Polycyclic aromatic hydrocarbons (PAHs) in urban stream sediments of Suzhou Industrial Park, an emerging eco-industrial park in China: Occurrence, sources and potential risk.

In this study, urban stream sediment samples were collected in the Suzhou Industrial Park (SIP), one of the earliest national demonstration eco-industrial parks of China. PAHs were analyzed in these sediments, and concentrations of total PAHs were 180-81,000 ng g-1 (5700 ± 14,000 ng g-1). Medium molecular weight (4- ring) PAHs were predominant (42 ± 12%), followed by high molecular weight (5- and 6- ring) PAHs (31 ± 10%). No correlation was found between concentrations of PAHs and land uses of SIP in this study. Diagnostic ratios and a positive matrix factorization (PMF) model indicated that coal/biomass combustion might be the primary PAH source (61%), followed by non-combustion sources (21%) and vehicular emission (18%). According to the spatial analysis, PAHs in the sediments of SIP might be mainly associated with the coal/biomass combustion in the northeast industrial zone. Residential & commercial activities seem not to be the major causes of PAH contamination. Total PAH toxic equivalent concentrations, effect range low/effect range median values, and mean effects range-median quotient all showed that PAHs were present at a low toxicity risk level in most regions of the SIP. However, vigilance is required at some sampling sites with extremely high PAH concentrations or high mean effects range-median quotient.

Volatilization of polycyclic aromatic hydrocarbons (PAHs) over the North Pacific and adjacent Arctic Ocean: The impact of offshore oil drilling.

Air and seawater samples were collected in 2016 over the North Pacific Ocean (NPO) and adjacent Arctic Ocean (AO), and Polycyclic Aromatic Hydrocarbons (PAHs) were quantified in them. Atmospheric concentrations of ∑15 PAHs (gas + particle phase) were 0.44-7.0 ng m-3 (mean = 2.3 ng m-3), and concentrations of aqueous ∑15 PAHs (dissolved phase) were 0.82-3.7 ng L-1 (mean = 1.9 ng L-1). Decreasing latitudinal trends were observed for atmospheric and aqueous PAHs. Results of diagnostic ratios suggested that gaseous and aqueous PAHs were most likely to be related to the pyrogenic and petrogenic sources, respectively. Three sources, volatilization, coal and fuel oil combustion, and biomass burning, were determined by the PMF model for gaseous PAHs, with percent contributions of 10%, 44%, and 46%, respectively. The 4- ring PAHs underwent net deposition during the cruise, while some 3- ring PAHs were strongly dominated by net volatilization, even in the high latitude Arctic region. Offshore oil/gas production activities might result in the sustained input of low molecular weight 3- ring PAHs to the survey region, and further lead to the volatilization of them. Compared to the gaseous exchange fluxes, fluxes of atmospheric dry deposition and gaseous degradation were negligible. According to the extrapolated results, the gaseous exchange of semivolatile aromatic-like compounds (SALCs) may have a significant influence on the carbon cycling in the low latitude oceans, but not for the high latitude oceans.

Recent Advances in the Study of the Remediation of Polycyclic Aromatic Compound (PAC)-Contaminated Soils: Transformation Products, Toxicity, and Bioavailability Analyses.

Polycyclic aromatic compounds (PACs) encompass a diverse group of compounds, often found in historically contaminated sites. Different experimental techniques have been used to remediate PACs-contaminated soils. This brief review surveyed over 270 studies concerning remediation of PACs-contaminated soils and found that, while these studies often measured the concentration of 16 parent polycyclic aromatic hydrocarbons (PAHs) pre- and post-remediation, only a fraction of the studies included the measurement of PAC-transformation products (PAC-TPs) and other PACs (n = 33). Only a few studies also incorporated genotoxicity/toxicity/mutagenicity analysis pre- and post-remediation (n = 5). Another aspect that these studies often neglected to include was bioavailability, as none of the studies that included measurement of PAH-TPs and PACs included bioavailability investigation. Based on the literature analysis, future remediation studies need to consider chemical analysis of PAH-TPs and PACs, genotoxicity/toxicity/mutagenicity, and bioavailability analyses pre- and post-remediation. These assessments will help address numerous concerns including, among others, the presence, properties, and toxicity of PACs and PAH-TPs, risk assessment of soil post-remediation, and the bioavailability of PAH-TPs. Other supplementary techniques that help assist these analyses and recommendations for future analyses are also discussed.

