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.

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.

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.

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.

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.

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.

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.

Room-to-Room Variability of Airborne Polychlorinated Biphenyls in Schools and the Application of Air Sampling for Targeted Source Evaluation.

Airborne polychlorinated biphenyl (PCB) concentrations are higher indoors than outdoors due to their historical use in building materials and their presence in modern paints and surface treatments. For some populations, including school children, PCB levels indoors result in inhalation exposures that may be greater than or equivalent to exposure through diet. In a school, PCB exposure may come from multiple sources. We hypothesized that there are both Aroclor and non-Aroclor sources within a single school and that PCB concentration and congener profiles differ among rooms within a single building. To evaluate this hypothesis and to identify potential localized sources, we measured airborne PCBs in nine rooms in a school. We found that schoolroom concentrations exceed outdoor air concentrations. Schoolroom concentrations and congener profiles also varied from one room to another. The concentrations were highest in the math room (35.75 ng m-3 ± 8.08) and lowest in the practice gym (1.54 ng m-3 ± 0.35). Rooms in the oldest wing of the building, originally constructed between 1920 and 1970, had the highest concentrations. The congener distribution patterns indicate historic use of Aroclor 1254 as well as modern sources of non-Aroclor congeners associated with paint pigments and surface coatings. Our findings suggest this noninvasive source identification method presents an opportunity for targeted source testing for more cost-effective prioritization of materials remediation in schools.

Detection and Quantification of Polychlorinated Biphenyl Sulfates in Human Serum.

Polychlorinated biphenyls (PCBs) are persistent toxic chemicals with both legacy sources (e.g., Aroclors) and new sources (e.g., unintentional contaminants in some pigments and varnishes). PCB sulfates are derived from further metabolism of hydroxylated PCBs (OH-PCBs), which are oxidative metabolites of PCBs. While OH-PCBs and PCB sulfates are implicated in multiple toxicological effects, studies of PCB sulfates in human serum have been limited by available analytical procedures. We have now developed a method for extraction of PCB sulfates from serum followed by differential analysis with, and without, sulfatase-catalyzed hydrolysis to OH-PCBs. A sulfatase from Helix pomatia was purified by affinity chromatography, and it displayed broad specificity for PCB sulfates without contaminant glucuronidase activity. Following sulfatase-catalyzed hydrolysis of the PCB sulfates extracted from serum, the corresponding OH-PCBs were derivatized to methoxy-PCBs and quantitated by GC-MS/MS. In a pooled sample of human serum, we identified 10 PCB sulfates, with three PCB sulfate congeners exhibiting the highest concentrations from 1200 to 3970 pg/g of serum. In conclusion, we have developed a sensitive and specific method for the determination of PCB sulfates in human serum.

Tracking POPs in Global Air from the First 10 Years of the GAPS Network (2005 to 2014).

The Global Atmospheric Passive Sampling (GAPS) network, initiated in 2005 across 55 global sites, supports the global monitoring plan (GMP) of the Stockholm Convention on Persistent Organic Pollutants (POPs) by providing information on POP concentrations in air on a global scale. These data inform assessments of the long-range transport potential of POPs and the effectiveness evaluation of chemical regulation efforts, by observing changes in concentrations over time. Currently, measurements spanning 5-10 sampling years are available for 40 sites from the GAPS Network. This study was the first time that POP concentrations in air were reported on a global scale for an extended time period and the first to evaluate worldwide trends with an internally consistent sample set. For consistency between sampling years, site- and sample specific sampling rates were calculated with a new, public online model, which accounts for the effects of wind speed variability. Concentrations for legacy POPs in air between 2005 and 2014 show different trends for different organochlorine pesticides (OCPs) and polychlorinated biphenyls (PCBs). The POPs discussed in this study were chosen due to being the most frequently detected, with detection at the majority of sites. PCB, endosulfan, and hexachlorocyclohexane (HCH) concentrations in air are decreasing at most sites. The global trends reflect global sources and recycling of HCH, ongoing emissions from old stockpiles for PCBs, and recent use restrictions for endosulfan. These chlorinated OCPs continue to present exposure threat to humans and ecosystems worldwide. Concentrations of other OCPs, such as chlordanes, heptachlor and dieldrin, are steady and/or declining slowly at the majority of sites, reflecting a transition from primary to secondary sources (i.e., re-emission from reservoirs where these POPs have accumulated historically) which now control ambient air burdens.

Polychlorinated Biphenyls in Food.

We measured the concentrations of 205 polychlorinated biphenyl (PCB) congeners in 26 food items: beef steak, butter, canned tuna, catfish, cheese, eggs, french fries, fried chicken, ground beef, ground pork, hamburger, hot dog, ice cream, liver, luncheon meat, margarine, meat-free dinner, milk, pizza, poultry, salmon, sausage, shrimp, sliced ham, tilapia, and vegetable oil. Using Diet History Questionnaire II, we calculated the PCB dietary exposure in mothers and children participating in the AESOP Study in East Chicago, Indiana, and Columbus Junction, Iowa. Salmon had the highest concentration followed by canned tuna, but fish is a minor contributor to exposure. Other animal proteins are more important sources of PCB dietary exposure in this study population. Despite the inclusion of few congeners and food types in previous studies, we found evidence of a decline in PCB concentrations over the last 20 years. We also found strong associations of PCB congener distributions with Aroclors in most foods and found manufacturing byproduct PCBs, including PCB11, in tilapia and catfish. The reduction in PCB levels in food indicates that dietary exposure is comparable to PCB inhalation exposures reported for the same study population.

Comprehensive Subchronic Inhalation Toxicity Assessment of an Indoor School Air Mixture of PCBs.

