Lisa A. Rodenburg

Organic PM2.5 : Fractionation by Polarity, FTIR Spectroscopy, and OM/OC Ratio for the Pittsburgh Aerosol

A polarity-based extraction/fractionation method validated with standard compounds was used to characterize organic aerosol samples collected during the Pittsburgh Air Quality Study (PAQS). Organic extracts were separated into 5 polarity classes by sequential elution with hexane, dichloromethane, ethyl acetate, acetone, and methanol. Organic mass (OM) and carbon mass (OC) were measured in samples, their extracts, and their corresponding fractions yielding OM/OC ratios and the contribution of each polarity fraction to total OM. The study average OM/OC ratio for each fraction [(OM/OC)fraction] varied from 1.37 for the hexane fraction to 2.25 for the methanol fraction. OM/OC ratios for “non-extractable” organics ((OM/OC)N-E) were also predicted; the study average (OM/OC)N - E was 2.54, consistent with ratios of 2.1–3.2 for water-soluble organic aerosol species. Annual average ratios with and without the contributions of the “non-extractable” material [(OM/OC)total and (OM/OC)extract, respectively] were 2.05 ± 0.18(1σ) and 1.91 ± 0.24(1σ), similar to OM/OC of atmospherically relevant oligomers and aged aerosols measured elsewhere. Ratios were somewhat higher during summer/winter than spring/fall, probably because of a greater contribution of oxidized species such as dicarboxylic acids (summer), levoglucosan (winter and/or summer), and humic-like-substances (HULIS; winter and/or summer). We hypothesize that the OM/OC of atmospheric aerosols approaches a value of 1.9–2.1 as it ages and oligomerizes in the atmosphere. The annual-average contributions of each fraction to the total collected OM mass were, 16.8, 14.0, 11.7, 11.5, 19.3, and 26.7% for the hexane-, dichloromethane-, ethyl acetate-, acetone-, methanol-, and “non-extractable” fractions, respectively. Thus non-polar and very polar species dominated the OM mass throughout the year. Fourier transformed infrared (FTIR) spectroscopy was used to further characterize the composition of extracts and fractions. This method can be used to fractionate organic PM for toxicological studies as well as organic aerosol characterization.

PCB dechlorination enhancement in Anacostia River sediment microcosms

In situ treatment of PCB contaminated sediments via microbial dechlorination is a promising alternative to dredging, which may be reserved for only the most contaminated areas. Reductive dechlorination of low levels of weathered PCB mixtures typical of urban environments may occur at slow rates. Here, we report that biostimulation and bioaugmentation enhanced dechlorination of low concentration (2.1 mg PCBs/kg dry weight) historical PCBs in microcosms prepared with Anacostia River, Washington, DC, sediment. Treatments included electron donors butyrate, lactate, propionate and acetate (1 mM each); alternate halogenated electron acceptors (haloprimers) tetrachlorobenzene (TeCB, 25 microM), pentachloronitrobenzene (PCNB, 25 microM), or 2,3,4,5,6-PCB (PCB116, 2.0 microM); and/or bioaugmentation with a culture containing Dehalococcoides ethenogenes strain 195 (3 x 10(6)cells/mL). Dechlorination rates were enhanced in microcosms receiving bioaugmentation, PCNB and PCNB plus bioaugmentation, compared to other treatments. Microcosm subcultures generated after 415 days and spiked with PCB116 showed sustained capacity for dechlorination of PCB116 in PCNB, PCNB plus bioaugmentation, and TeCB treatments, relative to other treatments. Analysis of Chloroflexi 16S rRNA genes showed that TeCB and PCNB increased native Dehalococcoides spp. from the Pinellas subgroup; however this increase was correlated to enhanced dechlorination of low concentration weathered PCBs only in PCNB-amended microcosms. D. ethenogenes strain 195 was detected only in bioaugmented microcosms and decreased over 281 days. Bioaugmentation with D. ethenogenes strain 195 increased PCB dechlorination rates initially, but enhanced capacity for dechlorination of a model congener, PCB116, after 415 days occurred only in microcosms with enhanced native Dehalococcoides spp.

