Benzo[a]pyrene toxicokinetics in humans following dietary supplementation with 3,3'-diindolylmethane (DIM) or Brussels sprouts.

Utilizing the atto-zeptomole sensitivity of UPLC-accelerator mass spectrometry (UPLC-AMS), we previously demonstrated significant first-pass metabolism following escalating (25-250 ng) oral micro-dosing in humans of [14C]-benzo[a]pyrene ([14C]-BaP). The present study examines the potential for supplementation with Brussels sprouts (BS) or 3,3'-diindolylmethane (DIM) to alter plasma levels of [14C]-BaP and metabolites over a 48-h period following micro-dosing with 50 ng (5.4 nCi) [14C]-BaP. Volunteers were dosed with [14C]-BaP following fourteen days on a cruciferous vegetable restricted diet, or the same diet supplemented for seven days with 50 g of BS or 300 mg of BR-DIM® prior to dosing. BS or DIM reduced total [14C] recovered from plasma by 56-67% relative to non-intervention. Dietary supplementation with DIM markedly increased Tmax and reduced Cmax for [14C]-BaP indicative of slower absorption. Both dietary treatments significantly reduced Cmax values of four downstream BaP metabolites, consistent with delaying BaP absorption. Dietary treatments also appeared to reduce the T1/2 and the plasma AUC(0,∞) for Unknown Metabolite C, indicating some effect in accelerating clearance of this metabolite. Toxicokinetic constants for other metabolites followed the pattern for [14C]-BaP (metabolite profiles remained relatively consistent) and non-compartmental analysis did not indicate other significant alterations. Significant amounts of metabolites in plasma were at the bay region of [14C]-BaP irrespective of treatment. Although the number of subjects and large interindividual variation are limitations of this study, it represents the first human trial showing dietary intervention altering toxicokinetics of a defined dose of a known human carcinogen.

Wildfire Impact on Indoor and Outdoor PAH Air Quality.

Air quality impacts from wildfires are poorly understood, particularly indoors. As frequencies increase, it is important to optimize methodologies to understand and reduce chemical exposures from wildfires. Public health recommendations use air quality estimates from outdoor stationary air monitors, discounting indoor air conditions, and do not consider chemicals in the vapor phase, known to elicit adverse effects. We investigated vapor-phase polycyclic aromatic hydrocarbons (PAHs) in indoor and outdoor air before, during, and after wildfires using a community-engaged research approach. Paired passive air samplers were deployed at 15 locations across four states. Twelve unique PAHs were detected only in outdoor air during wildfires, highlighting a PAH exposure mixture for future study. Heavy-molecular-weight (HMW) outdoor PAH concentrations and average Air Quality Index (AQI) values were positively correlated (p < 0.001). Indoor PAH concentrations were higher in 77% of samples across all sampling events. Even during wildfires, 58% of sampled locations still had higher indoor PAH air concentrations. When AQI values exceeded 140 (unhealthy for sensitive groups), outdoor PAH concentrations became similar to or higher than indoors. Cancer and noncancer inhalation risk estimates from vapor-phase PAHs were higher indoors than outdoors, regardless of the wildfire impact. Consideration of indoor air quality and vapor-phase PAHs could inform public health recommendations regarding wildfires.

Inter-method reliability of silicone exposome wristbands and urinary biomarker assays in a pregnancy cohort.