Formation of PAH Derivatives and Increased Developmental Toxicity during Steam Enhanced Extraction Remediation of Creosote Contaminated Superfund Soil.

Steam enhanced extraction (SEE) is an in situ thermal remediation technique used to remove and recover polycyclic aromatic hydrocarbons (PAHs) from contaminated soils. However, limited studies have been conducted on the formation of PAH derivatives during and after SEE of PAH contaminated soils. Creosote contaminated soil samples collected from the Wyckoff-Eagle Harbor Superfund site were remediated with laboratory scale SEE. The samples were quantified for unsubstituted PAHs and their derivatives and assessed for developmental toxicity, pre- and post-SEE. Following SEE, unsubstituted PAH concentrations decreased, while oxygenated PAH concentrations increased in soil and aqueous extracts. Differences in developmental toxicity were also measured and linked to the formation of PAH derivatives. Additive toxicity was measured when comparing unfractionated extracts to fractionated extracts in pre- and post-SEE samples. SEE is effective in removing unsubstituted PAHs from contaminated soil, but other, potentially more toxic, PAH derivatives are formed.

Development of a high-throughput in vivo screening platform for particulate matter exposures.

Particulate matter (PM) exposure is a public health burden with poorly understood health effect mechanisms and lacking an efficient model to compare the vast diversity of PM exposures. Zebrafish (Danio rerio) are amenable to high-throughput screening (HTS), but few studies have investigated PM toxicity in zebrafish, despite the multitude of advantages. To develop standardized exposure procedures, the urban PM standard reference material (SRM) 1649b was used to systematically determine sample preparation methods, design experimental controls, determine concentration ranges and evaluation procedures. Embryos (n = 32/treatment) were dechorionated and placed into 96-well plates containing SRM1649b (0-200 µg/mL) at 6 h post fertilization (hpf). Developmental toxicity was assessed at 24 and 120 hpf by evaluating morphological changes, embryonic/larval photomotor behavior, and mortality. Differences from blank medium and particle controls were observed for all biological responses measured. Differences due to SRM1649b concentration and preparation method were also observed. Exposure to SRM1649b from DMSO extraction was associated with changes in morphology and mortality and hypoactivity in photomotor responses compared to the DMSO control for the whole particle suspension (76, 68%) and soluble fraction (59, 54%) during the embryonic and larval stages, respectively. Changes in behavioral responses were not observed following exposure to the insoluble fraction of SRM1649b from DMSO extraction. The toxicity bias from PM preparation provided further impetus to select a single HTS exposure method. Based on the biological activity results, the soluble fraction of SRM1649b from DMSO extraction was selected and shown to have concentration dependent cyp1a/GFP expression. This rapid, sensitive and consistently scalable model is a potentially cost-effective vertebrate approach to study the toxicology of PM from diverse locations, and provides a path to identifying the toxic material(s) in these samples, and discover the mechanisms of toxicity.

Automating data analysis for two-dimensional gas chromatography/time-of-flight mass spectrometry non-targeted analysis of comparative samples.

