In vitro approaches to assess bioavailability and human gastrointestinal mobilization of food-borne polychlorinated biphenyls (PCBs).

This study reports on the potential for gastrointestinal (GI) mobilization and bioavailability of food-borne PCBs in humans. The development and validation of a GI simulator and operational protocols, developed in compliance with the requirements of German DIN 19738 risk assessment test procedure, are presented. Food, naturally contaminated with PCBs, was homogenized with simulated saliva fluid and shaken in the GI simulator with simulated gastric fluids (containing pepsin, mucine) for 2 h at 37 degrees C. Afterwards, the simulated intestinal fluids (containing pepsin, mucine, trypsin, pancreatin, bile) were added and the mixture shaken for a further 6 h prior to centrifugation and filtration using Buchner funnels to separate the undigested GI residues from GI fluids. PCBs were recovered from GI residues and fluids by Soxhlet and liquid-liquid extraction respectively, cleaned up using silica-SFE, and analyzed by gas chromatography mass spectrometry detection (GC-MSD). Detailed studies with fish indicate variations in mobilization and bioavailability of Sigma PCBs (28, 52, 101, 118, 153, 138 and 180). For example, the bioavailable fractions (fractions mobilized) in mackerel, salmon, crab and prawn were 0.77, 0.60, 0.54, and 0.72 respectively of the Sigma PCBs initially present in these food samples. The bioavailable fraction was dependent on the physicochemical characteristics of the PCBs. In mackerel bioavailable fractions for individual PCB congeners ranged from 0.47-0.82, from 0.30-0.70 in salmon, 0.44-0.64 in crab and in prawn from 0.47-0.77. Future studies will focus on understanding better, the variability in bioavailable fractions to be expected for different foodstuffs, in addition to tissue culture techniques using human gut cell lines to investigate a simultaneous mobilization and absorption of food-borne PCBs.

Comparison of levels of polychlorinated biphenyls in edible oils and oil-based products--possible link to environmental factors.

Food consumption has been widely reported to be the main source of human exposure to PCBs. A total of 47 samples of food products on sale in supermarkets in the United Kingdom were thus analyzed for PCBs to determine residual levels in oil and oil-based products. The objective was to compare the measured levels of total PCBs (Sigma PCBs) in food products to those reported in various environmental compartments. Combined extraction and online clean up was achieved using Accelerated Solvent Extraction (ASE) to recover target analytes for analysis by GC-MSD (gas chromatography mass spectrometry). Sigma PCBs (ng/g) in each product were in the ranges of 4.73-44.38 edible oil; 1.40-6.18 mayonnaise; 1.21-6.25 salad cream; 1.28-5.64 seafood sauce, and 0.97-15.08 exotic dressing. The level of human exposure to PCBs in all products was < 1 microg/kg body weight/day when considering a 70 kg male or 57 kg female, possibly reflecting the reported decline of PCBs in the environment.

Impact of drying and composting procedures on the concentrations of 4-nonylphenols, di-(2-ethylhexyl)phthalate and polychlorinated biphenyls in anaerobically digested sewage sludge.

Enhanced treatments of sewage sludge produce a more manageable product for agricultural use by stabilizing the material, removing water, and reducing the possibility of pathogen transfer. We investigated the impact of pilot-scale composting and drying of sludge on physicochemical characteristics and on the concentrations of some organic contaminants. During the 143 day composting procedure, organic matter fell 22% and moisture by half. Concentrations of 4-nonylphenols (4-NPs) fell by 88% and di-(2-ethylhexyl) phthalate (DEHP) by 60%; losses continued throughout the procedure. Losses of total polychlorinated biphenyls (PCBs) were 11%, mostly from the lower molecular weight congeners, suggesting volatilization as the most likely loss mechanism. The drying process was much shorter, 40 days, yet organic matter content decreased by 27% and moisture by 85%. Losses of 4-NPs (39%) and DEHP (22%) were less than in composting and stopped when moisture content became constant. There were no losses of PCBs. Both treatments are simple, practical procedures that reduce the volume of waste and are applicable in situ on farms. Composting would be the method of choice for reducing organic contaminants but requires much longer times than drying.

The influence of different temperature programmes on the bioremediation of polycyclic aromatic hydrocarbons (PAHs) in a coal-tar contaminated soil by in-vessel composting.