Silicone wristbands act as passive environmental samplers capable of detecting and measuring concentrations of a variety of chemicals. They offer a noninvasive method to collect complex exposure data in large-scale epidemiological studies. We evaluated the inter-method reliability of silicone wristbands and urinary biomarkers in the New Hampshire Birth Cohort Study. A subset of study participants (n = 96) provided a urine sample and wore a silicone wristband for 7 days at approximately 12 gestational weeks. Women were instructed to wear the wristbands during all their normal activities. Concentrations of urinary compounds and metabolites in the urine and parent compounds in wristbands were compared. High detection rates were observed for triphenyl phosphate (76.0%) and benzophenone (78.1%) in wristbands, although the distribution of corresponding urinary concentrations of chemicals did not differ according to whether chemicals were detected or not detected in wristbands. While detected among only 8.3% of wristbands, median urinary triclosan concentrations were higher among those with triclosan detected in wristbands (9.04 ng/mL) than without (0.16 ng/mL). For most chemicals slight to fair agreement was observed across exposure assessment methods, potentially due to low rates of detection in the wristbands for chemicals where observed urinary concentrations were relatively low as compared to background concentrations in the general population. Our findings support the growing body of research in support of deploying silicone wristbands as an important exposure assessment tool.

Exposure to an Environmental Mixture of Polycyclic Aromatic Hydrocarbons Induces Hepatic Cytochrome P450 Enzymes in Mice.

Cytochrome P450 enzymes (CYPs) play an important role in bioactivating or detoxifying polycyclic aromatic hydrocarbons (PAHs), common environmental contaminants. While it is widely accepted that exposure to PAHs induces CYPs, effectively increasing rates of xenobiotic metabolism, dose- and time-response patterns of CYP induction are not well-known. In order to better understand dose- and time-response relationships of individual CYPs following induction, we exposed B6129SF1/J mice to single or repeated doses (2-180 µmol/kg/d) of benzo[a]pyrene (BaP) or Supermix-10, a mixture of the top 10 most abundant PAHs found at the Portland Harbor Superfund Site. In hepatic microsomes from exposed mice, we measured amounts of active CYPs using activity-based protein profiling and total CYP expression using global proteomics. We observed rapid Cyp1a1 induction after 6 h at the lowest PAH exposures and broad induction of many CYPs after 3 daily PAH doses at 72 h following the first dose. Using samples displaying Cyp1a1 induction, we observed significantly higher metabolic affinity for BaP metabolism (Km reduced 3-fold), 3-fold higher intrinsic clearance, but no changes to the Vmax. Mice dosed with the highest PAH exposures exhibited 1.7-5-fold higher intrinsic clearance rates for BaP compared to controls and higher Vmax values indicating greater amounts of enzymes capable of metabolizing BaP. This study demonstrates exposure to PAHs found at superfund sites induces enzymes in dose- and time-dependent patterns in mice. Accounting for specific changes in enzyme profiles, relative rates of PAH bioactivation and detoxification, and resulting risk will help translate internal dosimetry of animal models to humans and improve risk assessments of PAHs at superfund sites.

Improvements in identification and quantitation of alkylated PAHs and forensic ratio sourcing.

Parent and alkylated polycyclic aromatic hydrocarbons (PAHs) are present in a number of different sources in varying proportions depending on the source material and weathering. This range of PAH sources can make it difficult to determine the origin of exposure(s). Ratios of alkylated and parent PAHs have been applied as a forensic tool to distinguish between different sources. However, few studies have examined PAH ratios comprehensively as indicators for sourcing beyond a single study area or matrix type. In this paper, we introduce an expanded analytical method based on ASTM D7363-13a which we adapted for a gas chromatography triple quadrupole mass spectrometry instrument. The modifications increase selectivity and sensitivity compared to the ASTM method. We added five alkylated series to the method. This method has then been applied to 22 independent forensic ratios. We evaluated the method and the forensic ratios with certified reference materials and known environmental samples. This analytical method and thirteen PAH ratios were found to accurately predict sources of PAHs.

Nicotine, Cotinine, and Tobacco-Specific Nitrosamines Measured in Children's Silicone Wristbands in Relation to Secondhand Smoke and E-cigarette Vapor Exposure.

