzymes are highly selective catalysts and more effort is required in the use of fast monitoring technologies to find suitable enzyme systems. Despite the methodological limitations discussed in detail, the automated tool provides a routine on-line screening of various enzymatic reactions to identify potential enzymes that degrade CECs. Graphical abstract A chip-based robotic nano-ESI-MS tool to rapidly monitor enzymatic degradation of environmentally relevant emerging contaminants.

In this study, a fast and rugged method is presented for the analysis of PCBs, PAHs, PBDEs and PCDD/Fs in biological tissues using a simple Quick, Easy, Cheap, Efficient, Rugged and Safe (QuEChERS) extraction and a clean-up by Gel Permeation Chromatography (GPC) and silica Solid Phase Extraction (SPE). Development was performed on blue mussels (Mytilus edulis) and Atlantic salmon (Salmo salar) for evaluation of two ranges of lipid and water content of biological tissues. Statistical validation was performed with Atlantic salmon samples. Forty-five PAHs were analyzed including the priority list of the US EPA and the European Union with 41 PCBs, 24 PBDEs and 17 PCDD/Fs. Instrumental analyses were performed on Gas Chromatography - High Resolution Mass Spectrometry (GC-HRMS). Accuracy was evaluated for PCBs and PCDD/Fs with a certified reference material furnished by the National Research Council Canada (NRCC) and also compared with results obtained by the conventional Soxhlet extraction. Statistical validation showed recoveries for PCBs, PAHs, PBDEs and PCDD/Fs close to 100% with average Relative Standard Deviation (RSD) lower than 10% and internal standard recoveries in the range of 70% with average RSD ranging from 5-15%. Average calculated Method Detection Limits (MDLs) were lower than 0.05μg/Kg for PCBs, 0.2μg/Kg for PAHs and PBDEs and 1ng/Kg for PCDD/Fs. The method is a faster and cheaper alternative to the time-consuming conventional method that has been used in most environmental laboratories., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Commonly used as flame retardants, polybrominated diphenyl ethers (PBDEs) are routinely detected in the environment, animals, and humans. Although these persistent organic pollutants are increasingly recognized as having serious health implications, particularly for children, this is the first study, to our knowledge, to investigate an intervention for human elimination of bioaccumulated PBDEs. Objectives. To determine the efficacy of blood, urine, and perspiration as PBDE biomonitoring mediums; assess excretion of five common PBDE congeners (28, 47, 99, 100, and 153) in urine and perspiration; and explore the potential of induced sweating for decreasing bioaccumulated PBDEs. Results. PBDE congeners were not found in urine samples; findings focus on blood and perspiration. 80% of participants tested positive in one or more body fluids for PBDE 28, 100% for PBDE 47, 95% for PBDE 99, and 90% for PBDE 100 and PBDE 153. Induced perspiration facilitated excretion of the five congeners, with different rates of excretion for different congeners. Conclusion. Blood testing provides only a partial understanding of human PBDE bioaccumulation; testing of both blood and perspiration provides a better understanding. This study provides important baseline evidence for regular induced perspiration as a potential means for therapeutic PBDE elimination. Fetotoxic and reproductive effects of PBDE exposure highlight the importance of further detoxification research.

An analytical method was developed and optimized for the quantification of 16 polycyclic aromatic hydrocarbons (PAHs) and 12 oxygenated PAHs in Taxus baccata leaves. Emphasis was given to the development of an in-cell cleanup step using pressurized solvent extraction, a cleanup step using solid-phase extraction, and the instrumental analysis by GC-HRMS. Different extraction temperatures (between 50 and 200 °C) and Florisil quantities were evaluated for the extraction process. Based on the evaluation of both recoveries and matrix effect factors, a temperature of 200 °C and 1 g Florisil was selected as the optimum. However, the in-cell cleanup was not sufficient in the long term due to increasing chromatographic peak broadening, and further cleanup was necessary. Solid-phase extraction (using Florisil) was evaluated, and breakthrough curves were acquired for all target compounds to determine the optimal elution volume and avoiding matrix interference. Recoveries of the target compounds ranged from 58 to 87 % for the PAHs and from 5 to 105 % for the oxy-PAHs. Matrix effects were determined for all individual target compounds. The optimized method was applied to T. baccata samples obtained from ten sampling locations in Ghent, Belgium. This is the first biomonitoring study in Ghent for PAHs and oxy-PAHs. The presence of significant amounts of toxicologically relevant oxygenated PAHs (Oxy-PAHs) (can enhance ROS formation in human lung cells) in T. baccata was confirmed (max ∑Oxy-PAHs: 230 ng/g; max ∑PAHs: 389 ng/g). This means that these oxygenated PAHs are important pollutants and should be included in future monitoring studies.

