Intracity occurrence and distribution of airborne PCB congeners in Chicago.

To evaluate the magnitude and extent of airborne PCBs in an urban area, we measured and investigated the temporal and spatial behavior of atmospheric concentrations of individual polychlorinated biphenyl (PCB) congeners as well as the sum of all congeners (ΣPCB) in both gas and particle phases at 27 locations across the City of Chicago in a single year (2009). In total, 141 gas-phase air samples were collected, including 22 pairs (44 samples) deployed at the same time but at two different locations, and 46 particle-phase samples. ΣPCB in the gas-phase ranged from 80 to 3000 pg/m3, with a geometric mean (GM) of 530 pg/m3, whereas particle-phase ranged from 8 to 160 pg/m3, with a GM of 28 pg/m3. We found the temporal variability to be about three times larger than the variability over space for all gas-phase congeners and ΣPCB. Around 50% of the sample PCB profiles resembled a mixture of a 1:1 vapor Aroclor mixture of 1016 + 1254, with most of the rest (30%) showing enrichment of PCB 3 (>0.1), which did not match any Aroclor profiles. PCB 11 contributed to ~5% in all samples. The fractions of PCB congeners bound to particles ranged from 0.001 to 0.97. Our analysis shows that airborne PCBs are widely distributed across Chicago and confirms that most locations have a similar PCB distribution, but differ in the concentration levels. Volatilization continues to be the main release process of PCBs into the atmosphere, including both Aroclor and non-Aroclor congeners.

Microbial communities in polychlorinated biphenyl (PCB)-contaminated wastewater lagoon sediments: PCB congener, quantitative PCR, and 16S rRNA gene amplicon sequencing datasets.

The potential for aerobic and anaerobic microbial natural attenuation of PCBs in freshwater sediments is described by PCB congener, quantitative PCR, and 16S rRNA gene amplicon sequencing datasets generated, in duplicate, from 27 sediment samples collected from a PCB-contaminated freshwater lagoon (54 samples total). Sediment samples were subjected to a hexane PCB extraction protocol and the concentrations of 209 PCB congeners were determined in hexane extracts by gas chromatography with a tandem mass spectrometry detection. DNA was extracted from sediments sediment samples and used for qPCR and 16S rRNA amplicon sequencing. The abundance of 16S rRNA genes (i.e., Dehalococcoides and putative dechlorinating Chloroflexi) and functional genes (i.e., reductive dehalogenase (rdhA) and biphenyl dioxygenase (bphA)) associated with aerobic and anaerobic PCB biodegradation, along with the total 16S rRNA genes abundance, was determined by SYBR green qPCR. The microbial community composition and structure in all sediment samples was obtained by 16S rRNA gene amplicon sequencing. Primers targeting the 16S rRNA gene V4 region were used to produce 16S rRNA gene amplicons that were sequencing with the high-throughput Illumina MiSeq platform and sequencing chemistry. The 16S rRNA gene sequencing dataset along with PCB congener and qPCR datasets included as metadata, could be reused in meta-analyses that aim to determine microbial community interactions in contaminated environments, and uncover relationships between microbial community structure and environmental variable (e.g., PCB congener concentrations).

Signal Processing Methods to Interpret Polychlorinated Biphenyls in Airborne Samples.

The main contribution of this interdisciplinary work is a robust computational framework to autonomously discover and quantify previously unknown associations between well-known (target) and potentially unknown (non-target) toxic industrial air pollutants. In this work, the variability of polychlorinated biphenyl (PCB) data is evaluated using a combination of statistical, signal processing, and graph-based informatics techniques to interpret the raw instrument signal from gas chromatography-mass spectrometry (GC/MS/MS) data sets. Specifically, minimum mean-squared techniques from the adaptive signal processing literature are extended to detect and separate coeluted (overlapped) peaks in the raw instrument signal. A graph-based visualization is provided which bridges two complementary approaches to quantitative pollution studies: (i) peak-cognizant target analysis (limits data analysis to few well-known compounds) and (ii) chemometric analysis (statistical large-scale data analysis) that is agnostic of specific compounds. Further, peak fitting techniques based on L2 error minimization are employed to autonomously calculate the amount of each PCB present with a normalized mean square error of -18.4851 dB. Graph-based visualization of associations between known and unknown compounds are developed through principal component analysis and both fuzzy c-means (FCM) and k-means clustering techniques are implemented and compared. The efficiency of these methods are compared using 150 air samples analyzed for individual PCBs with GC/MS/MS against traditional target-only techniques that perform analysis across only the known (target) PCBs. Parameter optimization techniques are employed to evaluate the relative contribution of PCB signals against ten potential source signals representing legacy signatures from historical manufacture of Aroclors and modern sources of PCBs produced as by products of pigment and polymer manufacturing. Aroclors 1232, 1254, 1016, and 1221 as well as non-Aroclor 3, 3', dichlorobiphenyl (PCB 11) were found in many of the samples as unique source signals that describe PCB mixtures in air samples collected from Chicago, IL.

Determination of PCB fluxes from Indiana Harbor and Ship Canal using dual-deployed air and water passive samplers.

