Concentrations of Volatile Methyl Siloxanes in New York City Reflect Emissions from Personal Care and Industrial Use.

Volatile methyl siloxanes (VMS) are a group of organosilicon compounds of interest because of their potential health effects, their ability to form secondary organic aerosols, and their use as tracer compounds. VMS are emitted in the gas-phase from using consumer and personal care products, including deodorants, lotions, and hair conditioners. Because of this emission route, airborne concentrations are expected to increase with population density, although there are few studies in large urban centers. Here, we report summertime concentrations and daily variations of VMS congeners measured in New York City. Median concentrations of the 6 studied congeners, D3 (20 ng m-3), D4 (57 ng m-3), D5 (230 ng m-3), D6 (11 ng m-3), L5 (2.5 ng m-3), and L7 (1.3 ng m-3) are among the highest reported outdoor concentrations in the literature to date. Average congener ratios of D5:D4 and D5:D6 were consistent with previously reported emissions ratios, suggesting that concentrations were dominated by local emissions. Measured concentrations agree with previously published results from a Community Multiscale Air Quality model and support commonly accepted emissions rates for D4, D5, and D6 of 32.8, 135, and 6.1 mg per capita per day. Concentrations of D4, D5, D6, L5, and L7 and total VMS were significantly lower during the day than during the night, consistent with daytime oxidation reactivity. Concentrations of D3 did not show the same diurnal trend but exhibited a strong directional dependence, suggesting that it may be emitted by industrial point sources in the area rather than personal care product use. Concentrations of all congeners had large temporal variations but showed relatively weak relationships with wind speed, temperature, and mixing height.

Congener-Specific Emissions from Floors and Walls Characterize Indoor Airborne Polychlorinated Biphenyls.

To reconcile the federal regulation of material polychlorinated biphenyl (PCB) concentrations with recently implemented state regulations of airborne PCBs, there is a need to characterize the relationship between PCB emissions from surfaces and air concentrations. We hypothesized that the magnitude and congener distribution of emissions from floors and walls fully account for the airborne PCBs measured in rooms constructed during the height of PCB production and sales. We measured emissions of PCB congeners from various wall and floor materials using polyurethane foam passive emission samplers before and after hexane wiping. Our results revealed that PCB emissions from flooring adequately predicted the magnitude and congener distribution of PCBs observed in the room air. Emissions varied by material within a single building (5 × 103 ng m-2 day-1 from wood panel walls to 3 × 104 ng m-2 day-1 from vinyl tile) and within the same room. Yet congener distributions between material emission PCB profiles and room air PCB profiles were statistically similar. Hexane wiping significantly reduced PCB emissions (>60%), indicating the importance of surface films as an ongoing source of airborne PCBs. The magnitude and congener distribution of material bulk concentrations did not explain that of material emissions or air concentrations. Passive measurements of polychlorinated biphenyl emissions from floors in a university building predict the concentrations of PCBs in room air.

Polyurethane Foam Emission Samplers to Identify Sources of Airborne Polychlorinated Biphenyls from Glass-Block Windows and Other Room Surfaces in a Vermont School.

We hypothesized that emissions of polychlorinated biphenyls (PCBs) from Aroclor mixtures present in building materials explain their concentrations in school air. Here, we report a study of airborne concentrations and gas-phase emissions in three elementary school rooms constructed in 1958. We collected airborne PCBs using polyurethane foam passive air samplers (PUF-PAS, n = 6) and PCB emissions from building materials using polyurethane foam passive emission samplers (PUF-PES, n = 17) placed over flat surfaces in school rooms, including vinyl tile floors, carpets, painted bricks, painted drywall, and glass-block windows. We analyzed all 209 congeners represented in 173 chromatographic separations and found that the congener distribution in PUF-PES strongly resembled the predicted diffusive release of gas-phase PCBs from a solid material containing Aroclor 1254. Concentrations of airborne total PCBs ranged from 38 to 180 ng m-3, a range confirmed by an independent laboratory in the same school. These levels exceed action levels for all aged children set by the State of Vermont and exceed guidance levels set by the U.S. EPA for children under age 3. Emissions of PCBs from the glass-block windows (30,000 ng m-2 d-1) greatly exceeded those of all other surfaces, which ranged from 35 to 2700 ng m-2 d-1. This study illustrates the benefit of the direct measurement of PCB emissions to identify the most important building remediation needed to reduce airborne PCB concentrations in schools.