Polybrominated dibenzofurans (PBDFs) are a class of highly toxic environmental contaminants which comprises 135 structurally different congeners. While the gas chromatographic separation and analysis of the most polychlorinated dibenzofurans (PCDFs) are well-documented, comparably little data is currently available in the case of PBDFs. In this study dibenzofuran was brominated to give a mixture of ∼40 PBDFs with one to seven bromine atoms. This synthesis mixture was fractionated by both countercurrent chromatography (CCC) with the solvent system n-hexane/toluene/acetonitrile and non-aqueous reversed-phase high performance liquid chromatography (RP-HPLC) with acetonitrile as the mobile phase. All together 80 consecutive CCC fractions and 40 HPLC fractions were taken and analyzed for PBDFs by gas chromatography coupled to mass spectrometry (GC/MS). CCC and RP-HPLC offered orthogonal separation of the PBDF mixture. As a consequence, selected CCC fractions were further fractionated by RP-HPLC. In this way, eight PBDFs could be isolated and the structures of twelve PBDFs were elucidated by proton magnetic resonance spectroscopy ((1)H NMR)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The use of bisphenol A (BPA) has been restricted in many countries because of its potential health effects. As a result of these restrictions, a group of bisphenol analogues that are structurally similar to BPA have been developed as the alternatives for industrial applications. However, latest researches indicated that these chemicals have similar endocrine-disrupting effects as BPA in humans. Moreover, only a limited number of studies have attempted to monitor the exposure level in humans of other bisphenol analogues. In the present study, the concentrations of seven bisphenols, including bisphenol S (BPS), bisphenol F (BPF), bisphenol B (BPB), BPA, bisphenol AF (BPAF), tetrachlorobisphenol A (TCBPA) and tetrabromobisphenol A (TBBPA), in human urine samples were measured by liquid chromatography coupled to mass spectrometry (LC-MS/MS) following the enzymatic hydrolysis of glucuronidase/arylsulfatase and liquid-liquid extraction (LLE). Under the optimised conditions, high recoveries (81.6-116.8%) were obtained for all the analytes, and the relative standard deviations (RSD, %) were less than 16.4% (n=6). The isotopic internal standard calibration curves for each of the target compounds exhibited excellent linearity (r(2)>0.99) and the limit of quantification (LOQ) for the analytes in urine ranged from 0.024 to 0.310 ng mL(-1). The method was applied to investigate the urinary levels of these seven bisphenols in a cohort of residents living near a BPAF manufacturing plant in south China. BPS, BPF, BPA and BPAF were detected in urine samples at concentrations ranging from

Used frequently in food contact materials, bisphenol A (BPA) has been studied extensively in recent years, and ubiquitous exposure in the general population has been demonstrated worldwide. Characterizing within- and between-individual variability of BPA concentrations is important for characterizing exposure in biomonitoring studies, and this has been investigated previously in adults, but not in children. The aim of this study was to characterize the short-term variability of BPA in spot urine samples in young children. Children aged ≥2-<4 years (n=25) were recruited from an existing cohort in Queensland, Australia, and donated four spot urine samples each over a two day period. Samples were analysed for total BPA using isotope dilution online solid phase extraction-liquid chromatography-tandem mass spectrometry, and concentrations ranged from 0.53 to 74.5 ng/ml, with geometric mean and standard deviation of 2.70 ng/ml and 2.94 ng/ml, respectively. Sex and time of sample collection were not significant predictors of BPA concentration. The between-individual variability was approximately equal to the within-individual variability (ICC=0.51), and this ICC is somewhat higher than previously reported literature values. This may be the result of physiological or behavioural differences between children and adults or of the relatively short exposure window assessed. Using a bootstrapping methodology, a single sample resulted in correct tertile classification approximately 70% of the time. This study suggests that single spot samples obtained from young children provide a reliable characterization of absolute and relative exposure over the short time window studied, but this may not hold true over longer timeframes., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In the environment enzymes may play important and different roles at least in three cases: as main agents (as isolated, cell-bound or immobilized enzymes) in charge of either the transformation and/or degradation of compounds polluting the environment and the restoration of the polluted environment; as reliable and sensitive tools to detect and measure the amount and concentration of pollutants before, during and after the restoration process; as reliable, easy and sensitive indicators of quality and health status of the environment subjected to the restoration process. To our knowledge papers or reviews integrating findings on these three functions of enzymes are missing in literature. Therefore the main scope of the present paper is to briefly encompass general and specific concepts about roles of enzymes as decontaminating agents, pollutant assaying agents and indicators of environment safety. Examples chosen among those published very recently, supporting and confirming peculiarities, features, and performance of enzymatic agents will be illustrated., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Due to the high toxicity of endocrine disruptors (EDs), studies are being undertaken to design effective techniques for separation and detection of EDs in various matrices. Recently, research activities in this area have shown that a diverse range of chromatographic techniques are available for the quantification and analysis of EDs. Therefore, on the basis of significant, recent original publications, we aimed at providing an overview of different separation and detection methods for the determination of trace-level concentrations of selected EDs. The biological effects of EDs and current pretreatment techniques applied to EDs are also discussed. Various types of chromatographic techniques are presented for quantification, highlighting time- and cost-effective techniques that separate and quantify trace levels of multiple EDs from various environmental matrices. Reports related to methods for the quantification of EDs from various matrices primarily published since 2008 have been cited.

In order to perform environmental surveillance to track oral poliovirus vaccine-like poliovirus sensitively and conveniently, real-time PCR was developed and applied to a raw sewage concentrate. The real-time PCR method detected 0.01-0.1 TCID50 of 3 serotypes of Sabin strain specifically. The method also detected the corresponding serotypes of oral poliovirus vaccine-like poliovirus specifically, but detected neither wild poliovirus, except Mahoney for type 1 and Saukett for type 3, nor other enteric viruses, as far as examined. When real-time PCR was applied to environmental surveillance, the overall agreement rates between real-time PCR and the cell culture were 83.3% for all serotypes. Since real-time PCR has the advantages of rapid detection of viruses and minimum requirement of sampling volume as compared with ordinary cell culture, it is suitable to monitor oral poliovirus vaccine-like poliovirus in the environment, especially in areas where an oral vaccine is being replaced by an inactivated vaccine., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Environmental samples include a wide variety of complex matrices, with low concentrations of analytes and presence of several interferences. Sample preparation is a critical step and the main source of uncertainties in the analysis of environmental samples, and it is usually laborious, high cost, time consuming, and polluting. In this context, there is increasing interest in developing faster, cost-effective, and environmentally friendly sample preparation techniques. Recently, new methods have been developed and optimized in order to miniaturize extraction steps, to reduce solvent consumption or become solventless, and to automate systems. This review attempts to present an overview of the fundamentals, procedure, and application of the most recently developed sample preparation techniques for the extraction, cleanup, and concentration of organic pollutants from environmental samples. These techniques include: solid phase microextraction, on-line solid phase extraction, microextraction by packed sorbent, dispersive liquid-liquid microextraction, and QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe).

