Uptake of polychlorinated biphenyls (PCBs) from an aqueous medium by polyethylene, polyvinyl chloride, and polystyrene films.

The sorption of selected polychlorinated biphenyl (PCB) congeners (from tri to deca chlorinated) by three food-packaging plastic films [polyethylene, polyvinyl chloride (PVC), and polystyrene] from an aqueous solution was investigated. From the data generated, PCB uptake, partition, and diffusion coefficients were calculated for the various films. Polyethylene exhibited the highest PCB uptake, diffusion, and partition coefficients when compared to the other materials. Although PVC indicated larger sorption diffusion and partition coefficients for the lower chlorinated congeners than polystyrene, a reversal of this trend was observed for the higher congeners. For polyethylene and PVC, the PCB uptake decreased as the chlorine numbers in the congeners increased, confirming the correlation between increasing chlorination and increasing cohesive density within the PCB molecules. For polystyrene, the uptake decreased from tri to penta congeners, but showed an increase for the hexa, and then a decreased uptake until the deca chlorination. A comparison of the molecular sizes of the PCB congeners showed that the partition (Ke) and sorption diffusion (Ds) coefficients generally decreased with their increasing molar volumes. The resulting Ke values were used to determine the extent of sorption because these values indicate the affinity of PCBs for the plastic films. Results from this study can be of practical importance for cases of product quality related to the transfer of contaminants from the product to the packaging materials.

Determination of degradation products and pathways of mancozeb and ethylenethiourea (ETU) in solutions due to ozone and chlorine dioxide treatments.

The objective of the present study was to determine the degradation products of mancozeb and ethylenethiourea (ETU) and elucidate the possible degradation pathways in solution as a result of chemical oxidation using ozone and chlorine dioxide. This study was developed in a solution at 100 ppm of mancozeb and ETU concentration over the course of 60 min. Two different oxidizing agents used in this study were (1) ozone at 3 ppm and (2) chlorine dioxide at 20 ppm. Ozone was continuously provided throughout the course of the reaction. Degradation products were detected with high-resolution GC-MS. The total analysis time was 4 min per sample combined with rapid GC separation and time-of-flight mass spectrometry (TOFMS). Hydrolysis of mancozeb led to m/z 144 ion fragmentation, which is 5-imidazoledithiocarboxylic acid, as a major degradation product. ETU showed M(+) 102, which corresponds to its mass, indicating this compound was stable in distilled water and did not undergo hydrolysis during 60 min. The average retention times of mancozeb and ETU were approximately 181-189 and 210-230 s, respectively. Ozonation of mancozeb produced ETU as a major product. Treatment of ETU with ozone produced several degradation compounds. From prolonged ozonation, the CS(2) or CS group was removed. Overall, several byproducts identified were M(+) 60, M(+) 84, M(+) 163, M(+) 117, and M(+) 267 by ozone and M(+) 117, M(+) 86, and M(+) 163 by chlorine dioxide treatment. Several of these have been reported, but others have never been reported previously.

Chlorine and chlorine dioxide treatment to reduce or remove EBDCs and ETU residues in a solution.

Calcium hypochlorite (Ca(OCl)(2)) and chlorine dioxide (ClO(2)), common disinfecting and bleaching chemicals used in the food industry, are potent oxidizing agents. In this paper, the degradation effects of chlorine dioxide on mancozeb and ethylenethiourea (ETU) residues were investigated in a model system and compared with those of liquid chlorine, under various conditions such as differing concentration, pH, reaction time, and temperature. All samples were analyzed for residues by GLC and HPLC. Rate of mancozeb degradation was dependent on pH, with pH 4.6 being the most effective. Mancozeb residues decreased 40-100% with chlorine and chlorine dioxide treatments. ETU residue concentrations in mancozeb solutions were monitored over 60 min. Under controlled conditions, the ETU residue concentrations increased up to 15 min reaction time and then decreased in all three pH ranges. Treatment with both chlorine and chlorine dioxide at pH 4.6, yielded no ETU residues at both 10 and 21 degrees C. The results show that chlorine dioxide gives excellent degradation effects at lower concentrations than liquid chlorine.

The Decomposition of Daminozide (Alar) to Form Unsymmetrical Dimethylhydrazine (UDMH) in Heated, pH Adjusted, Canned Solutions.

Processing conditions were chosen to determine the influence of temperature, pH, and processing on model solutions containing daminozide residues. Daminozide (succinamic acid 2, 2-dimethylhydrazide) fortified solutions (12.5 ppm) containing 50mM NaH2PO4 and 24% sucrose (w/w) were adjusted to pH 3.0, 3.6, or 4.0 and either heated (100°C) for 0, 5, 10, or 15 min in sealed cans and cooled or heated (80°C) for 0, 5, or 10 min in open cans, sealed, heated (100°C) for 5 min, and cooled. Daminozide degradation due to heating was less than the HPLC detection limit (1.5 ppm) for all of the treatments. Unsymmetrical dimethylhydrazine (UDMH) concentration was significantly affected by heating time, pH, and processing. Heating of daminozide solutions in sealed cans produced approximately 1 ppm of UDMH for every minute of heating at 100°C. Heating of daminozide solutions in open cans at 80°C resulted in simultaneous production of UDMH in the solution and loss of UDMH through volatilization. Maximum degradation of daminozide was observed at pH 3.6.