Lab-scale biodegradation assay using passive samplers to determine microorganisms' ability to reduce polychlorinated biphenyl (PCB) volatilization from contaminated sediment.

Many PCB-degrading aerobes have been identified which may serve as bioaugmentation strains for aerobic, in situ bioremediation or in combination with dredging operations. The present work describes a lab-scale PCB biodegradation assay which can be used to screen potential bioaugmentation strains or consortia for their ability to decrease PCB mass flux from contaminated sediment to air through biodegradation of freely dissolved PCBs that have desorbed from sediment particles. The assay uses two types of passive samplers to simultaneously measure PCB mass that is freely dissolved in aqueous solution and PCB mass that has volatilized to the headspace of the bioreactor. Using this approach, relative comparisons of PCB mass accumulated in passive samplers between bioaugmented treatments and controls allow for practical assessment of a microbial strain's ability to reduce both freely dissolved and vapor phase PCB concentrations. The method is designed to be conducted using aliquots of homogenized, well-characterized, PCB-contaminated sediment gathered from a field site. This work details the experimental design methodology, required materials, bioreactor set-up, passive sampling, PCB-extraction, sample cleanup, and quantification protocols such that the biodegradation assay can be conducted or replicated. A step-by-step protocol is also included and annotated with photos, tips, and tricks from experienced analysts.•Relative comparisons of PCB mass accumulated in passive samplers between experimental treatments and controls allow for practical assessment of bioaugmentation strain's ability to reduce both freely dissolved and vapor phase PCB concentrations•Passive sampler preparation, deployment, PCB-extraction, cleanup procedures, and quantification are detailed step-by-step and annotated by experienced analysts.

Machine Learning-Assisted Identification and Quantification of Hydroxylated Metabolites of Polychlorinated Biphenyls in Animal Samples.

Laboratory studies of the disposition and toxicity of hydroxylated polychlorinated biphenyl (OH-PCB) metabolites are challenging because authentic analytical standards for most unknown OH-PCBs are not available. To assist with the characterization of these OH-PCBs (as methylated derivatives), we developed machine learning-based models with multiple linear regression (MLR) or random forest regression (RFR) to predict the relative retention times (RRT) and MS/MS responses of methoxylated (MeO-)PCBs on a gas chromatograph-tandem mass spectrometry system. The final MLR model estimated the retention times of MeO-PCBs with a mean absolute error of 0.55 min (n = 121). The similarity coefficients cos θ between the predicted (by RFR model) and experimental MS/MS data of MeO-PCBs were >0.95 for 92% of observations (n = 96). The levels of MeO-PCBs quantified with the predicted MS/MS response factors approximated the experimental values within a 2-fold difference for 85% of observations and 3-fold differences for all observations (n = 89). Subsequently, these model predictions were used to assist with the identification of OH-PCB 95 or OH-PCB 28 metabolites in mouse feces or liver by suggesting candidate ranking information for identifying the metabolite isomers. Thus, predicted retention and MS/MS response data can assist in identifying unknown OH-PCBs.

Occurrence of primary aromatic amines and nicotine in sediments collected from the United States.

Despite extensive use of primary aromatic amines (AAs) in consumer products, little is known about their occurrence in the environment. In this study, we investigated the occurrence of 14 AAs and nicotine in 75 sediment samples collected from seven estuarine and freshwater ecosystems in the Unites States. Additionally, risk quotients (RQs) were calculated to assess potential risks of these chemicals to aquatic organisms. Of the 14 AAs analyzed, seven of them were found in sediments. The sum concentrations of seven AAs in sediments were in the range of 10.2 to 1810 ng/g, dry wt (mean: 388 ng/g). Aniline was the most abundant compound, accounting for, on average, 53 % of the total concentrations. Nicotine was found in sediments at a concentration range of

Occurrence and spatial distribution of individual polychlorinated biphenyl congeners in residential soils from East Chicago, southwest Lake Michigan.