INTRODUCTION: Simple silicone wristbands (WB) hold promise for exposure assessment in children. We previously reported strong correlations between nicotine in WB worn by children and urinary cotinine (UC). Here, we investigated differences in WB chemical concentrations among children exposed to secondhand smoke from conventional cigarettes (CC) or secondhand vapor from electronic cigarettes (EC), and children living with nonusers of either product (NS). METHODS: Children (n = 53) wore three WB and a passive nicotine air sampler for 7 days and one WB for 2 days, and gave a urine sample on day 7. Caregivers reported daily exposures during the 7-day period. We determined nicotine, cotinine, and tobacco-specific nitrosamines (TSNAs) concentrations in WB, nicotine in air samplers, and UC through isotope-dilution liquid chromatography with triple-quadrupole mass spectrometry. RESULTS: Nicotine and cotinine levels in WB in children differentiated between groups of children recruited into NS, EC exposed, and CC exposed groups in a similar manner to UC. WB levels were significantly higher in the CC group (WB nicotine median 233.8 ng/g silicone, UC median 3.6 ng/mL, n = 15) than the EC group (WB nicotine median: 28.9 ng/g, UC 0.5 ng/mL, n = 19), and both CC and EC group levels were higher than the NS group (WB nicotine median: 3.7 ng/g, UC 0.1 ng/mL, n = 19). TSNAs, including the known carcinogen NNK, were detected in 39% of WB. CONCLUSIONS: Silicone WB show promise for sensitive detection of exposure to tobacco-related contaminants from traditional and electronic cigarettes and have potential for tobacco control efforts. IMPLICATIONS: Silicone WB worn by children can absorb nicotine, cotinine, and tobacco-specific nitrosamines, and amounts of these compounds are closely related to the child's urinary cotinine. Levels of tobacco-specific compounds in the silicone WB can distinguish patterns of children's exposure to secondhand smoke and e-cigarette vapor. Silicone WB are simple to use and acceptable to children and, therefore, may be useful for tobacco control activities such as parental awareness and behavior change, and effects of smoke-free policy implementation.

Pesticide exposure among Latinx child farmworkers in North Carolina.

BACKGROUND: Although pesticides have adverse effects on child health and development, little research has examined pesticide exposure among child farmworkers. This analysis addresses two specific aims: (1) describes pesticide exposure among Latinx child farmworkers in North Carolina, and (2) delineates factors associated with this pesticide exposure. METHODS: In 2018 (n = 173) and 2019 (n = 156) Latinx child farmworkers completed interviews and wore silicone wristbands for a single day to measure pesticide exposure. Wristbands were analyzed for 70 pesticides. RESULTS: Most Latinx child farmworkers were exposed to multiple pesticides; the most frequent were pyrethroids (69.9% in 2018, 67.9% in 2019), organochlorines (51.4% in 2018, 55.1% in 2019), and organophosphates (51.4% in 2018, 34.0% in 2019). Children were exposed to a mean of 2.15 pesticide classes in 2018 and 1.91 in 2019, and to a mean of 4.06 pesticides in 2018 and 3.34 in 2019. Younger children (≤15 years) had more detections than older children; children not currently engaged in farm work had more detections than children currently engaged in farm work. Migrant child farmworkers had more detections than nonmigrants. For specific pesticides with at least 20 detections, detections and concentrations were generally greater among children not currently engaged in farm work than children currently engaged. CONCLUSIONS: Children who live in farmworker communities are exposed to a plethora of pesticides. Although further research is needed to document the extent of pesticide exposure and its health consequences, sufficient information is available to inform the policy needed to eliminate this pesticide exposure in agricultural communities.

Toxicokinetics of benzo[a]pyrene in humans: Extensive metabolism as determined by UPLC-accelerator mass spectrometry following oral micro-dosing.

