Interactions between polycyclic aromatic hydrocarbons (PAHs) and titanium dioxide (TiO2) nanoparticles (NPs) can produce unforeseen photoproducts in the aqueous phase. Both PAHs and TiO2-NPs are well-studied and highly persistent environmental pollutants, but the consequences of PAH-TiO2-NP interactions are rarely explored. We investigated PAH photoproduct formation over time for benzo[a]pyrene (BaP), fluoranthene (FLT), and pyrene (PYR) in the presence of ultraviolet A (UVA) using a combination of analytical and computational methods including, identification of PAH photoproducts, assessment of expression profiles for gene indicators of PAH metabolism, and computational evaluation of the reaction mechanisms through which certain photoproducts might be formed. Chemical analyses identified diverse photoproducts, but all PAHs shared a primary photoproduct, 9,10-phenanthraquinone (9,10-PQ), regardless of TiO2-NP presence. The computed reaction mechanisms revealed the roles photodissociation and singlet oxygen chemistry likely play in PAH mediated photochemical processes that result in the congruent production of 9,10-PQ within this study. Our investigation of PAH photoproduct formation has provided substantial evidence of the many, diverse and congruent, photoproducts formed from physicochemically distinct PAHs and how TiO2-NPs influence bioavailability and time-related formation of PAH photoproducts.

Proposed workflow for down-selection of sorbents in synthetic and real stormwaters for optimized heavy metal and PFAS removal.

Abstract Lung cancer risk from exposure to ambient polycyclic aromatic hydrocarbons (PAHs) is expected to change significantly by 2050 compared to 2008 due to changes in climate and emissions. Integrating a global atmospheric chemistry model, a lung cancer risk model, and plausible future emissions trajectories of PAHs, we assess how global PAHs and their associated lung cancer risk will likely change in the future. Benzo(a)pyrene (BaP) is used as an indicator of cancer risk from PAH mixtures. From 2008 to 2050, the population‐weighted global average BaP concentrations under all RCPs consistently exceeded the WHO‐recommended limits, primarily attributed to residential biofuel use. Peaks in PAH‐associated incremental lifetime cancer risk shift from East Asia (4 × 10−5) in 2008 to South Asia (mostly India, 2–4 × 10−5) and Africa (1–2 × 10−5) by 2050. In the developing regions of Africa and South Asia, PAH‐associated lung cancer risk increased by 30–64% from 2008 to 2050, due to increasing residential energy demand in households for cooking, heating, and lighting, the continued use of traditional biomass use, increases in agricultural waste burning, and forest fires, accompanied by rapid population growth in these regions. Due to more stringent air quality policies in developed countries, their PAH lung cancer risk substantially decreased by ∼80% from 2008 to 2050. Climate change is likely to have minor effects on PAH lung cancer risk compared to the impact of emissions. Future policies, therefore, need to consider efficient combustion technologies that reduce air pollutant emissions, including incomplete combustion products such as PAH.

Phytoremediation has the potential to remove per- andpolyfluoroalkylsubstances (PFAS) from stormwater. However, there is currently limitedknowledge as to how plant type affects PFAS removal from stormwater,particularly in plants commonly used in stormwater bioswales. Thisgreenhouse study evaluated the abilities of ten different PacificNorthwest native plants to remove PFAS from stormwater. The PFAS includedC4-C10 perfluoroalkyl carboxylates; C4, C6, and C8 perfluoroalkylsulfonates; and C6 and C8 perfluoroalkyl sulfonamides (FASAs). Plantswere irrigated with the contaminated stormwater once a week for 10weeks. The presence of plants enhanced PFAS removal over the uncultivatedcontrols, with rushes and dicots having the highest total PFAS removalefficiencies ranging from 75 to 80%. The fate of the PFAS compoundswas ultimately controlled by their Log organic carbon/water partitioncoefficient (K (oc)) and molar volume. ThePFAS molar volume and Log K (oc) were stronglycorrelated with soil affinity (Pearson's r = 0.82 to 0.85), resulting in greater removal efficiencies of largerPFAS compounds. Conversely, molar volume and Log K (oc) values were strongly negatively correlated with bioconcentrationfactors (BCFs)(Pearson's r = -0.72to -0.82), resulting in the preferential bioaccumulation ofsmaller PFAS compounds. PFAS molar volume was also strongly negativelycorrelated with plant translocation factors (TFs)(Pearson's r = -0.88), resulting in a preferential accumulationof the smaller PFAS compounds in the above-ground biomass. Conversely,root BCFs were positively correlated with the PFAS molar volume andLog K (oc) for C4-C7 compounds (Pearson's r = 0.91 to 0.96) but became negatively correlated for C8-C10compounds (Pearson's r = -0.89 to -0.99)as competition for sorption with the surrounding soil increased. Theresulting chevron pattern indicated that the plant roots preferentiallyaccumulated those PFAS compounds that were too large and hydrophobicto easily translocate to the above-ground biomass but were also toosmall and hydrophilic to have a strong affinity for the surroundingsoil. Mass recovered for C6 and C8 FASAs was & LE;35% in all plantsand uncultivated control, indicating microbial transformation. Enrichmentof linear perfluorooctane sulfonate (L-PFOS) was observed in all plantcomponents (leaves, stems, and roots) relative to the stormwater influent.Finally, the removal of PFAS compounds from the stormwater could beaccurately modeled with a multivariate linear regression containingthe PFAS Log K (oc). Additional multivariatemodeling revealed that plants with higher evapotranspiration rateshad higher PFAS accumulations. However, evapotranspiration rates alonecould not accurately model plant PFAS accumulation, indicating thatother factors are also responsible for the differences observed. Inparticular, evapotranspiration rates were not successful in predictingplant PFBA accumulation. Rather, PFBA accumulation increased withincrease in root mass, TFs, and leaf BCFs. This suggested that carrier-mediatedtransport mechanisms were responsible for PFBA accumulation in plants.