Evidence for widespread dechlorination of polychlorinated biphenyls in groundwater, landfills, and wastewater collection systems.

One of the few pathways for environmental transformation of polychlorinated biphenyls (PCBs) is microbial dechlorination under anaerobic conditions, which is reported to occur in contaminated sediments of rivers, lakes and harbors. The goal of this work was to determine whether PCB dechlorination occurs in built waste treatment environments. We analyzed a large database on PCB congener concentrations in effluents and some influents of facilities in the Delaware River Basin. Positive matrix factorization was used to identify the sources of PCBs and to look for evidence of dechlorination. Seven factors were resolved from the data set of 89 congeners in 645 samples. Two of the resolved factors represented dechlorination signals. One of these was dominated by PCBs 4 and 19 and represents an advanced stage of dechlorination of Aroclors to di- and trichlorinated congeners. This dechlorination signal was most prevalent in effluents from sites with contaminated groundwater and from wastewater treatment plants (WWTPs) that serve combined sewers or treat landfill leachate. The other dechlorination signal appeared to represent an intermediate stage of dechlorination, because it was dominated by two coeluting groups of tetrachlorinated congeners: PCBs 44 + 47 + 65 and 45 + 51. This partial dechlorination signal was most prevalent in the 40 WWTPs with separate (sanitary) sewer systems, where it often comprised more than 20% of the PCBs in the effluents. Both dechlorination signals were present in WWTP influents, but were not observed in stormwater runoff, suggesting that dechlorination occurs in sewers. This work represents the first convincing evidence of PCB dechlorination occurring outside of contaminated aquatic sediments or anaerobic digesters. The results suggest that PCBs are dechlorinated by anaerobic bacteria in sewers, landfills, and contaminated groundwater. These two dechlorination signals comprise about 19% of the total loads of PCBs to the Delaware River from the sampled dischargers.

Source Apportionment of Polychlorinated Biphenyls in the Sediments of the Delaware River

Polychlorinated biphenyls (PCBs) are toxic, persistent, bioaccumulative compounds that threaten water quality in many areas, including the Delaware River. In 2003, total maximum daily loads for PCBs were promulgated for the tidal portion of the river, requiring the collection of a massive and unprecedented data set on PCBs in an urban estuary using state of the art, high-resolution high mass spectrometry (EPA method 1668 revision A). In previous publications, this data set has been examined using positive matrix factorization (PMF) to apportion PCB sources in the air, water, and permitted discharges to the river. Here, the same technique is used to apportion PCB sources in the sediment. This holistic approach allows the comparison of source types and magnitudes to the air, water, and sediment, and allows conclusions to be drawn about the cycling of PCBs in a typical urbanized estuary. A data set containing 87 chromatographic peaks representing 132 PCB congeners in 81 samples and 6 duplicated samples was analyzed. Seven factors were resolved. Three represent relatively unweathered Aroclors. Two were related to the non-Aroclor sources of diarylide yellow pigments and titanium tetrachloride production. The two remaining factors were probably originally related to Aroclors, but they are so highly weathered as to be unrecognizable as Aroclors, and thus have probably resided in the river for a long time. Comparing the abundance of the resolved PCB factors in the air, water, discharges, and sediment demonstrates that high molecular weight formulations, such as Aroclor 1260 and PCBs 206, 208, and 209 produced during titanium tetrachloride synthesis accumulate preferentially in the sediment, in keeping with their greater hydrophobicity. In contrast, lower molecular weight formulations, including the products of PCB dechlorination occurring in sewers, do not accumulate appreciably. PCB 11 from pigment use does accumulate in sediments and also seems to be distributed throughout the estuary via the atmosphere.

Source apportionment of polychlorinated biphenyls in the New York/New Jersey Harbor.