The use of biofilms for adsorption of sterols was investigated for the first time to evaluate sewage contamination in the Barigüi River, Curitiba (Brazil). The characteristics of a biofilm that favor its use in monitoring include the relatively rapid development of biofilms and their capacity to sorb hydrophobic compounds. Some fecal sterols considered to be biomarkers for human and animal feces have relatively high octanol-water partitioning coefficients (log KOW); thus, sterols were expected to be readily sorbed in the biofilms. The biofilms were developed on glass plates (0.48 m(2)) previously coated with a fine layer of stearic acid and supported by a PVC tube that was submersed in the river 20 cm above the river bottom. After a certain period of incubation time, the biofilm growth was scraped from the plates and analyzed for the following fecal steroids: coprostanol (5β-cholestan-3β-ol), epicoprostanol (5β-cholestan-3α-ol), cholesterol (5,6-cholesten-3β-ol), cholestanol (5α-cholestan-3β-ol), stigmastanol (24β-ethyl-5α-cholestan-3β-ol) and coprostanone (5β-cholestan-3-one). Six samples were collected between March 2012 and June 2012. All analyzed compounds were detected, and in general, cholesterol was present in high amounts (23 160-41.9 ng g(-1) dry biofilm). Variation among campaigns was observed in the distribution of sterols, with cholestanol showing the least variation among the samples. Sterol ratios that are commonly used for evaluating sewage contamination were calculated; these ratios indicated some periods of potential sewage influence. However, these sterol ratios are intended to be applied primarily for sediments and not for biological compartments; thus, the results must be carefully interpreted. Biofilms developed under natural conditions can be a tool for monitoring some important sterols that are used as biomarkers of fecal pollution.

The presence of organochlorine pesticides (OCPs) in biological and environmental samples has been studied for decades in many countries. Nonetheless, studies in Latin American countries like Colombia have been scarce. Determining the presence of OCPs in breast milk will be of relevance to assess exposures, potential health risks, and for surveillance among Latin American populations. Thirty-two breast-feeding mothers were selected to voluntarily participate in the study. Breast milk samples were analyzed for 10 OCPs (α-, β-, γ-, δ-HCH, Heptachlor, α-, γ-Chlordane, 4,4' DDT, 4,4' DDE, 4,4' DDD). Milk samples were analyzed using liquid-liquid extraction, followed by sulfuric acid clean-up, and quantified using GC/μECD. Results were confirmed by GC/MS. OCPs concentrations were normalized using fat content. In all but one sample, 4,4' DDE was quantified in concentrations ranging between<17 and 14948 ng g(-1) (ng of OCP per g of lipids), with a mean value of 203 ng g(-1). One woman had 4,4' DDE concentrations that were orders of magnitude above the average concentrations observed worldwide. Concentrations of 4,4' DDE in a second breast milk sample collected in a different time period of lactation from a sub-group of 13 women from the original participants, showed no statistically significant difference with the concentrations found in the first sample. Based on the results obtained from the Persistent Organic Pollutants Global Monitoring Plan report of 2009 of the Stockholm Convention, Colombia ranks fourth from bottom to top in terms of 4,4' DDE average concentrations., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The absence of well-validated biomarkers of manganese (Mn) exposure in children remains a major obstacle for studies of Mn toxicity. We developed a hair cleaning methodology to establish the utility of hair as an exposure biomarker for Mn and other metals (Pb, Cr, Cu), using ICPMS, scanning electron microscopy, and laser ablation ICPMS to evaluate cleaning efficacy. Exogenous metal contamination on hair that was untreated or intentionally contaminated with dust or Mn-contaminated water was effectively removed using a cleaning method of 0.5%Triton X-100 sonication plus 1 N nitric acid sonication. This cleaning method was then used on hair samples from children (n = 121) in an ongoing study of environmental Mn exposure and related health effects. Mean hair Mn levels were 0.121 μg/g (median = 0.073 μg/g, range = 0.011-0.736 μg/g), which are ∼4 to 70-fold lower than levels reported in other pediatric Mn studies. Hair Mn levels were also significantly higher in children living in the vicinity of active, but not historic, ferroalloy plant emissions compared to controls (P < 0.001). These data show that hair can be effectively cleaned of exogenous metal contamination, and they substantiate the use of hair Mn levels as a biomarker of environmental Mn exposure in children.