Non-targeted analysis of environmental samples, using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC × GC/ToF-MS), poses significant data analysis challenges due to the large number of possible analytes. Non-targeted data analysis of complex mixtures is prone to human bias and is laborious, particularly for comparative environmental samples such as contaminated soil pre- and post-bioremediation. To address this research bottleneck, we developed OCTpy, a Python™ script that acts as a data reduction filter to automate GC × GC/ToF-MS data analysis from LECO® ChromaTOF® software and facilitates selection of analytes of interest based on peak area comparison between comparative samples. We used data from polycyclic aromatic hydrocarbon (PAH) contaminated soil, pre- and post-bioremediation, to assess the effectiveness of OCTpy in facilitating the selection of analytes that have formed or degraded following treatment. Using datasets from the soil extracts pre- and post-bioremediation, OCTpy selected, on average, 18% of the initial suggested analytes generated by the LECO® ChromaTOF® software Statistical Compare feature. Based on this list, 63-100% of the candidate analytes identified by a highly trained individual were also selected by OCTpy. This process was accomplished in several minutes per sample, whereas manual data analysis took several hours per sample. OCTpy automates the analysis of complex mixtures of comparative samples, reduces the potential for human error during heavy data handling and decreases data analysis time by at least tenfold.

Implications of Bioremediation of Polycyclic Aromatic Hydrocarbon-Contaminated Soils for Human Health and Cancer Risk.

Bioremediation uses soil microorganisms to degrade polycyclic aromatic hydrocarbons (PAHs) into less toxic compounds and can be performed in situ, without the need for expensive infrastructure or amendments. This review provides insights into the cancer risks associated with PAH-contaminated soils and places bioremediation outcomes in a context relevant to human health. We evaluated which bioremediation strategies were most effective for degrading PAHs and estimated the cancer risks associated with PAH-contaminated soils. Cancer risk was statistically reduced in 89% of treated soils following bioremediation, with a mean degradation of 44% across the B2 group PAHs. However, all 180 treated soils had postbioremediation cancer risk values that exceeded the U.S. Environmental Protection Agency (USEPA) health-based acceptable risk level (by at least a factor of 2), with 32% of treated soils exceeding recommended levels by greater than 2 orders of magnitude. Composting treatments were most effective at biodegrading PAHs in soils (70% average reduction compared with 28-53% for the other treatment types), which was likely due to the combined influence of the rich source of nutrients and microflora introduced with organic compost amendments. Ultimately, bioremediation strategies, in the studies reviewed, were unable to successfully remove carcinogenic PAHs from contaminated soils to concentrations below the target cancer risk levels recommended by the USEPA.

Formation of Developmentally Toxic Phenanthrene Metabolite Mixtures by Mycobacterium sp. ELW1.

Mycobacterium sp. ELW1 co-metabolically degraded up to 1.8 µmol of phenanthrene (PHE) in ∼48 h, and hydroxyphenanthrene (OHPHE) metabolites, including 1-hydroxyphenanthrene (1-OHPHE), 3-hydroxyphenanthrene (3-OHPHE), 4-hydroxyphenanthrene (4-OHPHE), 9-hydroxyphenanthrene (9-OHPHE), 9,10-dihydroxyphenanthrene (1,9-OHPHE), and trans-9,10-dihydroxy-9,10-dihydrophenanthrene (trans-9,10-OHPHE), were identified and quantified over time. The monooxygenase responsible for co-metabolic transformation of PHE was inhibited by 1-octyne. First-order PHE transformation rates, kPHE, and half-lives, t1/2, for PHE-exposed cells were 0.16-0.51 h-1 and 1.4-4.3 h, respectively, and the 1-octyne controls ranged from 0.015-0.10 h-1 to 7.0-47 h, respectively. While single compound standards of PHE and trans-9,10-OHPHE, the major OHPHE metabolite formed by ELW1, were not toxic to embryonic zebrafish (Danio rerio), single compound standards of minor OHPHE metabolites, 1-OHPHE, 3-OHPHE, 4-OHPHE, 9-OHPHE, and 1,9-OHPHE, were toxic, with effective concentrations (EC50's) ranging from 0.5 to 5.5 µM. The metabolite mixtures formed by ELW1, and the reconstructed standard mixtures of the identified OHPHE metabolites, elicited a toxic response in zebrafish for the same three time points. EC50s for the metabolite mixtures formed by ELW1 were lower (more toxic) than those for the reconstructed standard mixtures of the identified OHPHE metabolites. Ten unidentified hydroxy PHE metabolites were measured in the derivatized mixtures formed by ELW1 and may explain the increased toxicity of the ELW1 metabolites mixture relative to the reconstructed standard mixtures of the identified OHPHE metabolites.