Benzo[a]pyrene (BaP), is a known human carcinogen (International Agency for Research on Cancer (IARC) class 1). The remarkable sensitivity (zepto-attomole 14C in biological samples) of accelerator mass spectrometry (AMS) makes possible, with de minimus risk, pharmacokinetic (PK) analysis following [14C]-BaP micro-dosing of humans. A 46 ng (5 nCi) dose was given thrice to 5 volunteers with minimum 2 weeks between dosing and plasma collected over 72 h. [14C]-BaPeq PK analysis gave plasma Tmax and Cmax values of 1.25 h and 29-82 fg/mL, respectively. PK parameters were assessed by non- compartment and compartment models. Intervals between dosing ranged from 20 to 420 days and had little impact on intra-individual variation. DNA, extracted from peripheral blood mononuclear cells (PBMCs) of 4 volunteers, showed measurable levels (LOD ~ 0.5 adducts/1011 nucleotides) in two individuals 2-3 h post-dose, approximately three orders of magnitude lower than smokers or occupationally-exposed individuals. Little or no DNA binding was detectable at 48-72 h. In volunteers the allelic variants CYP1B1*1/*⁎1, *1/*3 or *3/*3 and GSTM1*0/0 or *1 had no impact on [14C]-BaPeq PK or DNA adduction with this very limited sample. Plasma metabolites over 72 h from two individuals (one CYP1B1*1/*1 and one CYP1B1*3/*3) were analyzed by UPLC-AMS. In both individuals, parent [14C]-BaP was a minor constituent even at the earliest time points and metabolite profiles markedly distinct. AMS, coupled with UPLC, could be used in humans to enhance the accuracy of pharmacokinetics, toxicokinetics and risk assessment of environmental carcinogens.

Silicone Pet Tags Associate Tris(1,3-dichloro-2-isopropyl) Phosphate Exposures with Feline Hyperthyroidism.

Feline hyperthyroidism is the most commonly diagnosed endocrine-related disease among senior and geriatric housecats, but the causes remain unknown. Exposure to endocrine-disrupting compounds with thyroid targets, such as flame retardants (FRs), may contribute to disease development. Silicone passive sampling devices, or pet tags, quantitatively assessed the bioavailable FR exposures of 78 cats (≥7 y) in New York and Oregon using gas chromatography-mass spectrometry. Pet tags were analyzed for 36 polybrominated diphenyl ethers, six organophosphate esters (OPEs), and two alternative brominated FRs. In nonhyperthyroid cats, serum free thyroxine (fT4), total T4 (TT4), total triiodothyronine, and thyroid-stimulating hormone concentrations were compared with FR concentrations. Tris(1,3-dichloro-2-isopropyl) phosphate (TDCIPP) concentrations were higher in hyperthyroid pet tags in comparison to nonhyperthyroid pet tags (adjusted odds ratio, p < 0.07; Mantel-Cox, p < 0.02). Higher TDCIPP concentrations were associated with air freshener use in comparison to no use (p < 0.01), residences built since 2005 compared to those pre-1989 (p < 0.002), and cats preferring to spend time on upholstered furniture in comparison to no preference (p < 0.05). Higher TDCIPP concentrations were associated with higher fT4 and TT4 concentrations (p < 0.05). This study provides proof-of-concept data for the use of silicone pet tags with companion animals and further indicates that bioavailable TDCIPP exposures are associated with feline hyperthyroidism.

Development of an environmental health tool linking chemical exposures, physical location and lung function.