The New York/New Jersey Harbor (also known as the Hudson River Estuary) is heavily contaminated with polychlorinated biphenyls (PCBs) arising in part from inputs from the Upper Hudson River, which is a Superfund site containing historical PCB contamination, and also due to inputs from the New York City metropolitan area. The Contamination Assessment and Reduction Project (CARP) measured PCBs and other contaminants in ambient water samples collected throughout the Harbor region during 1998-2001. In order to investigate the sources of PCBs to the NY/NJ Harbor, this data base of PCB concentrations was analyzed using Positive Matrix Factorization (PMF). This analysis resolved seven factors that are thought to be associated with sources such as the Upper Hudson River, storm water runoff, combined sewer overflows (CSOs), and wastewater effluents. The PMF model also produced a factor that appears to be related to sites contaminated with Aroclor 1260. To the extent that the NY/NJ Harbor is typical of urbanized estuaries throughout the United States, these results suggest that storm water runoff is probably a significant source of PCBs to surface waters in urban areas.

The effect of co-substrate activation on indigenous and bioaugmented PCB dechlorinating bacterial communities in sediment microcosms

Microbial reductive dechlorination by members of the phylum Chloroflexi, including the genus Dehalococcoides, may play an important role in natural detoxification of highly chlorinated environmental pollutants, such as polychlorinated biphenyls (PCBs). Previously, we showed the increase of an indigenous bacterial population belonging to the Pinellas subgroup of Dehalococcoides spp. in Anacostia River sediment (Washington DC, USA) microcosms treated with halogenated co-substrates (“haloprimers”), tetrachlorobenzene (TeCB), or pentachloronitrobenzene (PCNB). The PCNB-amended microcosms exhibited enhanced dechlorination of weathered PCBs, while TeCB-amended microcosms did not. We therefore developed and used different phylogenetic approaches to discriminate the effect of the two different haloprimers. We also developed complementary approaches to monitor the effects of haloprimer treatments on 12 putative reductive dehalogenase (rdh) genes common to Dehalococcoides ethenogenes strain 195 and Dehalococcoides sp. strain CBDB1. Our results indicate that 16S rRNA gene-based phylogenetic analyses have a limit in their ability to distinguish the effects of two haloprimer treatments and that two of rdh genes were present in high abundance when microcosms were amended with PCNB, but not TeCB. rdh gene-based phylogenetic analysis supports that these two rdh genes originated from the Pinellas subgroup of Dehalococcoides spp., which corresponds to the 16S rRNA gene-based phylogenetic analysis.

Evidence for dechlorination of polychlorinated biphenyls and polychlorinated dibenzo-p-dioxins and -furans in wastewater collection systems in the New York metropolitan area.

Polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) are persistent organic pollutants targeted by the Stockholm Convention. Both contain aromatic chlorines and are subject to microbial dechlorination. Dechlorination of PCBs in sewers in the Delaware River basin was recently reported. In this work, two data sets on concentrations of PCBs and PCBs+PCDD/Fs in wastewater treatment plant influents and effluents were analyzed to look for evidence that these compounds undergo dechlorination in the sewers of the New York/New Jersey Harbor area. The two data sets come from the Contamination Assessment and Reduction Project (CARP) and were analyzed via Positive Matrix Factorization (PMF). Analysis of the data set containing only PCB concentrations suggests that PCBs are dechlorinated in the sewers of the NY/NJ Harbor via the same pathways observed in the sewers of the Delaware River basin and that advanced dechlorination of PCB mixtures is more likely to occur in combined sewers vs separate sanitary sewers. When the combined data set of PCBs+PCDD/Fs was analyzed, the factor containing PCB dechlorination products also contained high proportions of 1,2,3,4,6,7,8-heptachlorodibenzo-p-dioxin (HpCDD), a known product of the dechlorination of octachlorodibenzo-p-dioxin (OCDD), and other known dechlorination products of PCDD/Fs. Despite being the most abundant PCDD/F congener in all of the samples in the database, OCDD was a minor component in the dechlorination factor. This provides the first evidence that PCDD/Fs may be dechlorinated in sewers.

Source apportionment of polychlorinated biphenyls in Chicago air from 1996 to 2007.