Seasonal variations and source apportionment of complex polycyclic aromatic hydrocarbon mixtures in particulate matter in an electronic waste and urban area in South China.

Complex polycyclic aromatic hydrocarbon (PAH) mixtures including parent PAHs, high molecular weight PAHs (MW 302 PAHs), and halogenated PAHs (HPAHs) were measured in particulate matter (PM) in an urban area and a rural electronic waste area in South China. The concentrations of MW < 302 PAHs at two sites were not significantly different with annual means of 23.2 ± 17.2 and 33.7 ± 29.0 ng/m3, respectively. However the concentrations of both MW 302 PAHs (5.35 ± 3.72 ng/m3) and HPAH (49.9 pg/m3) were significantly higher at the e-waste site than the urban site (2.81 ± 2.36 ng/m3 and 28.2 ± 28.5 pg/m3), suggesting e-waste recycling being a significant source of these PAHs. The majority of PAHs exhibited higher concentrations in winter and spring and lower concentrations in fall and summer. Meteorological conditions and increased emissions of PAHs in northern China due to domestic heating in colder seasons are important factors influencing the PAH seasonal variations. Source apportionment by the chemical mass balance (CMB) model indicated that residential stoves (coal combustion), industrial boilers (coal combustion), biomass burning, and vehicular emission accounted for 38 ± 14%, 30 ± 11%, 22 ± 22%, and 10 ± 7% of the PAHs in the urban PM, respectively. Comparable contributions from these sources were also observed for PM at the e-waste site. PAH emission factors are needed for primitive e-waste recycling to further understand the importance of this source to ambient air.

Optimizing multi-dimensional high throughput screening using zebrafish.

The use of zebrafish for high throughput screening (HTS) for chemical bioactivity assessments is becoming routine in the fields of drug discovery and toxicology. Here we report current recommendations from our experiences in zebrafish HTS. We compared the effects of different high throughput chemical delivery methods on nominal water concentration, chemical sorption to multi-well polystyrene plates, transcription responses, and resulting whole animal responses. We demonstrate that digital dispensing consistently yields higher data quality and reproducibility compared to standard plastic tip-based liquid handling. Additionally, we illustrate the challenges in using this sensitive model for chemical assessment when test chemicals have trace impurities. Adaptation of these better practices for zebrafish HTS should increase reproducibility across laboratories.

Quantitation and prediction of sorptive losses during toxicity testing of polycyclic aromatic hydrocarbon (PAH) and nitrated PAH (NPAH) using polystyrene 96-well plates.

Developing zebrafish are increasingly being used for rapid assessments of chemical toxicity, and these assays are frequently conducted in multi-well plastic plates. This study investigated the sorptive behavior of polycyclic aromatic hydrocarbons (PAHs) and nitrated PAHs (NPAHs) to uncoated 96-well polystyrene plates typically used for zebrafish (Danio rerio) testing. We measured the percent sorption in the presence and absence of zebrafish embryos, at two exposure concentrations, as well as using two different procedures (addition of embryos to polystyrene plates either before analyte addition, or allowing 24h of equilibrium between analyte addition and embryo addition to the polystyrene plates). Following exposure, the plates were extracted with hexane and analyzed using gas chromatography coupled with mass spectrometry (GC/MS). Allowing 24h of pre-incubation between the addition of analytes and embryos did not significantly impact the percent sorption. The percent sorption was higher for both PAHs and NPAHs at the lower exposure concentration, and sorption was lower in the presence of zebrafish embryos. A mass balance model was developed to predict the sorption to polystyrene plates, based on the PAH and NPAH mass distribution ratios between polystyrene and water. While PAH sorption was significantly correlated with subcooled liquid solubility, NPAH sorption did not correlate with any of the physical-chemical properties investigated. This indicates the need to better understand the sorptive behavior of hydrophobic analytes to plastics, and to better account for sorptive losses during toxicity testing in polystyrene plates.

