Polycyclic Aromatic Hydrocarbons Biomarkers Research Articles

Can environmental factors increase oxidative responses in fish exposed to polycyclic aromatic hydrocarbons (PAHs)?

Relations among polycyclic aromatic hydrocarbons (PAHs), biomarkers of oxidative stress (lipid peroxidation, glutathione, and glutathione S-transferase activity), and the possible influence of environmental factors (temperature, pH, and salinity) were assessed in situ for specimens of Ramnogaster arcuata, a native estuarine fish. PAH levels found in the muscular tissue of R. arcuata ranged from 0.7 to 293.4 ng g−1 wet weight with petrogenic and pyrolytic inputs. Lipid peroxidation in the liver showed positive correlations (P < 0.05) with total PAHs (r = 0.66), 3-ring (r = 0.66) and 4-ring PAHs (r = 0.52) and glutathione in muscle (r = 0.58). Significant positive correlations (P < 0.05) were also evidenced between muscular glutathione with total (r = 0.62) and 3-ring PAHs (r = 0.75). Hepatic glutathione S-transferase negatively correlated with 4-ring PAHs (r = −0.58). These correlations suggest that lipid peroxidation and muscular glutathione could be good biomarkers for complex mixtures of PAHs, and hepatic glutathione S-transferase could be a suitable biomarker for 4-ring PAHs. Furthermore, significant correlations (P < 0.05) of environmental factors with PAH levels and biomarkers were observed, especially pH with 3-ring PAHs (r = −0.65), lipid peroxidation (r = −0.6), glutathione in the liver (r = −0.73) and muscle (r = −0.75); and temperature with 2-ring PAHs (r = −0.75) and glutathione in muscle (r = 0.51). The data suggest an influence of physicochemical parameters which could be driving a shift in PAH toxicity in R. arcuata. These results are essential for an integrated understanding of ecotoxicology and could help to predict environmental effects in present and future scenarios of ocean warming and acidification.

Methods to assess dermal exposures in occupational settings: a scoping review.

The dermal exposure route is expected to become increasingly significant relative to total worker exposure as inhalational exposure limits continue to decrease. However, standardization of occupational exposure assessment methods and scientific consensus are needed. This is the first scoping review mapping the literature across all dermal exposure assessment methods and their targeted substances/chemicals in occupational settings. Eligibility criteria broadly included studies reporting any noninvasive dermal exposure assessment method in an occupational setting. The literature search (Web of Science and MEDLINE) was restricted to peer-reviewed, primary literature published in the last 20 years (2002-2022). Titles/abstracts were dual independently screened. Data charting was performed by a single reviewer using standard template. All stages were pilot tested. The JBI (formerly, the Joanna Briggs Institute) scoping review methods and PRISMA-ScR checklist (Preferred Reporting Items for Systematic Reviews and Meta-Analyses extension for Scoping Reviews) were used. In total, 493 articles were data charted and categorized by 4 study types: methods development (22%), exposure assessment (51%), health outcomes (21%), and controls assessment (6%). Fourteen types of dermal exposure assessment methods were charted with biomarkers (51%), dosimeters (21%), and qualitative assessments such as questionnaires or surveys (17%) most common. Seventeen different chemicals/substances were charted; pesticides (28%) and polycyclic aromatic hydrocarbons (PAHs) (22%) associated with crude oil products and combustion were most common. Mapping between substances and exposure assessment method categories, pesticide dosimeters (11%), and PAH biomarker studies (14%) were most reported. Literature gaps were identified for cleaning agents, hair dyes, glycol ether, N,N-dimethylformamide/N-methyl-2-pyrrolidone, dioxins, and bisphenol A. To foster scientific consensus, standardization across study reporting is needed for describing: (i) exposure assessment methods used, (ii) worker tasking/conditions, (iii) targeted substances and substance state, and (iv) targeted exposure routes. Overall, this review categorizes, maps, and defines the scope of literature for occupational dermal exposure assessment methods.

Polycyclic Aromatic Hydrocarbons and Pancreatic Cancer: An Analysis of the Blood Biomarker, r-1,t-2,3,c-4-Tetrahydroxy-1,2,3,4-tetrahydrophenanthrene and Selected Metabolism Gene SNPs.