BACKGROUND: A challenge in environmental health research is collecting robust data sets to facilitate comparisons between personal chemical exposures, the environment and health outcomes. To address this challenge, the Exposure, Location and lung Function (ELF) tool was designed in collaboration with communities that share environmental health concerns. These concerns centered on respiratory health and ambient air quality. The ELF collects exposure to polycyclic aromatic hydrocarbons (PAHs), given their association with diminished lung function. Here, we describe the ELF as a novel environmental health assessment tool. METHODS: The ELF tool collects chemical exposure for 62 PAHs using passive sampling silicone wristbands, geospatial location data and respiratory lung function measures using a paired hand-held spirometer. The ELF was tested by 10 individuals with mild to moderate asthma for 7 days. Participants wore a wristband each day to collect PAH exposure, carried a cell phone, and performed spirometry daily to collect respiratory health measures. Location data was gathered using the geospatial positioning system technology in an Android cell-phone. RESULTS: We detected and quantified 31 PAHs across the study population. PAH exposure data showed spatial and temporal sensitivity within and between participants. Location data was used with existing datasets such as the Toxics Release Inventory and the National Oceanic and Atmospheric Administration (NOAA) Hazard Mapping System. Respiratory health outcomes were validated using criteria from the American Thoracic Society with 94% of participant data meeting standards. Finally, the ELF was used with a high degree of compliance (> 90%) by community members. CONCLUSIONS: The ELF is a novel environmental health assessment tool that allows for personal data collection spanning chemical exposures, location and lung function measures as well as self-reported information.

Systematic developmental neurotoxicity assessment of a representative PAH Superfund mixture using zebrafish.

Superfund sites often consist of complex mixtures of polycyclic aromatic hydrocarbons (PAHs). It is widely recognized that PAHs pose risks to human and environmental health, but the risks posed by exposure to PAH mixtures are unclear. We constructed an environmentally relevant PAH mixture with the top 10 most prevalent PAHs (SM10) from a Superfund site derived from environmental passive sampling data. Using the zebrafish model, we measured body burden at 48 hours post fertilization (hpf) and evaluated the developmental and neurotoxicity of SM10 and the 10 individual constituents at 24 hours post fertilization (hpf) and 5 days post fertilization (dpf). Zebrafish embryos were exposed from 6 to 120 hpf to (1) the SM10 mixture, (2) a variety of individual PAHs: pyrene, fluoranthene, retene, benzo[a]anthracene, chrysene, naphthalene, acenaphthene, phenanthrene, fluorene, and 2-methylnaphthalene. We demonstrated that SM10 and only 3 of the individual PAHs were developmentally toxic. Subsequently, we constructed and exposed developing zebrafish to two sub-mixtures: SM3 (comprised of 3 of the developmentally toxicity PAHs) and SM7 (7 non-developmentally toxic PAHs). We found that the SM3 toxicity profile was similar to SM10, and SM7 unexpectedly elicited developmental toxicity unlike that seen with its individual components. The results demonstrated that the overall developmental toxicity in the mixtures could be explained using the general concentration addition model. To determine if exposures activated the AHR pathway, spatial expression of CYP1A was evaluated in the 10 individual PAHs and the 3 mixtures at 5 dpf. Results showed activation of AHR in the liver and vasculature for the mixtures and some individual PAHs. Embryos exposed to SM10 during development and raised in chemical-free water into adulthood exhibited decreased learning and responses to startle stimulus indicating that developmental SM10 exposures affect neurobehavior. Collectively, these results exemplify the utility of zebrafish to investigate the developmental and neurotoxicity of complex mixtures.

Development of quantitative screen for 1550 chemicals with GC-MS.

With hundreds of thousands of chemicals in the environment, effective monitoring requires high-throughput analytical techniques. This paper presents a quantitative screening method for 1550 chemicals based on statistical modeling of responses with identification and integration performed using deconvolution reporting software. The method was evaluated with representative environmental samples. We tested biological extracts, low-density polyethylene, and silicone passive sampling devices spiked with known concentrations of 196 representative chemicals. A multiple linear regression (R2 = 0.80) was developed with molecular weight, logP, polar surface area, and fractional ion abundance to predict chemical responses within a factor of 2.5. Linearity beyond the calibration had R2 > 0.97 for three orders of magnitude. Median limits of quantitation were estimated to be 201 pg/µL (1.9× standard deviation). The number of detected chemicals and the accuracy of quantitation were similar for environmental samples and standard solutions. To our knowledge, this is the most precise method for the largest number of semi-volatile organic chemicals lacking authentic standards. Accessible instrumentation and software make this method cost effective in quantifying a large, customizable list of chemicals. When paired with silicone wristband passive samplers, this quantitative screen will be very useful for epidemiology where binning of concentrations is common. Graphical abstract A multiple linear regression of chemical responses measured with GC-MS allowed quantitation of 1550 chemicals in samples such as silicone wristbands.

