A factor analysis model with nonnegative constraints (FA) was used to apportion the sources of PAHs found in sediments of Lake Calumet and surrounding wetlands in southeast Chicago. Source profiles and contributions, with uncertainties, are determined with no prior knowledge of sources. The model includes scaling and backscaling of data with average PAH concentrations without sample normalization. This work is a follow-up to a study that used a chemical mass balance (CMB8.2) model to apportion sources to the same data set. Literature source profiles, modified based on gas/particle partitioning of individual PAHs, from eight PAH sources were considered for comparison. FA results for a two-source solution indicate coke oven (45%) and traffic (55%) are the primary PAH sources to Lake Calumet sediments. A six-source FA solution indicates that coke oven (47%) and traffic (45%) related sources are major PAH sources and wood burning-coal residential (2.3%) is a minor PAH source. From the six-source solution, two coke oven profiles are observed, a standard coke oven profile (33%), and a degraded or second coke oven profile (14%) low in phenanthrene and pyrene. Observed traffic related sources include gasoline engine (36%) exhaust and traffic tunnel air (9.3%). This work supports the previous study of Lake Calumet PAHs by CMB model. In addition, FA provides new insights since wood burning and secondary coke oven profiles were not recognized in the CMB model.
Nine sediment cores were collected from the Sheboygan River Inner Harbor, WI, and analyzed for polychlorinated biphenyl (PCB) congeners. Total PCBs ranged from approximately 0 to 161 mg/g. Positive matrix factorization (PMF) was applied to the PCB data setto determine source profiles. Two factors were determined to be significant. One factor resembled the original approximated PCB mixture of 50% Aroclor 1248 and 50% Aroclor 1254 and the other factor was a dechlorinated version of the mixture. An anaerobic dechlorination model was applied to the dechlorinated source profiles to quantify possible dechlorination pathways. It was found that dechlorination process H' provided the best fit for an individual process, and H' + M provides the best fit for combined processes. PMF source contributions, and plots of PCB concentration versus congener for individual samples, provide evidence of enhanced dechlorination at high concentrations (>40 ppm) and small amounts of dechlorination at low concentrations (<3 ppm). In addition, downward migration of lower chlorinated PCBs in core SR1a has occurred. Remediation dredging in the Upper Sheboygan River in 1989 and 1990 reintroduced PCBs to the water column and selective transport of PCB 18 is observed in core SR7.
Four sediment cores were collected from Lake Hartwell, SC, in 1987 and 1998 and analyzed for polychlorinated biphenyl (PCB) congeners. Total PCBs ranged from -0 to 58 microg/ g. Positive matrix factorization (PMF) was applied to the data sets to determine PCB source profiles. Two factors were determined for each data set. One factor resembled the original estimated PCB mixture of 80% Aroclor 1016 and 20% Aroclor 1254 and the other factor was a dechlorinated version of the mixture. Evidence of a dechlorination plateau is apparent from the PMF loading solutions because the dechlorinated congener profiles do not change from 1987 to 1998, butthe contribution to the profile from the dechlorinated factor increases from 73% (1987) to 87% (1998). PMF source contributions and plots of PCB concentration versus congener for individual samples provide evidence of enhanced dechlorination at high concentrations. After source apportionment an anaerobic dechlorination model was applied to the dechlorinated source profiles to quantify possible dechlorination pathways. It was found that dechlorination process M, extended to target biphenyl rings with up to six chlorines, provided the best fit for an individual process, and M + Q provides the best fit for combined processes, although M + LP also provides a similarfit. Process LP targets the higher chlorinated congeners and appears to dechlorinate PCBs in the sediments initially.
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