While the overall atmospheric polychlorinated biphenyl (PCB) levels in many urban areas are declining, it is not clear whether this decline is due to control strategies or merely due to natural attenuation. To investigate this issue, Positive Matrix Factorization (PMF) was used to identify the dominant sources of gas-phase PCBs in the atmosphere of Chicago, IL using a data set collected from 1996 to 2007 by the Integrated Atmospheric Deposition Network (IADN). Both the older PMF2 software and the newer EPA-sponsored PMF 3.0 software were employed. Both models resolved 5 factors, but they yielded somewhat different results in terms of the congener patterns of the factors and their temporal variation. The PMF2 software resolved factors that better resembled the original Aroclor formulations. While it is possible to apply an exponential decay model to this data set and derive statistically significant rate constants that indicate that ΣPCBs and some of the resolved factors are declining in Chicago air, examining plots of the 365-day moving average concentrations shows that they do not decrease in a fashion consistent with exponential decay. Instead, they display periods of decline as well as periods of increase. Thus an exponential decay model is not appropriate, and long-term time trends identified from this 12-year data set cannot be used to predict the future trends in PCB concentrations in the air of Chicago. Two of the five resolved factors resemble low MW Aroclors, and declined from 1996 to 2007. The other three factors, which represent the majority of the mass in the data set, are either not declining or actually increasing over time. Thus past efforts to eliminate PCBs from the Great Lakes ecosystem have been only marginally effective, if at all. Additional effort is needed to identify and eliminate atmospheric PCB sources in Chicago.

Water‐column concentrations and partitioning of polybrominated diphenyl ethers in the New York/New Jersey Harbor, USA

Despite the emerging concern regarding polybrominated diphenyl ethers (BDEs), very few measurements of BDE concentrations in ambient water have been published. In the present study, BDEs were measured in water samples from the New York/New Jersey Harbor (USA). Samples were taken in Raritan Bay west of Sandy Hook during four intensive sampling campaigns in 2000 and 2001. Congeners 17, 47, 99, 100, 153, 154, 183, and 209 were detected. Total BDE (σBDE) concentrations (average ± standard deviation) were 175 ± 75 ng/g in the particle phase and 110 ± 72 pg/L in the apparent dissolved phase. The deca-congener, BDE 209, constituted 85 and 9% of σBDEs in the particle and apparent dissolved phases, respectively. The σBDE levels are significantly higher than those measured in Lake Ontario, USA, and in The Netherlands, but they are similar to concentrations measured in Lake Michigan and San Francisco Bay (both USA). Calculated values of the organic carbon-water partition coefficient (KOC) were strongly correlated with literature values of the octanol-water partition coefficient (KOW). The data suggest that sorption of BDEs to colloids is important in this system, although quantifying the extent of colloid sorption is difficult.

Reactivity of Alkyl Polyhalides toward Granular Iron: Development of QSARs and Reactivity Cross Correlations for Reductive Dehalogenation

Attempts to develop quantitative structure-activity relationships (QSARs) for reductive dehalogenation by granular iron have been hindered by the unavailability of high quality predictor variables, have included relatively few compounds, and on occasion have relied on data lacking internal consistency. We herein investigate the reduction of 24 alkyl polyhalides by granular iron and the better-defined, homogeneous reductants Cr(H(2)O)(6)(2+) and an Fe(II) porphyrin. QSARs were constructed with a new set of computationally derived gas phase homolytic carbon-halogen bond dissociation energies and solvated one-electron reduction potentials determined using a quantum chemistry composite method (G3MP2). Reactivity cross correlations between reductant systems were also developed. Reactivity trends were generally consistent among all reductants and revealed pronounced structural influences. Compounds reduced at C-Br were orders of magnitude more reactive than analogues reduced at C-Cl; the number and identity of α- (Br ∼ Cl > CH(3) > F > H) and β-substituents (Br > Cl) also influenced reactivity. Nonlinearities encountered during QSAR and cross correlation development suggest that reactions of highly halogenated alkyl polyhalides with granular iron are limited by mass transfer, as supported by estimates of mass transfer coefficients. For species not suspected to exhibit mass transfer limitations, reasonably strong cross correlations and comparable substituent effects are consistent with dissociative electron transfer as the rate-determining step.