Silicone wristbands compared with traditional polycyclic aromatic hydrocarbon exposure assessment methods.

Currently there is a lack of inexpensive, easy-to-use technology to evaluate human exposure to environmental chemicals, including polycyclic aromatic hydrocarbons (PAHs). This is the first study in which silicone wristbands were deployed alongside two traditional personal PAH exposure assessment methods: active air monitoring with samplers (i.e., polyurethane foam (PUF) and filter) housed in backpacks, and biological sampling with urine. We demonstrate that wristbands worn for 48 h in a non-occupational setting recover semivolatile PAHs, and we compare levels of PAHs in wristbands to PAHs in PUFs-filters and to hydroxy-PAH (OH-PAH) biomarkers in urine. We deployed all samplers simultaneously for 48 h on 22 pregnant women in an established urban birth cohort. Each woman provided one spot urine sample at the end of the 48-h period. Wristbands recovered PAHs with similar detection frequencies to PUFs-filters. Of the 62 PAHs tested for in the 22 wristbands, 51 PAHs were detected in at least one wristband. In this cohort of pregnant women, we found more significant correlations between OH-PAHs and PAHs in wristbands than between OH-PAHs and PAHs in PUFs-filters. Only two comparisons between PAHs in PUFs-filters and OH-PAHs correlated significantly (rs = 0.53 and p = 0.01; rs = 0.44 and p = 0.04), whereas six comparisons between PAHs in wristbands and OH-PAHs correlated significantly (rs = 0.44 to 0.76 and p = 0.04 to <0.0001). These results support the utility of wristbands as a biologically relevant exposure assessment tool which can be easily integrated into environmental health studies. Graphical abstract PAHs detected in samples collected from urban pregnant women.

Comparative developmental toxicity of a comprehensive suite of polycyclic aromatic hydrocarbons.

Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental contaminants that occur in complex mixtures. Several PAHs are known or suspected mutagens and/or carcinogens, but developmental toxicity data is lacking for PAHs, particularly their oxygenated and nitrated derivatives. Such data are necessary to understand and predict the toxicity of environmental mixtures. 123 PAHs were assessed for morphological and neurobehavioral effects for a range of concentrations between 0.1 and 50 µM, using a high throughput early-life stage zebrafish assay, including 33 parent, 22 nitrated, 17 oxygenated, 19 hydroxylated, 14 methylated, 16 heterocyclic, and 2 aminated PAHs. Additionally, each PAH was evaluated for AHR activation, by assessing CYP1A protein expression using whole animal immunohistochemistry (IHC). Responses to PAHs varied in a structurally dependent manner. High-molecular weight PAHs were significantly more developmentally toxic than the low-molecular weight PAHs, and CYP1A expression was detected in five distinct tissues, including vasculature, liver, skin, neuromasts and yolk.

Cross-sectional study of social behaviors in preschool children and exposure to flame retardants.