Polycyclic aromatic compounds (PACs) are organic compounds commonly found in contaminated soil. Previous studies have shown the removal of polycyclic aromatic hydrocarbons (PAHs) in creosote-contaminated soils during steam enhanced extraction (SEE). However, less is known about the removal of alkyl-PAHs and heterocyclic compounds, such as azaarenes, and oxygen- and sulfur-heterocyclic PACs (OPACs and PASHs, respectively). Further, the impact of SEE on the freely dissolved concentration of PACs in soil as well as the soil bioactivity pre- and post-SEE have yet to be addressed. To fulfil these research gaps, chemical and bioanalytical analysis of a creosote-contaminated soil, collected from a U.S. Superfund site, pre- and post-SEE were performed. The decrease of 64 PACs (5-100%) and increase in the concentrations of nine oxygenated-PAHs (OPAHs) (150%) during SEE, some of which are known to be toxic and can potentially contaminate ground water, were observed. The freely dissolved concentrations of PACs in soil were assessed using polyoxymethylene (POM) strips and the concentrations of 66 PACs decreased post-SEE (1-100%). Three in vitro reporter gene bioassays (DR-CALUX (R), ER alpha-CALUX (R) and anti-AR CALUX (R)) were used to measure soil bioactivities pre- and post-SEE and all reporter gene bioassays measured soil bioactivity decreases post-SEE. Mass defect suspect screening tentatively identified 27 unique isomers of azaarenes and OPAC in the soil. As a remediation technique, SEE was found to remove alkyl-PAHs and heterocyclic PACs, reduce the concentrations of freely dissolved PACs, and decrease soil bioactivities.

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.

The oxidative potential (OP) of atmospheric fine particulate matter (PM2.5) has been linked to organic content, which includes polycyclic aromatic hydrocarbons (PAHs). The OP of 135 individual PAHs (including six subclasses) was measured using the dithiolthreitol (DTT) consumption assay. The DTT assay results were used to compute the concentration of each PAH needed to consume 50% of the DTT concentration in the assay (DTT50), and the reduction potential of the PAHs (ΔGrxn). Computed reduction potential results were found to match literature reduction potential values (r2 = 0.97), while DTT50 results had no correlations with the computed ΔGrxn values (r2 < 0.1). The GINI equality index was used to assess the electron distribution across the surface of unreacted and reacted PAHs. GINI values correlated with ΔGrxn in UPAH, HPAH, and OHPAH subclasses, as well as with all 135 PAHs in this study but did not correlate with DTT50, indicating that electron dispersion is linked to thermodynamic reactions and structural differences in PAHs, but not linked to the OP of PAHs. Three ambient PM2.5 filters extracts were measured in the DTT assay, alongside mixtures of analytical standards prepared to match PAH concentrations in the filter extracts to test if the OP follows an additive model of toxicity. The additive prediction model did not accurately predict the DTT consumption in the assay for any of the prepared standard mixtures or ambient PM2.5 filter extracts, indicating a much more complex model of toxicity for the OP of PAHs in ambient PM2.5. This study combined computed molecular properties with toxicologically relevant assay results to probe the OP of anthropogenically driven portions of ambient PM2.5, and results in a better understanding of the complexity of ambient PM2.5 OP.

