PubMed · 11767941
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F I Grunder. PAT Program Report: background and current status.. https://doi.org/10.1080/15298660108984684
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Pressurized liquid extraction (PLE) is a fully automated extraction technique for isolation of analytes from solid samples. This technique combines elevated temperature and pressure of liquid solvents during the extraction process. In this study the efficiency of a PLE system for the isolation of wide range of analytes (polychlorinated biphenyls and organic pesticides from sediments under different pressure and temperature conditions) was investigated. The temperature 100 degrees C and pressure 6.9 MPa (1000 p.s.i.; 1 p.s.i.=6894.76 Pa) were found to be the most efficient from all investigated conditions. Using these PLE parameters, the average recoveries for most of the analytes were in the range 80-105% and relative standard deviation was usually under 15%. The conditions of determination of analytes in the extracts using GC-MS were established. Some problems occurring during the analysis of real samples, such as coelution of analytes, were established. The influence of internal standard addition on the final analysis results was determined.
Information on the historical global production and consumption of polychlorinated biphenyls (PCBs) is urgently needed for estimating PCB fluxes to the environment and for interpreting global contamination patterns by these pollutants. This study presents the methodology, principal uncertainties and selected results from an inventory, aiming to quantify the global production and consumption of total PCBs as well as 22 PCB congeners. The available data on the historical production of PCBs and the chemical composition of various technical mixtures have been compiled from the literature. For some producers with less detailed information, the production of individual PCB constituents has been estimated to derive a global estimate for individual homologues and selected congeners. Information on imports, exports and consumption, as well as restrictions on production and imports, has further been compiled for individual countries. These data, along with assumptions on the trade between countries and regions, have been utilised to derive an estimate of the global historical consumption pattern. Although there are substantial uncertainties involved in these estimates, important aspects governing the large scale temporal and spatial patterns are most likely captured in these estimates. In particular, the information on imports and exports for the principal users of PCBs around the time of peak production is considered to be fairly reliable. The estimates account for a reported historical global production of approximately 1.3 million t PCBs, more than 70% of which are tri-, tetra- and pentachlorinated biphenyls. The results further suggest that almost 97% of the global historical use of PCBs have occurred in the Northern Hemisphere.
Na/NH3 reductions have been used to dehalogenate polychlorinated biphenyls (PCBs), chlorinated aliphatic hydrocarbons (CAHs) and pesticides at diffusion controlled rates at room temperature in model compound studies in both dry NH3 and when water was added. The rate ratio of dechlorination (aliphatic and aromatic compounds) versus reaction of the solvated electron with water is very large, allowing wet soils or sludges to be remediated without an unreasonable consumption of sodium. Several soils, purposely contaminated with 1,1,1-trichloroethane, 1-chlorooctane and tetrachloroethylene, were remediated by slurring the soils in NH3 followed by addition of sodium. The consumption of sodium per mole of chlorine removed was examined as a function of both the hazardous substrate's concentration in the soil and the amount of water present. The Na consumption per Cl removed increases as the amount of water increases and as the substrate concentration in soil decreases. However, remediation was still readily accomplished from 5000 to 3000ppm to sub ppm levels of RCl in the presence of substantial amounts of water. PCB- and dioxin-contaminated oils were remediated with Na/NH3 as were PCB-contaminated soils and sludges from contaminated sites. Ca/NH3 treatments also successfully remediated PCB-contaminated clay, sandy and organic soils but laboratory studies demonstrated that Ca was less efficient than Na when substantial amounts of water were present. The advantages of solvated electron reductions using Na/NH3 include: (1) very rapid dehalogenation rates at ambient temperature, (2) soils (even clay soils) break down into particles and slurry nicely in NH3, (3) liquid ammonia handling technology is well known and (4) removal from soils, recovery and recycle of ammonia is easy due to its low boiling point. Finally, dechlorination is extremely fast even for the 'corner' chlorines in the substrate Mirex (structure in Eq. (5)).