The performance of simple slit impactors for air sampling of mold contamination was compared under field conditions. Samples were collected side-by-side, outdoors in quadruplicates with Burkhard (ambient sampler) and Allergenco MK3 spore traps and with two identical Allergenco slit cassettes operated at diverse flow rates of 5 and 15 L/min, respectively. The number and types of mold spores in each sample were quantified by microscopy. Results showed all four single-stage slit impactors produced similar spore yields. Moreover, paired slit cassettes produced similar outcomes despite a three-fold difference in their sampling rate. No measurable difference in the amount or mix of mold spores per m(3)of air was detected. The implications for assessment of human exposures and interpretation of indoor/outdoor fungal burden are discussed. These findings demonstrate that slit cassettes capture most small spores, effectively and without bias, when operated at a range of flow rates including the lower flow rates used for personal sampling. Our findings indicate sampling data for mold spores correlate for different single stage impactor collection methodologies and that data quality is not deteriorated by operating conditions deviating from manufacturers' norms allowing such sampling results to be used for scientific, legal, investigative, or property insurance purposes. The same conclusion may not be applied to other particle sampling instruments and mulit-stage impactors used for ambient particulate sampling, which represent an entirely different scenario. This knowledge may help facilitate comparison between scientific studies where methodological differences exist.

No previous analytical procedures are available and validated for mercury speciation analysis in terrestrial animal tissues. This analysis is a difficult task both because the expected concentrations are low, since important accumulation process are not likely to occur, and also because there are not commercially available certified reference material. Thus, an analytical methodology has been developed and validated for mercury speciation for the specific case of terrestrial animal tissues. The proposed method is based on the quantitative extraction of the species by closed-vessel microwave assisted heating with an alkaline reagent, followed by ethylation. The ethylated derivatives were then submitted to head-space solid phase microextraction with a 100 μm polidimethylsiloxane-coated fiber, and desorbed onto a gas chromatograph coupled to atomic fluorescence detection via pyrolysis unit (HS-SPME-GC-pyro-AFS). Procedural detection limits were 31.8 ng g(-1) and 52.5 ng g(-1) for CH(3)Hg(+) and Hg(2+), respectively, for liver and 35.3 ng g(-1) and 58.1 ng g(-1) for CH(3)Hg(+) and Hg(2+), respectively, for kidney. These limits of detection are 5.5 and 6 times better than the obtained without solid phase microextraction for CH(3)Hg(+) and Hg(2+), respectively. The methodology was found linear up to 120 μg L(-1) and reproducible from one day to the following. It was validated with certified reference materials NCS ZC 71001 (beef liver) and BCR No 186 (pig kidney) for total mercury, calculated as the sum of species, and with spiked red deer liver and kidney for speciation. Finally, it was applied to the analysis of samples of red deer liver, red deer kidney and wild boar kidney coming from the Almadén's mercury mining area (Ciudad Real, Spain), the longest and largest producer of mercury in the world until its closure in 2002., (Copyright © 2012 Elsevier B.V. All rights reserved.)

We recently reported the discovery and identification of novel methoxylated polybrominated diphenoxybenzenes (MeO-PBDPBs) in herring gulls eggs from the Laurentian Great Lakes of North America. We presently investigated the temporal changes (1982-2010) in MeO-PBDPB concentrations and congener patterns, as well as chemical tracers of diet (ratios of carbon and nitrogen stable isotopes), in egg pool homogenates from five selected colony sites across the Great Lakes. Egg pool homogenates from the Channel-Shelter (C-S) Island (Lake Huron) contained ∑MeO-PBDPB concentrations orders of magnitude greater than those from other colonies, suggesting potential point contamination sources nearby. In the C-S Island egg pools, concentrations increased from the initial study year (31 ng/g wet weight) and peaked around the late 1990s, followed by a general decline until 2010. Over the period, concentrations generally increased in eggs from Fighting Island (Lake Erie), Toronto Harbour (Lake Ontario) and Big Sister Island (Lake Michigan) colonies, whereas the levels in Agawa Rock (Lake Superior) declined. Although other factors likely exist, changes over time in the carbon and nitrogen isotope tracers reflected a shift of the gull diet from aquatic to more terrestrial origins, and suggested this diet shift partially accounted for the temporal changes of ∑MeO-PBDPB levels in eggs from most colonies. The ratio of Br(6)- to Br(5)-MeO-PBDPB congeners generally decreased over time in the colonies at Channel-Shelter Island, Fighting Island and Agawa Rock. This suggested that Br(5)- versus Br(6)-MeO-PBDPB congeners and/or possibly their nonmethoxylated and higher brominated precursors may have been more abundant in diets of terrestrial origin. Notably, these MeO-PBDPB congeners are not "emerging" brominated substances, but rather "recently discovered" contaminants since, as of 2011, ∑MeO-PBDPB concentrations have been constantly in the range of 30-100 ng/g ww for at least the last 30 years.

Supramolecular complexes offer a new and efficient way for the monitoring and removal of many substances emanating from technical processes, fertilization, plant and animal protection, or e.g. chemotherapy. Such pollutants range from toxic or radioactive metal ions and anions to chemical side products, herbicides, pesticides to drugs including steroids, and include degradation products from natural sources. The applications involve usually fast and reversible complex formation, due to prevailing non-covalent interactions. This is of importance for sensing as well as for separation techniques, where the often expensive host compounds can then be reused almost indefinitely. Immobilization of host compounds, e.g. on exchange resins or on membranes, and their implementation in smart new materials hold particular promise. The review illustrates how the design of suitable host compounds in combination with modern sensing and separation methods can contribute to solve some of the biggest problems facing chemistry, which arise from the everyday increasing pollution of the environment.