BACKGROUND: Children are exposed to flame retardants from the built environment. Brominated diphenyl ethers (BDE) and organophosphate-based flame retardants (OPFRs) are associated with poorer neurocognitive functioning in children. Less is known, however, about the association between these classes of compounds and children's emotional and social behaviors. The objective of this study was to determine if flame retardant exposure was associated with measurable differences in social behaviors among children ages 3-5 years. METHODS: We examined teacher-rated social behaviors measured using the Social Skills Improvement Rating Scale (SSIS) and personal exposure to flame retardants in children aged 3-5 years who attended preschool (n = 72). Silicone passive samplers worn for 7 days were used to assess personal exposure to 41 compounds using gas chromatography-mass spectrophotometer. These concentrations were then summed into total BDE and total OPFR exposure prior to natural log transformation. Separate generalized additive models were used to evaluate the relationship between seven subscales of the SSIS and lnΣBDE or lnΣOPFR adjusting for other age, sex, adverse social experiences, and family context. RESULTS: All children were exposed to a mixture of flame retardant compounds. We observed a dose dependent relationship between lnΣOPFR and two subscales where children with higher exposures were rated by their preschool teachers as having less responsible behavior (p = 0.07) and more externalizing behavior problems (p = 0.03). Additionally, children with higher lnΣBDE exposure were rated by teachers as less assertive (p = 0.007). CONCLUSIONS: We observed a cross-sectional association between children's exposure to flame retardant compounds and teacher-rated social behaviors among preschool-aged children. Children with higher flame retardant exposures exhibited poorer social skills in three domains that play an important role in a child's ability to succeed academically and socially.

Measuring Personal Exposure to Organophosphate Flame Retardants Using Silicone Wristbands and Hand Wipes.

Organophosphate flame retardants (PFRs) are widely used as replacements for polybrominated diphenyl ethers in consumer products. With high detection in indoor environments and increasing toxicological evidence suggesting a potential for adverse health effects, there is a growing need for reliable exposure metrics to examine individual exposures to PFRs. Silicone wristbands have been used as passive air samplers for quantifying exposure in the general population and occupational exposure to polycyclic aromatic hydrocarbons. Here we investigated the utility of silicone wristbands in measuring exposure and internal dose of PFRs through measurement of urinary metabolite concentrations. Wristbands were also compared to hand wipes as metrics of exposure. Participants wore wristbands for 5 consecutive days and collected first morning void urine samples on 3 alternating days. Urine samples were pooled across 3 days and analyzed for metabolites of the following PFRs: tris(1,3-dichloroisopropyl) phosphate (TDCIPP), tris(1-chloro-2-isopropyl) phosphate (TCIPP), triphenyl phosphate (TPHP), and monosubstituted isopropylated triaryl phosphate (mono-ITP). All four PFRs and their urinary metabolites were ubiquitously detected. Correlations between TDCIPP and TCIPP and their corresponding urinary metabolites were highly significant on the wristbands (rs = 0.5-0.65, p < 0.001), which suggest that wristbands can serve as strong predictors of cumulative, 5-day exposure and may be an improved metric compared to hand wipes.

Emissions of Polycyclic Aromatic Hydrocarbons from Natural Gas Extraction into Air.

Natural gas extraction, often referred to as "fracking", has increased rapidly in the United States in recent years. To address potential health impacts, passive air samplers were deployed in a rural community heavily affected by the natural gas boom. Samplers were analyzed for 62 polycyclic aromatic hydrocarbons (PAHs). Results were grouped based on distance from each sampler to the nearest active well. Levels of benzo[a]pyrene, phenanthrene, and carcinogenic potency of PAH mixtures were highest when samplers were closest to active wells. PAH levels closest to natural gas activity were comparable to levels previously reported in rural areas in winter. Sourcing ratios indicated that PAHs were predominantly petrogenic, suggesting that PAH levels were influenced by direct releases from the earth. Quantitative human health risk assessment estimated the excess lifetime cancer risks associated with exposure to the measured PAHs. At sites closest to active wells, the risk estimated for maximum residential exposure was 0.04 in a million, which is below the U.S. Environmental Protection Agency's acceptable risk level. Overall, risk estimates decreased 30% when comparing results from samplers closest to active wells to those farthest from them. This work suggests that natural gas extraction is contributing PAHs to the air, at levels that would not be expected to increase cancer risk.

PAH and OPAH Flux during the Deepwater Horizon Incident.

