One century record of contamination by polycyclic aromatic hydrocarbons and polychlorinated biphenyls in core sediments from the southern Yellow Sea

Sixteen polycyclic aromatic hydrocarbons (PAHs) and 28 polychlorinated biphenyls (PCBs) were measured at a 2-cm interval in a core sample from the middle of the southern Yellow Sea for elucidating their historical variations in inflow and sources. The chronology was obtained using the Pb-210 method. PAHs concentrations decreased generally with depth and two climax values occurred in 14-16 cm and 20-22 cm layers, demonstrating that the production and usage of PAHs might reach peaks in the periods of 1956-1962 and 1938-1944. The booming economy and the navy battles of the Second World War might explain why the higher levels were detected in the two layers. The result of principal component analysis (PCA) revealed that PAHs were primarily owing to the combustion product. Down-cored variation of PCB concentrations was complex. Higher concentrations besides the two peaks being the same as PAHs were detected from 4 to 8 cm, depositing from 1980 to 1992, which probably resulted from the disposal of the out-dated PCB-containing equipment. The average Cl percentage of PCBs detected was similar to that of the mixture of Aroclor 1254 and 1242, suggesting they might origin from the dielectrical and heat-transfer fluid. The total organic carbon (TOC) content played a prevalent role in the adsorption of high molecular weight PAHs (>= 4-ring), while no obvious relationship among total PCBs, the concentration of congeners, and TOC was found.

Correct identification of polychlorinated biphenyls in temperature-programmed GC with ECD detection

A method has been developed for peak identification of PCBs in GC with ECD detection under different temperature programs and isothermal conditions on two commonly used columns (DB-5 and DB-1701). This was achieved by means of accurate calibration of retention times based on the concept of the relative retention index P-i and retention times of the selected PCB internal standards. The P-i was calculated from the predicted retention times with the database of the retention parameters (A, B) and the migration equations. Through comparison of the calibrated and experimental retention times of PCBs in technical samples, it was shown that the developed method was effective for correct PCB comprehensive, quantitative, congener-specific (CQCS) analyses.

A practical approach to the degradation of polychlorinated biphenyls in transformer oil

A practical and efficient disposal method for hydrodechlormation of polychlorinated biphenyls (PCBs) in transformer oil is reported. Transformer oil containing PCBs was treated by nanometric sodium hydride (nano-NaH) and transition metal catalysts. High destruction and removal efficiency (89.8%) can be attained by nano-NaH alone under mild conditions. The process exhibits apparent characteristics of a first order reaction. The reductive ability of nano-NaH was enhanced by the addition of transition metal catalysts. In the presence of TiCl4, 99.9% PCBs was hydrodechlorinated. The complex reducing reagents, Ni(OAc)(2) + i-PrONa, show extra hydrodechlorinating activity for di-chlorinated biphenyls. (c) 2004 Elsevier Ltd. All rights reserved.

Mortality among 24,865 workers exposed to polychlorinated biphenyls (PCBs) in three electrical capacitor manufacturing plants: a ten-year update.

The objective of this analysis was to evaluate mortality among a cohort of 24,865 capacitor-manufacturing workers exposed to polychlorinated biphenyls (PCBs) at plants in Indiana, Massachusetts, and New York and followed for mortality through 2008. Cumulative PCB exposure was estimated using plant-specific job-exposure matrices. External comparisons to US and state-specific populations used standardized mortality ratios, adjusted for gender, race, age and calendar year. Among long-term workers employed 3 months or longer, within-cohort comparisons used standardized rate ratios and multivariable Poisson regression modeling. Through 2008, more than one million person-years at risk and 8749 deaths were accrued. Among long-term employees, all-cause and all-cancer mortality were not elevated; of the a priori outcomes assessed only melanoma mortality was elevated. Mortality was elevated for some outcomes of a priori interest among subgroups of long-term workers: all cancer, intestinal cancer and amyotrophic lateral sclerosis (women); melanoma (men); melanoma and brain and nervous system cancer (Indiana plant); and melanoma and multiple myeloma (New York plant). Standardized rates of stomach and uterine cancer and multiple myeloma mortality increased with estimated cumulative PCB exposure. Poisson regression modeling showed significant associations with estimated cumulative PCB exposure for prostate and stomach cancer mortality. For other outcomes of a priori interest--rectal, liver, ovarian, breast, and thyroid cancer, non-Hodgkin lymphoma, Alzheimer disease, and Parkinson disease--neither elevated mortality nor positive associations with PCB exposure were observed. Associations between estimated cumulative PCB exposure and stomach, uterine, and prostate cancer and myeloma mortality confirmed our previous positive findings.