We have developed a method for measuring fluxes of PCBs from natural waters using air and water passive samplers deployed simultaneously in the Indiana Harbor and Ship Canal (IHSC). Net volatilization of Æ©PCBs was determined for 2017, and ranged from 1.4 to 2.8 µg m-2 d-1, with a median of 2.0 µg m-2 d-1. We confirm earlier findings that the IHSC experiences constant release of gas-phase PCBs. Gas-phase and freely-dissolved water Æ©PCB samples median were 4.0 ng m-3 and 14 ng L-1, both exhibiting increasing concentrations over the year of study, and with a strong positive correlation between them (R2 = 0.93 for Æ©PCBs). The relative concentrations of individual PCB congeners were very similar between air and water samples, and resemble Aroclor 1248, a mixture previously reported to contaminate the IHSC sediments. Monthly variability of the volatilization fluxes was primarily driven by the freely-dissolved water concentration changes (R2 = 0.87). Although different sampling methods were performed to estimate air-water fluxes between the month of August of 2006 and 2017, Æ©PCB net fluxes have decreased by more than 60%, suggesting that either dredging at IHSC from 2012 to 2017 or reduction of upstream sources have decreased the freely-dissolved water concentrations of PCBs, thus reducing the air-water net volatilization in IHSC. Finally, we have shown that this passive sampling approach represents a simple and cost-effective method to assess the air-water exchange of PCBs, increase analytical sensitivity, enable measurements over time, and reduce uncertainties related to unexpected episodic events.

Airborne PCBs and OH-PCBs Inside and Outside Urban and Rural U.S. Schools.

PCBs appear in school air because many school buildings were built when PCBs were still intentionally added to building materials and because PCBs are also present through inadvertent production in modern pigment. This is of concern because children are especially vulnerable to the toxic effects of PCBs. Here we report indoor and outdoor air concentrations of PCBs and OH-PCBs from two rural schools and four urban schools, the latter near a PCB-contaminated waterway of Lake Michigan in the United States. Samples (n = 108) were collected as in/out pairs using polyurethane foam passive air samplers (PUF-PAS) from January 2012 to November 2015. Samples were analyzed using GC/MS-MS for all 209 PCBs and 72 OH-PCBs. Concentrations inside schools were 1-2 orders of magnitude higher than outdoors and ranged from 0.5 to 194 ng/m3 (PCBs) and from 4 to 665 pg/m3 (OH-PCBs). Congener profiles were similar within each sampling location across season but different between schools and indicated the sources as Aroclors from building materials and individual PCBs associated with modern pigment. This study is the first cohort-specific analysis to show that some children's PCB inhalation exposure may be equal to or higher than their exposure through diet.

Release of Airborne Polychlorinated Biphenyls from New Bedford Harbor Results in Elevated Concentrations in the Surrounding Air.

Qualitatively and quantitatively, we have demonstrated that airborne polychlorinated biphenyl (PCB) concentrations in the air surrounding New Bedford Harbor (NBH) are caused by its water PCB emissions. We measured airborne PCBs at 18 homes and businesses near NBH in 2015, with values ranging from 0.4 to 38 ng m-3, with a very strong Aroclor 1242/1016 signal that is most pronounced closest to the harbor and reproducible over three sampling rounds. Using U.S. Environmental Protection Agency (U.S. EPA) water PCB data from 2015 and local meteorology, we predicted gas-phase fluxes of PCBs from 160 to 1200 µg m-2 day-1. Fluxes were used as emissions for AERMOD, a widely applied U.S. EPA atmospheric dispersion model, to predict airborne PCB concentrations. The AERMOD predictions were within a factor of 2 of the field measurements. PCB emission from NBH (110 kg year-1, average 2015) is the largest reported source of airborne PCBs from natural waters in North America, and the source of high ambient air PCB concentrations in locations close to NBH. It is likely that NBH has been an important source of airborne PCBs since it was contaminated with Aroclors more than 60 years ago.

Occurrence and Distribution of Two Hydroxylated Polychlorinated Biphenyl Congeners in Chicago Air.

We measured hydroxylated polychlorinated biphenyls (OH-PCBs) in both gas and particulate phases in 30 Chicago air samples, the first report of OH-PCBs in environmental air samples. Concentrations of 2OH-PCB2 and 6OH-PCB2 in both phases were similar to PCB2 measured in the same samples, from non-detect to 11 pgm-3 and 12 ngg-1 for the gas and particulate phases, respectively. We found that OH-PCB2s sorbed more to particulates than did PCB2; seasonal variability was larger than spatial variability across Chicago; and partial pressure and temperature strongly correlated with the two OH-PCBs (p<0.0001). Similar 6OH-PCB2:2OH-PCB2 ratios were found in our air samples and Aroclors, suggesting that Aroclors are a legacy source of OH-PCB2s to the atmosphere and appear to be volatilizing proportionally to PCBs in Aroclors. Although degradation by the hydroxyl radical has been proposed as an efficient loss process for airborne PCBs, we found no evidence that this mechanism results in the formation of OH-PCB2s.