Communicating Results of a Dietary Exposure Study Following Consumption of Traditionally Smoked Salmon.

One expectation of community-based participatory research (CBPR) is participant access to study results. However, reporting experimental data produced by studies involving biological measurements in the absence of clinical relevance can be challenging to scientists and participants. We applied best practices in data sharing to report the results of a study designed to explore polycyclic aromatic hydrocarbons absorption, metabolism, and excretion following consumption of traditionally smoked salmon by members of the Confederated Tribes of the Umatilla Indian Reservation (CTUIR). A dietary exposure study was developed, in which nine Tribal members consumed 50 g of traditionally smoked salmon and provided repeated urine samples over 24 hours. During recruitment, participants requested access to their data following analysis. Disclosing data is an important element of CBPR and must be treated with the same rigor as that given to the data analysis. The field of data disclosure is relatively new, but when handled correctly can improve education within the community, reduce distrust, and enhance environmental health literacy. Using the results from this study, we suggest mechanisms for sharing data with a Tribal community.

Relative Influence of Trans-Pacific and Regional Atmospheric Transport of PAHs in the Pacific Northwest, U.S.

The relative influences of trans-Pacific and regional atmospheric transport on measured concentrations of polycyclic aromatic hydrocarbons (PAHs), PAH derivatives (nitro- (NPAH) and oxy-(OPAH)), organic carbon (OC), and particulate matter (PM) less than 2.5 µm in diameter (PM2.5) were investigated in the Pacific Northwest, U.S. in 2010-2011. Ambient high volume PM2.5 air samples were collected at two sites in the Pacific Northwest: (1.) Mount Bachelor Observatory (MBO) in the Oregon Cascade Range (2763 m above sea level (asl)) and 2.) Confederated Tribes of the Umatilla Indian Reservation (CTUIR) in the Columbia River Gorge (CRG) (954 m asl). At MBO, the 1,8-dinitropyrene concentration was significantly positively correlated with the time a sampled air mass spent over Asia, suggesting that this NPAH may be a good marker for trans-Pacific atmospheric transport. At CTUIR, NOx, CO2, and SO2 emissions from a 585 MW coal fired power plant, in Boardman OR, were found to be significantly positively correlated with PAH, OPAH, NPAH, OC, and PM2.5 concentrations. By comparing the Boardman Plant operational time frames when the plant was operating to when it was shut down, the plant was found to contribute a large percentage of the measured PAH (67%), NPAH (91%), OPAH (54%), PM2.5 (39%), and OC (38%) concentrations at CTUIR and the CRG prior to Spring 2011 and likely masked trans-Pacific atmospheric transport events to the CRG. Upgrades installed to the Boardman Plant in the spring of 2011 dramatically reduced the plant's contribution to PAH and OPAH concentrations (by ∼72% and ∼40%, respectively) at CTUIR and the CRG, but not NPAH, PM2.5 or OC concentrations.

Aerobic Bioremediation of PAH Contaminated Soil Results in Increased Genotoxicity and Developmental Toxicity.