Polycyclic aromatic hydrocarbons (PAHs) and titanium dioxide (TiO2) nanoparticles (NPs) are photoactive environmental pollutants that can contaminate aquatic environments. Aqueous-phase interactions between PAHs and TiO2-NPs are of interest due to their emerging environmental relevance, particularly with the deliberate application of TiO2-NPs to remediate pollution events (e.g., oil spills). Our objective was to investigate anthracene (ANT) and phenanthrene (PHE) photoproduct formation and transformation following ultraviolet A (UVA) irradiation in the presence and absence of TiO2-NPs. ANT and PHE solutions were prepared alone or in combination with TiO2-NPs, UVA-irradiated, and either exposed to larval zebrafish or collected for chemical analyses of diverse hydroxylated PAHs (OHPAHs) and oxygenated PAHs (OPAHs). The expression profiles of genes encoding for enzymes involved in PAH metabolism showed PAH-specific and time-dependent inductions that demonstrated changes in PAH and photoproduct bioavailability in the presence of TiO2-NPs. Chemical analyses of PAH/NP solutions in the absence of zebrafish larvae identified diverse photoproducts of differing size and ring arrangements, which suggested photodissociation, recombination, and ring re-arrangements of PAHs occurred either during or following UVA irradiation. Both ANT and PHE solutions showed heightened oxidative potential following irradiation, but TiO2-NP-related increases in oxidative potential were PAH-specific. The exploitation of multiple analytical methods provided novel insights into distinct PAH photoactivity, TiO2-NP influence on photoproduct formation in a PAH-specific manner, and the significant role time plays in photochemical processes.

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 Sigma(15) PAHs (gas + particle phase) were 0.44-7.0 ng m(-3) (mean = 2.3 ng m(-3)), and concentrations of aqueous Sigma(15) PAHs (dissolved phase) were 0.82-3.7 ng L-1 (mean = 1.9 ng L-10). 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. (C) 2020 Elsevier Ltd. All rights reserved.

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.

Atmospheric fine particulate matter (PM2.5) transports polycyclic aromatic hydrocarbons (PAHs) regionally and globally, influencing the air quality of communities around the planet. Concentrations of 130 PAHs extracted from PM2.5, collected on a Native American Tribal Reservation in the Northern Puget Sound region of the American Pacific Northwest, were used to assess the air quality impacts of regional and local PAH sources, atmospheric transport, and human health implications. Wind coming from the southeast of the sampling locations increased the overall PAH concentration of the PM2.5, while winds from the southwest decreased the PAH concentration. Concentrations of PAH subclasses increased or decreased independently at the two sampling locations with different changes in wind patterns, changing the excess lifetime cancer risk significantly. No long-range transport was measured, but emissions from local and regional PAH sources were measured. Samples collected during regional wildfires showed increased PAH concentrations. Samples collected during predicted weather inversions resulted in the highest PAH concentrations, and up to a ten-fold increase in excess lifetime cancer risk over the normal days.

There is limited understanding of adverse health effect associations with chemical constituents of fine particulate matter (PM2.5) as well as the underlying mechanisms. We outlined a workflow to assess metrics, beyond concentration, using household and personal PM2.5 filter samples collected in India as a proof of concept for future large-scale studies. Oxidative potential, chemical composition (polycyclic aromatic hydrocarbons and elements), and bioactivity (developmental exposures in zebrafish) were determined. Significant differences were observed in all metrics between personal and household PM2.5 samples. This work established methods to characterize multiple metrics of PM2.5 to ultimately support the identification of more health-relevant metrics than concentration.

Accurate long-range atmospheric transport (LRAT) modeling of polycyclic aromatic hydrocarbons (PAHs) and PAH oxidation products (PAH-OPs) in secondary organic aerosol (SOA) particles relies on the known chemical composition of the particles. Four PAHs, phenanthrene (PHE), dibenzothiophene (DBT), pyrene (PYR), and benz(a)anthracene (BaA), were studied individually to identify and quantify PAH-OPs produced and incorporated into SOA particles formed by ozonolysis of α-pinene in the presence of PAH vapor. SOA particles were characterized using real-time in situ instrumentation, and collected on quartz fiber filters for offline analysis of PAHs and PAH-OPs. PAH-OPs were measured in all PAH experiments at equal or greater concentrations than the individual PAHs they were produced from. The total mass of PAH and PAH-OPs, relative to the total SOA mass, varied for different experiments on individual parent PAHs: PHE and 6 quantified PHE-OPs (3.0%), DBT and dibenzothiophene sulfone (4.9%), PYR and 3 quantified PYR-OPs (3.1%), and BaA and benz(a)anthracene-7,12-dione (0.26%). Further exposure of PAH-SOA to ozone generally increased the concentration ratio of PAH-OPs to PAH, suggesting longer atmospheric lifetimes for PAH-OPs, relative to PAHs. These data indicate that PAH-OPs are formed during SOA particle formation and growth.