Previous assessment of ecological risks within the Coeur d'Alene River Basin identified Pb as a key risk driver for ground-feeding songbirds. Because this conclusion was based almost exclusively on literature data, its strength was determined to range from low to moderate. With the support of the US Environmental Protection Agency (USEPA), the US Fish and Wildlife Service collected site-specific data to address the uncertainty associated with Pb risks to songbirds. These data, plus those from the previous Coeur d'Alene Basin ecological risk assessment, were integrated, and risks to ground-feeding songbirds were reevaluated. These site-specific data were also used to develop updated preliminary remedial goals (PRGs) for Pb in soils that would be protective of songbirds. Available data included site-specific Pb concentrations in blood, liver, and ingesta from 3 songbird species (American robin, song sparrow, and Swainson's thrush), colocated soil data, and soil data from other locations in the basin. Semi-log regression models based on the association between soil Pb and tissue Pb concentrations were applied to measured soil concentrations from the previous risk assessment to estimate Pb exposures in riparian and adjacent upland habitats throughout the Coeur d'Alene Basin. Measured and estimated tissue or dietary exposure was tabulated for 3 areas plus the reference, and then compared to multiple effects measures. As many as 6 exposure-effect metrics were available for assessing risk in any one area. Analyses of site-specific tissue- and diet-based exposure data indicate that exposure of ground-feeding songbirds to Pb in the Coeur d'Alene Basin is sufficient to result in adverse effects. Because this conclusion is based on multiple exposure-effect metrics that include site-specific data, the strength of this conclusion is high. Ecological PRGs were developed by integrating the site-specific regression models with tissue and dietary effect levels to create exposure models, which were solved for the soil concentration that produced an exposure estimate equal to the effect level (i.e., the ecological PRG). The lowest PRG obtained for any species' exposure-effect measure combination was 490 mg/kg for subclinical effects due to Pb in the blood of American robins; the highest was 7200 mg/kg for severe clinical effects due to Pb in the blood of song sparrows. Because the lowest ground-feeding songbird PRG was comparable to multiple cleanup goals developed for the basin (i.e., soil invertebrates, wildlife populations, and human health), in addition to the site-specific cleanup level of 530 mg Pb/kg sediment for the protection of waterfowl (USEPA 2002) the USEPA has made a risk-management determination that a site-specific Pb cleanup level of 530 mg/kg in soil would be protective of songbirds in the Coeur d'Alene Basin., (Copyright © 2011 SETAC.)

The main goal of this study was to test the usefulness of the Comet assay in the PLHC-1 hepatoma fish cell line as a tool for detecting the presence of genotoxic compounds in contaminated marine sediments. The system has been tested using both model chemicals (benzo[a]pyrene (B[a]P) and ethyl methanesulfonate (EMS)) and extracts of sediment samples obtained with solvent dichloromethane/methanol. For all of the analysed sediment extracts as well as for the model chemicals a concentration dependent genotoxic effect was observed. The sediment with the highest observed genotoxic potential was additionally extracted using various solvents in order to test which class of compounds, according to their polarity, is most responsible for the observed genotoxic effect. Non-polar solvents (cyclohexane and dichloromethane) yielded stronger genotoxic effect but the highest level of DNA damage was determined after exposure to sediment extract obtained with the solvent mixture dichloromethane/methanol which extracts a wide range of contaminants. Our results indicate that the PLHC-1 cell line is a suitable in vitro model in sediment genotoxicity assessment and encourage the use of fish cell lines as versatile tools in ecogenotoxicology., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

The study of chemical impurities trapped in solid precipitation and accumulated in polar ice sheets and high-elevation, midlatitude cold glaciers over the last several hundreds of years provides a unique way to reconstruct our changing atmosphere from the preindustrial era to the present day. Numerous ice core studies of inorganic species have already evaluated the effects of growing anthropogenic emissions of SO(2) or NO(x) on the chemical composition of the atmosphere in various regions of the world. While it was recently shown that organic species dominate the atmospheric aerosol mass, the contribution of anthropogenic emissions to their budget remains poorly understood. The study of organics in ice is at the infancy stage, and it still is difficult to draw a consistent picture of the organic content of polar ice from sparse available data. A UV oxidation method and IR quantification of CO(2) was optimized to obtain measurements of dissolved organic carbon content as low as a few ppbC. Stringent working conditions were defined to prevent contamination during the cleaning of ice. Measurements in various ice cores corresponding to preindustrial times revealed dissolved organic carbon content of less than 10 ppbC in Antarctica and up to 75 ppbC in alpine ice.

Despite a history of pesticide usage, few data exist on their concentrations in air and soil of Southern Africa. To add to the understanding of the processes controlling the fate of organic contaminants in arid regions, the levels, spatial trends, and seasonal variability of pesticides were studied in air and soil from Botswana. XAD resin-based passive air samplers (PAS) were deployed at 15 sites across the country from May 2006 to May 2007. Soil samples were collected from the vicinity of nine of the PAS sampling sites. In addition, 27 24-h high-volume air samples were collected in Maun, at the southeastern edge of the Okavango Delta, every two weeks for one year. Levels of pesticides in PAS were low, with α-endosulfan and lindane being most abundant. Concentrations in soils were extremely low and only soils with high organic carbon contained notable amounts of dieldrin and traces of other pesticides. In particular, air and soil from the Okavango Delta had very low levels even though the area had repeatedly been sprayed with DDT and endosulfan in the past. Air samples from Eastern Botswana, where the majority of the population lives, contained higher levels. Higher air concentrations of α-endosulfan occurred during summer and higher HCB levels occurred in winter. This seasonality was related with neither minor seasonal changes in temperature nor hydrological seasonal events such as the rainy season or the flooding of the Okavango Delta. Thus, the observed spatial and seasonal patterns are more likely related to pesticide usage pattern than to environmental factors or historical use. High temperature and low organic matter content limit the uptake capacity of most subtropical soils for pesticides. No evidence was found that sorption to dry mineral matter plays a major role. Arid soils in subtropical regions are therefore neither a major reservoir of organic contaminants nor do they constitute a significant long-term source of pesticides to the atmosphere.