The biodegradation of 16 US. EPA-listed polycyclic aromatic hydrocarbons (sigma PAHs), with accompanying humification and microbial community structure changes during simulated in-vessel composting-bioremediation of an aged coal-tar-contaminated soil amended with green waste were studied over 56 days. The experimental design compared one constant temperature profile (TC=38 degrees C) with three variable temperature profiles (TP1, TP2 and TP3), including treatment at 70 degrees C to comply with regulatory requirements. Greatest sigma PAHs removal (75.4+/-0.1%; k(1)=0.026 day(-1), R(2)=0.98) occurred at TC=38 degrees C compared to all variable temperature profiles TP1 (62.1+/-11.0%; k(1)=0.016 day(-1), R(2)=0.93), TP2 (71.8+/-8.2%; k(1)=0.021 day(-1), R(2)=0.95) and TP3 (45.3+/-9.7%; k(1)=0.010 day(-1), R(2)=0.91). This study proved that using thermophilic temperatures (70 degrees C) towards the end of in-vessel composting processes (TP2) resulted in greater sigma PAHs removal than using other variable temperature profiles (TP1, TP3), as long as the increase was stepwise via an intermediate temperature (55 degrees C). Phospholipid fatty acid (PLFA) signatures indicated that use of thermophilic temperatures towards the end of the in-vessel composting-bioremediation (TP2) resulted in a higher fungal to bacterial PLFA ratio and a lower Gram-positive to Gram-negative (G(+)/G(-)) bacterial ratio. Fluorescence excitation-emission matrix (EEM) showed the presence of peaks typical of humic-like (Ex/Em wavelength pair approximately 340/460 nm) and fulvic-acid-like (Ex/Em wavelength pair approximately 245/460 nm) substances, indicating mineralization and/or maturation of the compost. Varying the temperature during in-vessel composting to comply with regulatory requirements for pathogen control, promoted contaminant biodegradation, microbial activity and compost maturation.

Residues of polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides in organically-farmed vegetables.

The residues of polyaromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs) in soils from organic farms and their uptake by four varieties of organic-produced potatoes and three varieties of organic carrots from England were investigated. Samples of the soils, crop peels and cores were all Soxhlet-extracted in triplicate, cleaned up by open-column chromatography and analysed by a multi-residue analytical method using gas chromatography with mass selective detection. The concentrations of PAHs, PCBs and OCPs in soils from organic farms ranged from 590+/-43 to 2301+/-146 microg/kg, 3.56+/-0.73 to 9.61+/-1.98 microg/kg and 52.2+/-4.9 to 478+/-111 microg/kg, respectively. Uptake by different crop varieties were 8.42+/-0.93 to 40.1+/-4.9 microg/kg sigmaPAHs, 0.83+/-0.19 to 2.68+/-0.94 microg/kg sigmaPCBs and 8.09+/-0.83 to 133+/-27 microg/kg sigmaOCPs. Residue uptake from soils depended on plant variety; Desiree potato and Nairobi carrot varieties were more susceptible to PAH contamination. Likewise, uptake of PCBs and OCPs depended on potato variety. There were significant positive correlations between the PCB and OCP concentrations (P<0.05) in soils and carrots but no significant correlation was found between the concentrations of any contaminants in soils and potatoes. Peeling carrots and potatoes was found to remove 52-100% of the contaminant residues depending on crop variety and the properties of the contaminants. Soil-crop bioconcentration factors (BCFs) decreased with increasing logK(ow) for PAHs up to about 4.5 and for PCBs up to about 6.5, above which no changes were discernible for either class of contaminants. No relationship was observed between soil-crop BCFs and logK(ow) for OCPs, most likely because their concentrations were low and variable.

In-vessel composting--bioremediation of aged coal tar soil: effect of temperature and soil/green waste amendment ratio.

The biodegradation of 16 United States Environmental Protection Agency (USEPA)-listed polycyclic aromatic hydrocarbons (PAHs) present in contaminated soil from a manufactured gas plant site was investigated using laboratory-scale in-vessel composting-bioremediation reactors over 8 weeks. The influence of temperature (T, 38, 55, and 70 degrees C) and soil/green waste ratio (S:GW, 0.6:1, 0.7:1, 0.8:1, and 0.9:1) was investigated. A comparative study using a temperature profile during in-vessel composting-bioremediation to meet current regulatory requirements was also investigated. Temperature and amendment ratio were found to be important operating parameters for PAH removal for in-vessel composting-bioremediation of aged coal tar-contaminated soil. After 8 weeks of continuous treatment, the highest removal of 16 USEPA PAHs was observed at T=38 degrees C and S:GW=0.8:1 (75.2%). Lower removal of 16 USEPA PAHs was observed for temperature profile treatment (60.8%). We recommend that when conventional composting processes using temperature profiles to meet regulatory requirements for pathogen control need to be used, these should start with a prolonged mesophilic stage (6 weeks in this investigation) followed by thermophilic, cooling, and maturation stages.

Analysis of 4-nonylphenols, phthalates, and polychlorinated biphenyls in soils and biosolids.