ADVERTISEMENT RETURN TO ISSUECommentNEXTBetter Science by Beating Back BiasStaci SimonichStaci SimonichMore by Staci Simonich and David L. Sedlak*David L. SedlakMore by David L. SedlakCite this: Environ. Sci. Technol. 2019, 53, 5, 2271–2272Publication Date (Web):February 21, 2019Publication History Published online21 February 2019Published inissue 5 March 2019https://pubs.acs.org/doi/10.1021/acs.est.9b00810https://doi.org/10.1021/acs.est.9b00810editorialACS PublicationsCopyright © 2019 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views1912Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (393 KB) Get e-AlertscloseSUBJECTS:Environmental science,Quality management Get e-Alerts

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.

ADVERTISEMENT RETURN TO ISSUEEditorialNEXTEditor's Choice for the Best Papers Published in ES&T Letters in 2018Bruce E. LoganBruce E. LoganMore by Bruce E. Loganhttp://orcid.org/0000-0001-7478-8070, Daniel SchlenkDaniel SchlenkMore by Daniel Schlenk, Staci L. Massey SimonichStaci L. Massey SimonichMore by Staci L. Massey Simonichhttp://orcid.org/0000-0003-2325-4217, and William A. ArnoldWilliam A. ArnoldMore by William A. Arnoldhttp://orcid.org/0000-0003-0814-5469Cite this: Environ. Sci. Technol. Lett. 2019, 6, 4, 197–198Publication Date (Web):April 9, 2019Publication History Received13 March 2019Accepted14 March 2019Published online9 April 2019Published inissue 9 April 2019https://pubs.acs.org/doi/10.1021/acs.estlett.9b00161https://doi.org/10.1021/acs.estlett.9b00161editorialACS PublicationsCopyright © 2019 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views1957Altmetric-Citations-LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (305 KB) Get e-AlertscloseSUBJECTS:Coating materials,Computer simulations,Impurities,Uranium Get e-Alerts

Polycyclic aromatic hydrocarbons (PAHs) undergo transformation reactions with atmospheric photochemical oxidants, such as hydroxyl radicals (OH•), nitrogen oxides (NOx), and ozone (O3). The most common PAH-transformation products (PAH-TPs) are nitrated, oxygenated, and hydroxylated PAHs (NPAHs, OPAHs, and OHPAHs, respectively), some of which are known to pose potential human health concerns. We sampled four theoretical approaches for predicting the location of reactive sites on PAHs (i.e., the carbon where atmospheric oxidants attack), and hence the chemoselectivity of the PAHs. All computed results are based on density functional theory (B3LYP/6-31G(d) optimized structures and energies). The four approaches are (1) Clar's prediction of aromatic resonance structures, (2) thermodynamic stability of all OHPAH adduct intermediates, (3) computed atomic charges (Natural Bond order, ChelpG, and Mulliken) at each carbon on the PAH, and (4) average local ionization energy (ALIE) at atom or bond sites. To evaluate the accuracy of these approaches, the predicted PAH-TPs were compared to published laboratory observations of major NPAH, OPAH, and OHPAH products in both gas and particle phases. We found that the Clar's resonance structures were able to predict the least stable rings on the PAHs but did not offer insights in terms of which individual carbon is most reactive. The OHPAH adduct thermodynamics and the ALIE approaches were the most accurate when compared to laboratory data, showing great potential for predicting the formation of previously unstudied PAH-TPs that are likely to form in the atmosphere.

Non-targeted analysis of environmental samples, using comprehensive two-dimensional gas chromatography coupled with time-of-flight mass spectrometry (GC x 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 (TM) script that acts as a data reduction filter to automate GC x GC/ToF-MS data analysis from LECO (R) ChromaTOF (R) 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 (R) ChromaTOF (R) 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. (C) 2018 Elsevier B.V. All rights reserved.