The dental practice is associated with a high risk of infections, both for patients and healthcare operators, and the environment may play an important role in the transmission of infectious diseases. A microbiological environmental investigation was carried out in six dental clinics as a pilot study for a larger multicentre study that will be performed by the Italian SItI (Society of Hygiene, Preventive Medicine and Public Health) working group "Hygiene in Dentistry". Microbial contamination of water, air and surfaces was assessed in each clinic during the five working days of the week, before and during treatments. Air and surfaces were also examined at the end of the daily activity. A wide variation was found in microbial environmental contamination, both within the participating clinics and relative to the different sampling times. Microbial water contamination in Dental Unit Water Systems (DUWS) reached values of up to 26x10(4)cfu/mL (colony forming units per millilitre). P. aeruginosa was found in 33% of the sampled DUWS and Legionella spp. in 50%. A significant decrease in the Total Viable Count (TVC) was recorded during the activity. Microbial air contamination showed the highest levels during dental treatments and tended to decrease at the end of the working activity (p<0.05). Microbial buildup on surfaces increased significantly during the working hours. As these findings point out, research on microbial environmental contamination and the related risk factors in dental clinics should be expanded and should also be based on larger collections of data, in order to provide the essential knowledge aimed at targeted preventive interventions., (Copyright 2010 Elsevier B.V. All rights reserved.)

A total of 3.4 tonnes of household waste (HW) that had a controlled composition were autoclaved in the presence of saturated steam for 1 h at the nominal temperature levels of 130, 160 and 200 degrees C. The levels of Cd, Cr, Cu, Pb, Hg, Ni, and Zn were examined in samples of the fibrous, predominantly-biodegradable fraction (floc) derived from the autoclaved HW, aqueous extracts from floc, and the condensate from steam that was released from the reactor. This data was used to study the impact of the overall levels of potential toxic elements (PTEs) in HW feed and autoclaving process parameters on the levels of PTEs in floc. No consistent correlation was found to exist between the levels of PTEs in HW feed and those in the produced floc. This was primarily attributed in the inherent variability of PTEs in waste materials. Autoclaving temperature, pressure and mixing were all found to affect the mobilization and removal of PTEs from HW and their presence in floc. Temperature/pressure appeared to increase PTE removal through the condensate path, although that removal had only a negligible impact on the contents of PTEs in floc. Autoclaving temperature correlated positively, although not significantly at a 95% confidence level, with the levels of Pb and Zn in floc. On the other hand, it correlated negatively with the Hg content in floc. Increasing temperature/pressure also increased the water extraction of PTEs from floc, with the exception of Cr. However, in the context of producing high quality compost, the extraction rates were too low to bring about a substantial decrease of PTEs in floc.

The recovery operations following the 2001 attacks with Bacillus anthracis spores were complicated due to the unprecedented need for large-area surface sampling and decontamination protocols. Since this event, multiple reports have been published describing recovery efficiencies of several surface sampling materials. These materials include fibrous swabs of various compositions, cloth wipes, vacuum socks, and adhesive tapes. These materials have reported recovery efficiencies ranging from approximately 20% to 90% due to the many variations in their respective studies including sampling material, composition of surface sampled, concentration of contaminant, and even the method of deposition and sample processing. Additionally, the term recovery efficiency is crudely defined and could be better constructed to incorporate variations in contaminated surface composition and end user needs. While significant efforts in devising protocols for large-area surface sampling have been undertaken in the years since the anthrax attacks, there is still a general lack of consensus in optimal sampling materials and the methodology in which they are evaluated. Fortunately, sampling efforts are continuing to be supported, and the knowledge gaps in our procedures, methodology, and general understanding of sampling mechanisms are being investigated which will leave us better prepared for the future.

Advances towards sustainable land management necessitate application of a broader portfolio of decision-support tools that improve evaluation of contaminated land. Over the last decade regulators have directed concerted effort towards rationalization of risk-based contaminated land policies recognizing bioavailability and bioaccessibility as concepts to be incorporated into risk assessments. The desire for a precise and rapid method to inform consideration of bioavailability and bioaccessibility to support risk assessment of contaminated land has never been greater. This study presents a comprehensive appraisal of both emerging non-exhaustive extraction techniques (subcritical water extraction and Brij 700 extraction) developed to reflect polycyclic aromatic hydrocarbon (PAH) bioaccessibility to microorganisms as well as formerly demonstrated methodologies (the use of cyclodextrins and butanol extraction). Application of unified evaluation criteria across different techniques enabled comparison not only from the bioaccessibility prediction perspective but also analysis of economical (cost of extraction) and practical (such as extraction time) measures. Whilst the use of cyclodextrins was the best predictor of the bioaccessible fraction for the majority of compounds, other methods appeared more cost- and time-effective. Juxtaposition of the techniques presented in this study assists establishing cost-benefit trade-offs of different non-exhaustive extraction techniques and contributes to tailoring information on contaminant bioaccessibility to support risk evaluation on contaminated sites.