Few in vivo inhalation studies have explored the toxicity of environmentally relevant mixtures of polychlorinated biphenyls (PCBs). The manufacture of industrial PCBs was banned in 1978, but PCBs continue to be formed in industrial and consumer products. Schools represent a significant source of airborne exposures to legacy and nonlegacy PCBs, placing children at risk. To evaluate the impact of these exposures, we generated an airborne mixture of PCBs, called the School Air Mixture (SAM), to match the profile of an older school from our adolescent cohort study. Female Sprague-Dawley rats were exposed either to SAM or filtered air in nose-only exposure systems, 4 h/day for 4 weeks. Congener-specific air and tissue PCB profiles were assessed using gas chromatography with tandem mass spectrometry (GC-MS/MS). PCB exposures recapitulated the target school air profile with a similarity coefficient, cos θ of 0.83. PCB inhalation yielded µg/g ∑209 PCB levels in tissues. Neurobehavioral testing demonstrated a modest effect on spatial learning and memory in SAM-exposed rats. PCB exposure induced oxidative stress in the liver and lungs, affected the maturational stages of hematopoietic stem cells, reduced telomerase activity in bone marrow cells, and altered the gut microbiota. This is the first study to emulate PCB exposures in a school and comprehensively evaluate toxicity.

PCB Emissions from Paint Colorants.

Polychlorinated biphenyls (PCBs) are known human carcinogens that are byproducts of pigment manufacturing and found in colorants used to tint consumer paints sold in the United States and elsewhere. PCBs have the potential to be emitted from paint containing these pigments. To quantify the gas-phase emissions of ∑PCBs, we used polyurethane foam (PUF) to capture emissions from freshly applied colorants. Some PCB emissions were detected on the PUF after 1 day. After 6 weeks, all PCBs found in the colorant were also found on the PUF. Even the fully chlorinated PCB209 was emitted from green colorant. Mono- and dichlorinated PCBs were released from the colorant at a faster rate than the higher chlorinated congeners. By the end of the experiment, all the lower chlorinated congeners were absent from the colorant while more than 75% of the higher chlorinated congeners remained in the sample. The rate of PCB emissions from paint colorants is a function of the surface/air equilibrium coefficient, and the presence of water accelerates the emissions. Although concentrations of PCBs in colorants are less than 285 ng g-1, PCB emissions from colorants in paint can cause environmentally relevant concentrations of ≥500 pg m-3 within hours of painting a room.

Emissions of Tetrachlorobiphenyls (PCBs 47, 51, and 68) from Polymer Resin on Kitchen Cabinets as a Non-Aroclor Source to Residential Air.

Both Aroclor and non-Aroclor sources of airborne polychlorinated biphenyls (PCBs) were found in residential homes. We deployed passive air samplers at 16 residences and found PCB-47, PCB-51, and PCB-68 to account for up to 50% of measured indoor ΣPCBs (2700 pg m-3). Although PCB-47 and PCB-51 are neurotoxins present in Aroclor mixtures (<2.5 and <0.3 wt %, respectively), we found them at much higher levels than expected for any Aroclor source. PCB-68 is not present in Aroclor mixtures. Another non-Aroclor congener, PCB-11, a byproduct of pigment manufacturing, was found inside and outside of every household and was frequently the predominate congener. We conducted direct measurements of surface emissions and identified finished cabinetry to be a major source of PCB-47, PCB-51, and PCB-68. We hypothesize that these congeners are inadvertent byproducts of polymer sealant manufacturing and produced from the decomposition of 2,4-dichlorobenzoyl peroxide used as an initiator in free-radical polymerization of polyester resins. The presence of these three compounds in polymer products, such as silicone, has been widely noted, but to our knowledge they have never been shown to be a significant environmental source of PCBs.

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.

A Model Using Local Weather Data to Determine the Effective Sampling Volume for PCB Congeners Collected on Passive Air Samplers.

We have developed and evaluated a mathematical model to determine the effective sampling volumes (Veff) of PCBs and similar compounds captured using polyurethane foam passive air samplers (PUF-PAS). We account for the variability in wind speed, air temperature, and equilibrium partitioning over the course of the deployment of the samplers. The model, provided as an annotated Matlab script, predicts the Veff as a function of physical-chemical properties of each compound and meteorology from the closest Integrated Surface Database (ISD) data set obtained through NOAA's National Centers for Environmental Information (NCEI). The model was developed to be user-friendly, only requiring basic Matlab knowledge. To illustrate the effectiveness of the model, we evaluated three independent data sets of airborne PCBs simultaneously collected using passive and active samplers: at sites in Chicago, Lancaster, UK, and Toronto, Canada. The model provides Veff values comparable to those using depuration compounds and calibration against active samplers, yielding an average congener specific concentration method ratio (active/passive) of 1.1 ± 1.2. We applied the model to PUF-PAS samples collected in Chicago and show that previous methods can underestimate concentrations of PCBs by up to 40%, especially for long deployments, deployments conducted under warming conditions, and compounds with log Koa values less than 8.

Metabolism and metabolites of polychlorinated biphenyls.

Abstract The metabolism of polychlorinated biphenyls (PCBs) is complex and has an impact on toxicity, and thereby on the assessment of PCB risks. A large number of reactive and stable metabolites are formed in the processes of biotransformation in biota in general, and in humans in particular. The aim of this document is to provide an overview of PCB metabolism, and to identify the metabolites of concern and their occurrence. Emphasis is given to mammalian metabolism of PCBs and their hydroxyl, methylsulfonyl, and sulfated metabolites, especially those that persist in human blood. Potential intracellular targets and health risks are also discussed.