The formation of more polar and toxic polycyclic aromatic hydrocarbon (PAH) transformation products is one of the concerns associated with the bioremediation of PAH-contaminated soils. Soil contaminated with coal tar (prebioremediation) from a former manufactured gas plant (MGP) site was treated in a laboratory scale bioreactor (postbioremediation) and extracted using pressurized liquid extraction. The soil extracts were fractionated, based on polarity, and analyzed for 88 PAHs (unsubstituted, oxygenated, nitrated, and heterocyclic PAHs). The PAH concentrations in the soil tested, postbioremediation, were lower than their regulatory maximum allowable concentrations (MACs), with the exception of the higher molecular weight PAHs (BaA, BkF, BbF, BaP, and IcdP), most of which did not undergo significant biodegradation. The soil extract fractions were tested for genotoxicity using the DT40 chicken lymphocyte bioassay and developmental toxicity using the embryonic zebrafish (Danio rerio) bioassay. A statistically significant increase in genotoxicity was measured in the unfractionated soil extract, as well as in four polar soil extract fractions, postbioremediation (p < 0.05). In addition, a statistically significant increase in developmental toxicity was measured in one polar soil extract fraction, postbioremediation (p < 0.05). A series of morphological abnormalities, including peculiar caudal fin malformations and hyperpigmentation in the tail, were measured in several soil extract fractions in embryonic zebrafish, both pre- and postbioremediation. The increased toxicity measured postbioremediation is not likely due to the 88 PAHs measured in this study (including quinones), because most were not present in the toxic polar fractions and/or because their concentrations did not increase postbioremediation. However, the increased toxicity measured postbioremediation is likely due to hydroxylated and carboxylated transformation products of the 3- and 4-ring PAHs (PHE, 1MPHE, 2MPHE, PRY, BaA, and FLA) that were most degraded.

Heterogeneous reactions of particulate matter-bound PAHs and NPAHs with NO3/N2O5, OH radicals, and O3 under simulated long-range atmospheric transport conditions: reactivity and mutagenicity.

The heterogeneous reactions of ambient particulate matter (PM)-bound polycyclic aromatic hydrocarbons (PAHs) and nitro-PAHs (NPAHs) with NO3/N2O5, OH radicals, and O3 were studied in a laboratory photochemical chamber. Ambient PM2.5 and PM10 samples were collected from Beijing, China, and Riverside, California, and exposed under simulated atmospheric long-range transport conditions for O3 and OH and NO3 radicals. Changes in the masses of 23 PAHs and 20 NPAHs, as well as the direct and indirect-acting mutagenicity of the PM (determined using the Salmonella mutagenicity assay with TA98 strain), were measured prior to and after exposure to NO3/N2O5, OH radicals, and O3. In general, O3 exposure resulted in the highest relative degradation of PM-bound PAHs with more than four rings (benzo[a]pyrene was degraded equally well by O3 and NO3/N2O5). However, NPAHs were most effectively formed during the Beijing PM exposure to NO3/N2O5. In ambient air, 2-nitrofluoranthene (2-NF) is formed from the gas-phase NO3 radical- and OH radical-initiated reactions of fluoranthene, and 2-nitropyrene (2-NP) is formed from the gas-phase OH radical-initiated reaction of pyrene. There was no formation of 2-NF or 2-NP in any of the heterogeneous exposures, suggesting that gas-phase formation of NPAHs did not play an important role during chamber exposures. Exposure of Beijing PM to NO3/N2O5 resulted in an increase in direct-acting mutagenic activity which was associated with the formation of mutagenic NPAHs. No NPAH formation was observed in any of the exposures of the Riverside PM. This was likely due to the accumulation of atmospheric degradation products from gas-phase reactions of volatile species onto the surface of PM collected in Riverside prior to exposure in the chamber, thus decreasing the availability of PAHs for reaction.

Polystyrene plastic: a source and sink for polycyclic aromatic hydrocarbons in the marine environment.

Polycyclic aromatic hydrocarbons (PAHs) on virgin polystyrene (PS) and PS marine debris led us to examine PS as a source and sink for PAHs in the marine environment. At two locations in San Diego Bay, we measured sorption of PAHs to PS pellets, sampling at 0, 1, 3, 6, 9, and 12 months. We detected 25 PAHs using a new analytical method with comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry. Several congeners were detected on samples before deployment. After deployment, some concentrations decreased (1,3-dimethylnaphthalene and 2,6-methylnaphthalene), while most increased [2-methylanthracene and all parent PAHs (PPAHs), except fluorene and fluoranthene], suggesting that PS debris is a source and sink for PAHs. When sorbed concentrations of PPAHs on PS are compared to the five most common polymers [polyethylene terephthalate (PET), high-density polyethylene (HDPE), polyvinyl chloride (PVC), low-density polyethylene (LDPE), and polypropylene (PP)], PS sorbed greater concentrations than PP, PET, and PVC, similar to HDPE and LDPE. Most strikingly, at 0 months, PPAHs on PS ranged from 8 to 200 times greater than on PET, HDPE, PVC, LDPE, and PP. The combination of greater PAHs in virgin pellets and large sorption suggests that PS may pose a greater risk of exposure to PAHs upon ingestion.