Sediment contamination is a significant issue. Assessment, management, and monitoring of contaminated sediment require routine analyses of a large volume of sediment samples, which require significant preparation time including extraction of contaminants from samples prior to analysis. This work tested a new method of extracting contaminants from sediment based on the use of rapid, successive pressurization cycles, which involve compression of a gas into the extractive solvent in contact with the sediment immediately followed by decompression via venting. The technique improved extraction amounts and shortened preparation time. Tested were PCB and PAH contaminated sediment samples from various locations of the US, including the Passaic River, St. Louis River, Waukegan Harbor, and Wells National Estuarine Research Reserve. The results were compared to those of Soxhlet extraction. Specifically, the extraction of 15 g of sediment with 50 mL of hexane-acetone (1:1) mixture at room temperature using 10 rapid, successive pressure cycles with N(2) attaining 1.0 MPa during compression was complete within 15 min. Using the new technique, consistently more PAHs and PCBs were extracted from the sediments in comparison to Soxhlet extraction. Extraction was evaluated according to key factors including the number of compression-decompression cycles, compression pressure, sample amount, moisture, and pressurizing gas type. The heightened extraction performance was explained by cyclic changes in gas solubility during repetitive compression and decompression steps, which introduce mechanisms to fragment sediment aggregates resulting in increased contaminant exposure and extraction.

There are presented method approach to analysis of the monitoring results of food chemical safety in real time; offered the model of present and research of montoring results for reveal of importanceb pollutions.

We studied tree swallows (Tachycineta bicolor) at the Sangamo National Priorities List (NPL) site and a reference area (Little Grassy) within Crab Orchard National Wildlife Refuge, Illinois, USA, to evaluate the bioavailability of polychlorinated biphenyls (PCBs) at the NPL site following remediation. Tree swallow eggs and 12- to 17-d-old chicks were collected from April to June 2004 and 2005. Total egg PCB concentrations in eggs did not differ between years at Sangamo; mean concentrations at Sangamo in 2004 to 2005 (4,452 ng/g) were higher than those from Little Grassy in 2004 (351 ng/g; p = 0.002) and 2005 (705 ng/g; p = 0.007). A positive PCB dilution in chicks is equivalent to relatively large amounts of exposure and absorption. Total PCB daily dilution in chicks in 2004 and 2005 averaged 92.4 and -203 ng/g/d at Sangamo and -21.8 and -42.7 ng/g/d at Little Grassy. Dioxin toxic equivalents (TEQs) in eggs in 2004 and 2005 were 1,844 and 676 pg/g at Sangamo and 165 and 128 pg/g at Little Grassy. Mean TEQs in chicks in 2004 and 2005 were 117 and 23.8 pg/g body weight at Sangamo and 0.8 and 0.7 pg/g body weight at Little Grassy. Total PCB concentrations in eggs and chicks at Sangamo and Little Grassy appeared to be comparable to other PCB-contaminated and reference sites. Our data demonstrate that tree swallows using the Sangamo site continue to accumulate significant quantities of PCBs seven years after remedial actions. These findings prompted a reevaluation of remediation at the site and underscore the importance of postremediation monitoring of ecological receptors, particularly in cases involving persistent environmental contaminants.

Aims: Having and executing a well-defined and validated sampling protocol is critical following a purposeful release of a biological agent for response and recovery activities, for clinical and epidemiological analysis and for forensic purposes. The objective of this study was to address the need for validated sampling and analysis methods called out by the General Accounting Office and others to systematically compare the collection efficiency of various swabs and wipes for collection of bacterial endospores from five different surfaces, both porous and nonporous. This study was also designed to test the collection and extraction solutions used for endospore recovery from swabs and wipes., Methods and Results: Eight collection tools, five swabs and three wipes, were used. Three collection/preservation solutions were evaluated: an ink jet aerosol generator was used to apply Bacillus subtilis endospores to five porous and nonporous surfaces. The collection efficiencies of the swabs and wipes were compared using a statistical multiple comparison analysis., Conclusions: The ScottPure wipe had the highest collection efficiency and phosphate-buffered saline (PBST) with 0.3% Tween was the best collection solution of those tested., Significance and Impact of the Study: Validated sampling for potential biological warfare is of significant importance and this study answered some relevant questions.

This report reviews past research on hair analysis development for organic contaminants from the point of view of analytical procedures, successful applications and their limitations. For the past 20 years, hair analysis for organic pollutants has received more and more attention, since it is non-invasive, easily available and ethically not prioritized. New methods such as SFE, SPME and INAA have been developed to make the analysis more accurate and reliable. Furthermore, the correlation of contamination levels between hair samples and ambient air or internal tissues has been found by hair analysis and short-term and long-term exposure assessment in combination. However, there are still some limitations of hair analysis to be a validated risk assessment tool for many compounds. Some limitations had been of the past, some have not been fully investigated and need still further study. In this way, hair analysis can be the key to successfully biomonitor organic contaminations.

The market place is considered to be an important centre of daily life of campus community. In India, as in Europe and the USA, other forms of shopping have emerged significantly and now predominate, for instance department stores and supermarkets. Though, it is suffered from poor waste management, but the place could be a potential source for obtaining non-conventional energy. The present study examined the quality of market waste management of the Indian Institute of Technology Campus along with the feasibility of biogas production from leachate generated in the waste. Solid wastes from different storage locations of the market place were collected and analyzed. The characteristics of solid wastes were found to be degradable in nature. The wastes, composed of 85% of vegetable origin, were placed in a container and water was added to to generate leachate. The self-purification efficiency of leachate was also studied in the Indian environment and compared with research findings in the USA under an identical moisture application rate. Leachate characterization was investigated both under saturated and submerged conditions. The treatability of leachate was studied in a laboratory-scale up-flow anaerobic filter with hollow burnt clay rings as packing media. It was observed that 4,000-6,000 mg/l would be the optimum range of inlet chemical oxygen demand (COD) concentration for leachate treatment because of the inhibitory effect of ammonia, sulphide, volatile fatty acids and toxic metals in high concentrations at higher strengths of leachate. The gas production rate was found to be at a maximum at 38 degrees C and containing 70-75% methane. From experimental data, it was revealed that 83% COD was removed with input COD concentration of 5,475 mg/l at 2 days hydraulic retention time with biogas yield coefficients of 0.61. The present study also investigated the removal efficiency of chloride, ammonia, sulphide and nitrate.