Investigations into the determination of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) by capillary gas chromatography

Factors involved in the determination of PAHs (16 priority PAHs as an example) and PCBs (10 PCB congeners, representing 10 isomeric groups) by capillary gas chromatography coupled with mass spectrometry (GC/MS, for PAHs) and electron capture detection (GC/ECD , for PCBs) were studied, with emphasis on the effect of solvent. Having various volatilities and different polarities, solvent studied included dichloromethane, acetonitrile, hexan e, cyclohexane, isooctane, octane, nonane, dodecane, benzene, toluene, p-xylene, o-xylene, and mesitylene. Temperatures of the capillary column, the injection port, the GC/MS interface, the flow rates of carrier gas and make-up gas, and the injection volume were optimized by one factor at a time method or simplex optimization method. Under the optimized conditions, both peak height and peak area of 16 PAHs, especially the late-eluting PAHs, were significantly enhanced (1 to 500 times) by using relatively higher boiling point solvents such as p-xylene and nonane, compared with commonly used solvents like benzene and isooctane. With the improved sensitivity, detection limits of between 4.4 pg for naphthalene and 30.8 pg for benzo[g,h,i]perylene were obtained when p-xylene was used as an injection solvent. Effect of solvent on peak shape and peak intensity were found to be greatly dependent on temperature parameters, especially the initial temperature of the capillary column. The relationship between initial temperature and shape of peaks from 16 PAHs and 10 PCBs were studied and compared when toluene, p-xylene, isooctane, and nonane were used as injection solvents. If a too low initial temperature was used, fronting or split of peaks was observed. On the other hand, peak tailing occurred at a too high initial column temperature. The optimum initial temperature, at which both peak fronting and tailing were avoided and symmetrical peaks were obtained, depended on both solvents and the stationary phase of the column used. On a methyl silicone column, the alkane solvents provided wider optimum ranges of initial temperature than aromatic solvents did, for achieving well-shaped symmetrical GC peaks. On a 5% diphenyl: 1% vinyl: 94% dimethyl polysiloxane column, when the aromatic solvents were used, the optimum initial temperature ranges for solutes to form symmetrical peaks were improved to a similar degree as those when the alkanes were used as injection solvents. A mechanism, based on the properties of and possible interactions among the analyte, the injection solvent, and the stationary phase of the capillary column, was proposed to explain these observations. The effect of initial temperature on peak height and peak area of the 16 PAHs and the 10 PCBs was also studied. The optimum initial temperature was found to be dependent on the physical properties of the solvent used and the amount of the solvent injected. Generally, from the boiling point of the solvent to 10 0C above its boiling point was an optimum range of initial temperature at which cthe highest peak height and peak area were obtained.

Organochlorine pesticides and polychlorinated biphenyls in soil and water samples in the northeastern part of São Paulo State, Brazil

Detailed analyses of persistent organic pollutants (POPs) such as organochlorine pesticides (OCPs), hexachlorocyclohexane (HCH) isomers (HCHs), dichlorodiphenyltrichloro ethane (DDT) and its metabolites (DDTs) and congeners of polychlorinated biphenyls (PCBs) in soil and surface water from the northeastern São Paulo, Brazil allowed the evaluation of the contamination status, distribution and possible pollution sources. The pesticides and PCBs demonstrated markedly different distributions, reflecting different agricultural, domestic and industrial usage in each region studied. The ranges of HCH, DDT, and PCBs concentrations in the soil samples were 0.05-0.92, 0.12-11.01, 0.02-0.25 ng g(-1) dry wt, respectively, and in the surface water samples were 0.02-0.6, 0.02-0.58 and 0.02-0.5 ng l(-1), respectively. Overall elevated levels of DDT and PCB were recorded in region 2, a site very close to melting, automotive batteries industries, and agricultural practice regions. High ratios of metabolites of DDT to DDT isomers revealed the recent use of DDT in this environment. The sources of contamination are closely related to human activities, such as domestic and industrial discharge, street runoff, agricultural pesticides and soil erosion, due to deforestation as well as atmospheric transport. (c) 2006 Elsevier Ltd. All rights reserved.