When sewage sludge is added to agricultural land, organic chemicals contaminants are also added. The fate of these chemicals, particularly those shown to have oestrogenic potential, has received much research and regulatory interest in recent years. A method was developed for the analysis of 4-nonylphenols, phthalates, and PCB congeners in soils, mesophilic anaerobially digested dewatered (MADD) sewage sludge, and MADD sludge-amended soil. After Soxhlet-extraction, the 4-nonylphenols and phthalates were separated from the PCBs on an isolute cyanopropyl SPE cartridge and analysed by GC-MS directly. The PCBs were acid treated on a Bakerbond PCB-A cartridge, then passed through a gel filtration column of Biobeads SX-3 resin, before GC-MS analysis. The method was successfully validated and then used for routine analysis, where average recoveries of the surrogate standards were 83+/-17% (4-n-heptylphenol), 96+/-11% (dimethyl-tere-phthalate), 101+/-12% (dibenzyl-phthalate), and 79+/-13% (PCBs 6, 54, 104, 155, and 198).

Laboratory studies of the remediation of polycyclic aromatic hydrocarbon contaminated soil by in-vessel composting.

The biodegradation of 16 polycyclic aromatic hydrocarbons (PAHs), listed as priority pollutants by the USEPA, present in a coal-tar-contaminated soil from a former manufactured gas plant site was investigated using laboratory-scale in-vessel composting reactors to determine the suitability of this approach as a bioremediation technology. Preliminary investigations were conducted over 16 weeks to determine the optimum soil composting temperature (38, 55 and 70 degrees C). Three tests were performed; firstly, soil was composted with green-waste, with a moisture content of 60%. Secondly, microbial activity was HgCl2-inhibited in the soil green-waste mixture with a moisture content of 60%, to evaluate abiotic losses, while in the third experiment only soil was incubated at the three different temperatures. PAHs and microbial populations were monitored. PAHs were lost from all treatments with 38 degrees C being the optimum temperature for both PAH removal and microbial activity. Calculated activation energy values (E(a)) for total PAHs suggested that the main loss mechanism in the soil-green waste reactors was biological, whereas in the soil reactors it was chemical. Total PAH losses in the soil-green waste composting mixtures were by pseudo-first order kinetics at 38 degrees C (k = 0.013 day(-1), R2 = 0.95), 55 degrees C (k = 0.010 day(-1), R2 = 0.76) and at 70 degrees C (k = 0.009 day(-1), R2 = 0.73).

Polychlorinated biphenyls in bile of patients with biliary tract cancer.

BACKGROUND: Polychlorinated biphenyls (PCBs) are anthropogenic, organic compounds. Although banned in the 1970s, PCBs are poorly biodegradable and hence ubiquitous in the environment. They accumulate in adipose tissue and are implicated various malignancies, including breast and pancreatic cancer. The hepatobiliary system is the main excretory route for such xenobiotic toxins. Incidence rates of intrahepatic biliary tract cancer are increasing worldwide. Measurement and comparison of PCB levels in bile from human patients with benign and malignant bile duct disease has not previously been done. OBJECTIVES: To compare PCB concentrations in bile from patients with malignant (n=8) and non-malignant (n=7) biliary disease. METHODS AND RESULTS: Fifteen human bile samples, collected endoscopically, were analysed using gas chromatography mass spectrometry for seven target PCB congeners (28, 52, 101, 118, 153, 138, and 180), known to occur in the environment and food. Amongst males, total PCB concentrations in bile ranged from 6 ng mL(-1) (aged 73 years) to 49 ng mL(-1) (aged 90 years); and in females between 8 ng mL(-1) (aged 33 years) to 43 ng mL(-1) (aged 67 years) bile. Although there was no overall difference in mean PCB levels between non-cancer and cancer patients, levels of congener 28 were significantly higher in patients with biliary tract cancer (p<0.05). CONCLUSIONS: Despite the banning of PCBs over 30 years ago, these xenobiotics are present in the bile of patients with biliary disease. PCB levels tend to increase with age, suggesting chronic bioaccumulation. Further research is necessary to investigate the relevance of increased levels of congener 28 in bile in biliary tract cancer.

Development of hazard analysis by critical control points (HACCP) procedures to control organic chemical hazards in the agricultural production of raw food commodities.

Hazard Analysis by Critical Control Points (HACCP) is a systematic approach to the identification, assessment, and control of hazards in the food chain. Effective HACCP requires the consideration of all chemical microbiological, and physical hazards. However, current procedures focus primarily on microbiological and physical hazards, while chemical aspects of HACCP have received relatively little attention. In this article we discuss the application of HACCP to organic chemical contaminants and the problems that are likely to be encountered in agriculture. We also present generic templates for the development of organic chemical contaminant HACCP procedures for selected raw food commodities, that is, cereal crops,raw meats, and milk.