The aim of this research was to evaluate the possible contamination by heavy metals of milk from cows bred on various farms in Calabria. The concentrations of heavy metals were determined in 40 samples of bovine milk from the various dairy farms. Each sample, homogenized and powdered, was mineralized in a microwave oven. Quantitative analyses of Cd, Cr, Cu, Pb and Se were performed using an atomic absorption spectrophotometer with graphite furnace; As was analyzed by hot vapor generation technique and Zn with the flame method. As regards toxic heavy metals, highest values are those of As (g.m. 37.90 microg/kg w.w.) and Pb (g.m. 1.32 microg/kg w.w.), while lowest concentrations are those of Cd (g.m. 0.02 microg/kg w.w). With regard to essential metals, Zn (g.m. 2016 microg/kg w.w) and Se (g.m. 13.24 microg/kg w.w.) showed the highest concentrations, followed by Cr (g.m. 2.03 microg/kg w.w.) and Cu (g.m. 1.98 microg/kg w.w.). Further investigations of the levels of heavy metals (As) in a greater number of milk samples from various zones of Calabria are necessary, both to examine this problem from the clinical epidemiological point of view and to identify the possible causes of milk contamination.

Microorganism Pseudomonas species P2 metabolizes polychlorinated biphenyls (PCBs) and biphenyl, producing the whole spectrum of intermediates, among them coloured intermediates, which are suitable for the monitoring of PCBs degradation by optical sensors. Knowledge of chemical structures and conditions of development of colour metabolites is necessary for application of optical analytical methods. The main goal of this work was the isolation and identification of intermediates from the biodegradation of the mixture of low chlorinated biphenyls (Delor-103), which is based on the solid phase extraction (SPE) of the whole mixture using LiChrolut EN cartridges, then silylation of the extract as one way to the identification of one part of intermediates by GC-MS, and acetylation of the extract as a way for the further concentration and analysis of more polar chlorobiphenylols and chlorobiphenyldiols. The combination of SPE and following acetylation allows to obtain chlorobiphenylols and chlorobiphenyldiols as an almost pure fraction. The acetylation method could be also used instead SPE procedure with the same final concentration effect. Using the simulation mass spectrometry program, two new compounds, dihydrodihydroxytrichloro- and tetrahydrodihydroxytrichlorobiphenyl, as silylderivatives, were identified.

Dichlorodiphenyltrichloroethane (DDT), organochlorine pesticide, byanother way cumulative pesticide is banned in mostdeveloped countries. Whatever, it is still used in many countries in the Third World. This work consist to check whether this chemical compound is still used in Senegal. The biomarker of pollution by this pesticide for this research was mango leaves (mango tree is widespread in Senegal) open to accumulate halogenated hydrocarbons. Leaves sample were taken in many sites in the centerline of Dakar-Thiès (Senegal), then analysed by gas chromatography. The results allowed to note the presence of DDT and its metabolites [(dichlorodiphenyltrichloroethylen (DDE), (dichlorodiphenyltrichloroethane (DDD)] in most of samples. The comparison of DDT content in relation to those of the principal metabolite allowed to make the difference according to sample sites, an old contamination of an utilisation more or less recent of this pesticide. From those results, we can conclude that DDT, typical pesticide by its big persistence is still used in some spherical zones in this country, in particular in farming gardening zones.

A multiresidue solid-phase extraction (SPE) method for the isolation and subsequent gas chromatographic determination of organochlorine and organophosphorus pesticide residues in low-moisture, nonfatty products is described. Residues are extracted from samples with an acetonitrile/water mixture. Cleanup of the extract is performed using graphitized carbon black and anion exchange SPE columns, and analysis is performed by gas chromatography with Hall electrolytic conductivity and flame photometric detection. Recovery data was obtained by fortifying corn, oats and wheat with pesticides. The average recoveries were 79-123% for eight organochlorine and 51-122% for 28 organophosphorus pesticide residues. The limit of quantitation for chlorpyriphos was 0.05 ppm using the Hall electrolytic conductivity detector and < 0.005 ppm using the flame photometric detector.

The successful introduction of genetically modified and genetically engineered microorganisms into the environment requires a quantitative evaluation of the survival and dispersion of the microorganisms and specific gene(s) in the environment. The objective of this article is to examine the applicability, suitability, and significance of existing and new methods for detecting and monitoring the recombinant genes or organisms introduced into the environment. Conventional microbiological method(s) involving the selective and differential growth of microorganism(s) adn other quantitative approaches such as the most-probable-number (MPN) method and direct microscopic observation (e.g., acridine orange direct count analysis) have drawbacks and are not specific or universally applicable. Direct enumeration by immunofluorescence by the use of fluorescent dye seems more sensitive although still not perfect. However, the molecular methodologies such as the use of gene probes, plasmid epidemiology, antibiotic resistant marker strains, and protein electrophoresis and bacteriophage sensitivity are receiving more attention. As yet, the technology of DNA:DNA hybridization appears to be very useful, sensitive, and accurate for detecting and monitoring the microorganisms in the environment, although improvements are required. New approaches can be developed which may include biochemical signature compounds as well as gene cassettes to be used in a complementary fashion with conventional and molecular techniques for quantifying specific genotypes and genes in the environment.