Quantification of complex polycyclic aromatic hydrocarbon mixtures in standard reference materials using comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry.

This research is the first to quantify complex PAH mixtures in NIST SRMs using comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC/ToF-MS), with and without extract cleanup, and reports previously unidentified PAH congeners in the NIST SRMs. We tested a novel, high orthogonality GC column combination (LC-50×NSP-35), as well as with a commonly used column combination (Rtx-5ms×Rxi-17) for the quantification of a complex mixture of 85 different PAHs, including parent (PAHs), alkyl- (MPAHs), nitro- (NPAHs), oxy- (OPAHs), thio- (SPAHs), bromo- (BrPAHs), and chloro-PAHs (ClPAHs) in extracts from two standard reference materials: NIST SRM1650b (diesel particulate matter), with cleanup and NIST SRM1975 (diesel particulate extract), with and without extract cleanup. The LC-50×NSP-35 column combination resulted in an average absolute percent difference of 33.8%, 62.2% and 30.8% compared to the NIST certified PAH concentrations for NIST SRM1650b, NIST SRM1975 with cleanup and NIST SRM1975 without cleanup, while the Rtx-5ms×Rxi-17 resulted in an absolute percent difference of 38.6%, 67.2% and 79.6% for NIST SRM1650b, NIST SRM1975 with cleanup and NIST SRM1975 without cleanup, respectively. This GC×GC/ToF-MS method increases the number of PAHs detected and quantified in complex environmental extracts using a single chromatographic run. Without clean-up, 7 additional compounds were detected and quantified in NIST SRM1975 using the LC-50×NSP-35 column combination. These results suggest that the use of the LC-50×NSP-35 column combination in GC×GC/ToF-MS not only results in better chromatographic resolution and greater orthogonality for the separation of complex PAH mixtures, but can also be used for the accurate quantification of complex PAH mixtures in environmental extracts, such as diesel particulate matter, without silica gel cleanup.

Inhalation cancer risk associated with exposure to complex polycyclic aromatic hydrocarbon mixtures in an electronic waste and urban area in South China.

Atmospheric particulate matter samples were collected from May 2010 to April 2011 in a rural e-waste area and in Guangzhou, South China, to estimate the lifetime inhalation cancer risk from exposure to parent polycyclic aromatic hydrocarbons (PAHs), high molecular weight PAHs (MW 302 PAHs), and halogenated PAHs (HPAHs). Seasonal variations in the PAH concentrations and profiles within and between the e-waste and urban areas indicated different PAH sources in the two areas. Benzo[b]fluoranthene, benzo[a]pyrene, dibenz[ah]anthracene, and dibenzo[al]pyrene made the most significant contribution to the inhalation cancer risk. MW 302 PAHs accounted for 18.0% of the total cancer risk in the e-waste area and 13.6% in the urban area, while HPAHs made a minor contribution (<0.1%) in both the areas. The number of lifetime excess lung cancers due to exposure to parent PAHs, MW 302 PAHs, and HPAHs ranged from 15.1 to 1198 per million people in the e-waste area and from 9.3 to 737 per million people in Guangzhou. PAH exposure accounted for 0.02 to 1.94% of the total lung cancer cases in Guangzhou. On average, the inhalation cancer risk in the e-waste area was 1.6 times higher than in the urban area. The e-waste dismantling activities in South China led to higher inhalation cancer risk due to PAH exposure than the urban area.