We report individual polychlorinated biphenyl congeners and the sum of all congeners (ΣPCB) in residential soils of East Chicago, Indiana. ΣPCB in soils ranged from 20 to 1700 ng/g dry weight (DW), with a geometric mean of 120 ng/g DW. These values are significantly higher than other locations, but similar or lower to locations nearby well-known PCB contamination sites. No PCB spatial distribution pattern was observed. PCB concentrations increase with total organic carbon in the soils and proximity to Indiana Harbor and Ship Canal (IHSC), where sediments are contaminated with PCBs. Most samples are similar in their PCB distribution and Aroclor 1254 yielded the highest similarity to all the samples. A fifth of the samples highly resemble other PCB profiles such as EPA background and Cedar Rapids Iowa soils, and volatilization from Lake Michigan, whereas volatilization from IHSC could not explain the PCBs found in soils. IHSC was expected to be the main source of PCBs in the nearby soils. It is possible that soils are impacted by variety of known and unknown sources, including volatilization from Lake Michigan, resulting in a regional PCB signal. Although PCB concentrations are higher than other locations, samples were below the current US EPA non-cancer residential soil level remediation goal for dioxin TEQ.

Assessment of Polychlorinated Biphenyls and Their Hydroxylated Metabolites in Postmortem Human Brain Samples: Age and Brain Region Differences.

Exposure to polychlorinated biphenyls (PCBs) and their hydroxylated metabolites (OH-PCBs) has been implicated in neurodevelopmental disorders. However, the distribution of PCBs and OH-PCBs in the human brain has not been characterized. This study investigated the age-, sex-, and brain region-specific distribution of all 209 PCBs using gaschromatography-tandem mass spectrometry (GC-MS/MS) in neonatal (N = 7) and adult (N = 7) postmortem brain samples. OH-PCB analyses were performed by GC-MS/MS (as methylated derivatives) and, in a subset of samples, by nontarget liquid chromatography high-resolution mass spectrometry (Nt-LCMS). Fourteen higher chlorinated PCB congeners were observed with a detection frequency >50%. Six lower chlorinated PCBs were detected with a detection frequency >10%. Higher chlorinated PCBs were observed with higher levels in samples from adult versus younger donors. PCB congener profiles from adult donors showed more similarities across brain regions and donors than younger donors. We also assess the potential neurotoxicity of the PCB residues in the human brain with neurotoxic equivalency (NEQ) approaches. The median ΣNEQs, calculated for the PCB homologues, were 40-fold higher in older versus younger donors. Importantly, lower chlorinated PCBs made considerable contributions to the neurotoxic potential of PCB residues in some donors. OH-PCBs were identified for the first time in a small number of human brain samples by GC-MS/MS and Nt-LCMS analyses, and all contained four or fewer chlorine.

PCB Sulfates in Serum from Mothers and Children in Urban and Rural U.S. Communities.

Serum samples from 24 subjects (6 mother-daughter and 6 mother-son dyads) in a rural community (Columbus Junction, Iowa) and 24 subjects (6 mother-daughter and 6 mother-son dyads) in an urban community (East Chicago, Indiana) were analyzed for 74 sulfated metabolites of polychlorinated biphenyls (PCBs). We detected significantly higher mean concentrations of total assessed PCB sulfates in the urban group (110-8900 ng/g fresh weight of serum, mean = 3400 ng/g, standard error = 300) than in the rural cohort (530-6700 ng/g fresh weight of serum, mean = 1800 ng/g, standard error = 500). Eight PCB sulfate congeners (4-PCB 2 sulfate, 4'-PCB 2 sulfate, 2'-PCB 3 sulfate, 4'-PCB 3 sulfate, 4-PCB 11 sulfate, 4'-PCB 18 sulfate, 4'-PCB 25 sulfate, and 4-PCB 52 sulfate) contributed over 90% of the total assessed PCB sulfates in most individuals. The serum samples were enriched in PCB sulfates with fewer than 5 chlorine atoms, and this congener distribution differed from those of PCBs and hydroxylated PCBs in previous studies in the same communities. Regression analysis indicated several significant congener-specific correlations in mother-child dyads, and these relationships differed by location and by mother-daughter or mother-son dyads. This is the first study reporting a broad range of PCB sulfates in populations from urban and rural areas.

Hydroxylated Polychlorinated Biphenyls Are Emerging Legacy Pollutants in Contaminated Sediments.