Passive sampling devices were used to measure air vapor and water dissolved phase concentrations of 33 polycyclic aromatic hydrocarbons (PAHs) and 22 oxygenated PAHs (OPAHs) at four Gulf of Mexico coastal sites prior to, during and after shoreline oiling from the Deepwater Horizon oil spill (DWH). Measurements were taken at each site over a 13 month period, and flux across the water-air boundary was determined. This is the first report of vapor phase and diffusive flux of both PAHs and OPAHs during the DWH. Vapor phase sum PAH and OPAH concentrations ranged between 6.6 and 210 ng/m(3) and 0.02 and 34 ng/m(3) respectively. PAH and OPAH concentrations in air exhibited different spatial and temporal trends than in water, and air-water flux of 13 individual PAHs was shown to be at least partially influenced by the DWH incident. The largest PAH volatilizations occurred at the sites in Alabama and Mississippi at nominal rates of 56 000 and 42 000 ng/m(2) day(-1) in the summer. Naphthalene was the PAH with the highest observed volatilization rate of 52 000 ng/m(2) day(-1) in June 2010. This work represents additional evidence of the DWH incident contributing to air contamination, and provides one of the first quantitative air-water chemical flux determinations with passive sampling technology.

PAH Accessibility in Particulate Matter from Road-Impacted Environments.

Snowmelt, surface runoff, or stormwater releases in urban environments can result in significant discharges of particulate matter-bound polycyclic aromatic hydrocarbons (PAHs) into aquatic environments. Recently, more-specific activities such as road-tunnel washing have been identified as contributing to contaminant load to surface waters. However, knowledge of PAH accessibility in particulate matter (PM) of urban origin that may ultimately be released into urban surface waters is limited. In the present study, we evaluated the accessibility of PAHs associated with seven distinct (suspended) particulate matter samples collected from different urban sources. Laboratory-based infinite sink extractions with silicone rubber (SR) as the extractor phase demonstrated a similar pattern of PAH accessibility for most PM samples. Substantially higher accessible fractions were observed for the less-hydrophobic PAHs (between 40 and 80% of total concentrations) compared with those measured for the most-hydrophobic PAHs (<5% of total concentrations). When we focused on PAHs bound to PM from tunnel-wash waters, first-order desorption rates for PAHs with log Kow > 5.5 were found in line with those commonly found for slowly or very slowly desorbing sediment-associated contaminants. PAHs with log Kow < 5.5 were found at higher desorbing rates. The addition of detergents did not influence the extractability of lighter PAHs but increased desorption rates for the heavier PAHs, potentially contributing to increases in the toxicity of tunnel-wash waters when surfactants are used. The implications of total and accessible PAH concentrations measured in our urban PM samples are discussed in a context of management of PAH and PM emission to the surrounding aquatic environment. Although we only fully assessed PAHs in this work, further study should consider other contaminants such as OPAHs, which were also detected in all PM samples.

Completing the Link between Exposure Science and Toxicology for Improved Environmental Health Decision Making: The Aggregate Exposure Pathway Framework.

Driven by major scientific advances in analytical methods, biomonitoring, computation, and a newly articulated vision for a greater impact in public health, the field of exposure science is undergoing a rapid transition from a field of observation to a field of prediction. Deployment of an organizational and predictive framework for exposure science analogous to the "systems approaches" used in the biological sciences is a necessary step in this evolution. Here we propose the aggregate exposure pathway (AEP) concept as the natural and complementary companion in the exposure sciences to the adverse outcome pathway (AOP) concept in the toxicological sciences. Aggregate exposure pathways offer an intuitive framework to organize exposure data within individual units of prediction common to the field, setting the stage for exposure forecasting. Looking farther ahead, we envision direct linkages between aggregate exposure pathways and adverse outcome pathways, completing the source to outcome continuum for more meaningful integration of exposure assessment and hazard identification. Together, the two frameworks form and inform a decision-making framework with the flexibility for risk-based, hazard-based, or exposure-based decision making.