We measured the concentrations of 837 hydroxylated polychlorinated biphenyls (OH-PCBs, in 275 chromatographic peaks) and 209 polychlorinated biphenyls (PCBs, in 174 chromatographic peaks) in sediments from New Bedford Harbor in Massachusetts, Altavista wastewater lagoon in Virginia, and the Indiana Harbor and Ship Canal in Indiana, USA and in the original commercial PCB mixtures Aroclors 1016, 1242, 1248, and 1254. We used the correlation between homologues and the peak responses to quantify the full suite of OH-PCBs including those without authentic standards available. We found that OH-PCB levels are approximately 0.4% of the PCB levels in sediments and less than 0.0025% in Aroclors. The OH-PCB congener distributions of sediments are different from those of Aroclors and are different according to sites. We also identified a previously unknown compound, 4-OH-PCB52, which together with 4'-OH-PCB18 made up almost 30% of the OH-PCBs in New Bedford Harbor sediments but less than 1.2% in the Aroclors and 3.3% in any other sediments. This indicates site-specific environmental transformations of PCBs to OH-PCBs. We conclude that the majority of OH-PCBs in these sediments are generated in the environment. Our findings suggest that these toxic breakdown products of PCBs are prevalent in PCB-contaminated sediments and present an emerging concern for humans and ecosystems.

Distinguishing Aroclor and non-Aroclor sources to Chicago Air.

Many polychlorinated biphenyl (PCB) congeners are found in both legacy Aroclor mixtures and modern materials, and both contribute to PCBs levels in ambient air. The various sources of PCBs make it difficult to quantify the relative importance of emissions from remaining legacy materials and emissions of PCBs released from production and use of modern products. To address this challenge, we utilized active and passive sampling, analytical methods optimized for PCBs, and Positive Matrix Factorization (PMF) and cos theta to examine the chemical signature of PCBs in Chicago air. Here we report our findings for over 640 samples collected over 7 years and analyzed for all 209 congeners. We conclude that Aroclor sources (1254, 1016/1242, and 1260) are consistent and dominant contributors to Chicago air. However, non-Aroclors sources accounted for 13%-16% of the total PCBs measured. Our analysis indicates non-Aroclor sources explain 99% of PCB11, 90% of PCB 68, and 58-69% of congeners with 8 to 10 chlorines in Chicago air. All of these are known to be emitted from paints or silicone polymers. Additionally, we identified over 20 congeners that have non-Aroclor contributions of more than 50% including PCB 3 (4-monochlorobiphenyl, 83% non-Aroclor) as well as 7 congeners of unknown sources: PCBs 43, 46, 55, 89, 96, 137, and 139 + 140. Non-Aroclor emission sources contribute to the entire range of congeners from mono- to deca-chlorobiphenyls. We found evidence of highly localized non-Aroclor sources including a signature similar to that of green paint. We also found source signals similar to the PCB congeners volatilizing from and absorbing to neighboring Lake Michigan. The measured profiles vary from season to season: lower chlorinated congeners dominate in winter months while higher chlorinated congeners contribute more in summer.

Toxicity Assessment of 91-Day Repeated Inhalation Exposure to an Indoor School Air Mixture of PCBs.

School indoor air contaminated with polychlorinated biphenyls (PCBs) released from older building materials and paint pigments may pose health risks to children, as well as teachers and staff, by inhalation of PCBs. The health effects of long-term inhalation exposure to PCBs are poorly understood. We conducted a comprehensive toxicity assessment of 91-day repeated inhalation exposure to a lab-generated mixture of PCBs designed to emulate indoor school air, combining transcriptomics, metabolomics, and neurobehavioral outcomes. Female Sprague-Dawley rats were exposed to school air mixture (SAM+) at a concentration of 45.5 ± 5.9 µg/m3 ∑209PCB or filtered air 4 h/day, 6 days/week for 13 weeks using nose-only exposure systems. The congener-specific PCB body burden was quantified in major tissues using GC-MS/MS. The generated SAM+ vapor recapitulated the target school air profile with a similarity coefficient, cos θ of 0.91. PCB inhalation yielded 875-9930 ng/g ∑209PCBlipid weight levels in tissues in the following ascending order: brain < liver < lung < serum < adipose tissue. We observed that PCB exposure impaired memory, induced anxiety-like behavior, significantly reduced white blood cell counts, mildly disrupted metabolomics in plasma, and influenced transcription processes in the brain with 274 upregulated and 58 downregulated genes. With relatively high exposure and tissue loading, evidence of toxicity from half the end points tested was seen in the rats.

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.