Exposure to polycyclic aromatic hydrocarbons (PAHs), byproducts of incomplete combustion, and their effects on the development of cancer are still being evaluated. Recent studies have analyzed the relationship between PAHs and tobacco or dietary intake in the form of processed foods and smoked/well-done meats. This study aims to assess the association of a blood biomarker and metabolite of PAHs, r-1,t-2,3,c-4-tetrahydroxy-1,2,3,4-tetrahydrophenanthrene (PheT), dietary intake, selected metabolism SNPs, and pancreatic cancer. Demographics, food-frequency data, SNPs, treatment history, and levels of PheT in plasma were determined from 400 participants (202 cases and 198 controls) and evaluated based on pancreatic adenocarcinoma diagnosis. Demographic and dietary variables were selected based on previously published literature indicating association with pancreatic cancer. A multiple regression model combined the significant demographic and food items with SNPs. Final multivariate logistic regression significant factors (p-value < 0.05) associated with pancreatic cancer included: Type 2 Diabetes [OR = 6.26 (95% CI = 2.83, 14.46)], PheT [1.03 (1.02, 1.05)], very well-done red meat [0.90 (0.83, 0.96)], fruit/vegetable servings [1.35 (1.06, 1.73)], recessive (rs12203582) [4.11 (1.77, 9.91)], recessive (rs56679) [0.2 (0.06, 0.85)], overdominant (rs3784605) [3.14 (1.69, 6.01)], and overdominant (rs721430) [0.39 (0.19, 0.76)]. Of note, by design, the level of smoking did not differ between our cases and controls. This study does not provide strong evidence that PheT is a biomarker of pancreatic cancer susceptibility independent of dietary intake and select metabolism SNPs among a nonsmoking population.

Baseline data and associations between urinary biomarkers of polycyclic aromatic hydrocarbons, blood pressure, hemogram, and lifestyle among wildland firefighters.

Available literature has found an association between firefighting and pathologic pathways leading to cardiorespiratory diseases, which have been linked with exposure to polycyclic aromatic hydrocarbons (PAHs). PAHs are highlighted as priority pollutants by the European Human Biomonitoring Initiative in occupational and non-occupational contexts. This cross-sectional study is the first to simultaneously characterize six creatinine-adjusted PAHs metabolites (OHPAHs) in urine, blood pressure, cardiac frequency, and hemogram parameters among wildland firefighters without occupational exposure to fire emissions (> 7 days), while exploring several variables retrieved via questionnaires. Overall, baseline levels for total OHPAHs levels were 2 to 23-times superior to the general population, whereas individual metabolites remained below the general population median range (except for 1-hydroxynaphthalene+1-hydroxyacenaphtene). Exposure to gaseous pollutants and/or particulate matter during work-shift was associated with a 3.5-fold increase in total OHPAHs levels. Firefighters who smoke presented 3-times higher total concentration of OHPAHs than non-smokers (p < 0.001); non-smoker females presented 2-fold lower total OHPAHs (p = 0.049) than males. 1-hydroxypyrene was below the recommended occupational biological exposure value (2.5 μg/L), and the metabolite of carcinogenic PAH (benzo(a)pyrene) was not detected. Blood pressure was above 120/80 mmHg in 71% of subjects. Firefighters from the permanent intervention team presented significantly increased systolic pressure than those who performed other functions (p = 0.034). Tobacco consumption was significantly associated with higher basophils (p = 0.01-0.02) and hematocrit (p = 0.03). No association between OHPAHs and blood pressure was found. OHPAHs concentrations were positively correlated with monocyte, basophils, large immune cells, atypical lymphocytes, and mean corpuscular volume, which were stronger among smokers. Nevertheless, inverse associations were observed between fluorene and pyrene metabolites with neutrophils and eosinophils, respectively, in non-smokers. Hemogram was negatively affected by overworking and lower physical activity. This study suggests possible associations between urinary PAHs metabolites and health parameters in firefighters, that should be further assessed in larger groups.

Estimating personal exposures to household air pollution and plastic garbage burning among adolescent girls in Jalapa, Guatemala

Waste collection services are uncommon in rural areas of low-resource countries, causing waste accumulation and subsequent dumping and burning of garbage. Air pollution from household garbage burning, including plastics, has been observed in Jalapa, Guatemala in addition to household air pollution (HAP) from cooking. Adolescent girls often help with these cooking and household tasks, but little is known about their exposures. We characterized 24-h exposures to HAP and household garbage burning in adolescent girls by measuring fine particulate matter (PM2.5), black carbon (BC), urinary biomarkers of polycyclic aromatic hydrocarbons (PAHs), bisphenol A (BPA), and phthalates. We recruited 60 girls between 13 and 17 years of age who helped with cooking activities and lived with participants of the Household Air Pollution Intervention Network (HAPIN) trial. We recruited n = 30 girls each from the control (wood-burning stove) and intervention (liquefied petroleum gas stove) arms. We also measured real-time kitchen concentrations of BC in 20 homes (33%). PM2.5 and BC were measured in n = 21 control and n = 20 intervention participants. Median concentrations of personal PM2.5 and BC and kitchen BC were lower (p < 0.05) in the intervention arm by 87%, 80%, and 85%, respectively. PAH metabolite concentrations were lower (p < 0.001) for all nine metabolites in intervention (n = 26) compared to control participants (n = 29). Urinary BPA concentrations were 66% higher in participants who reported using cosmetics (p = 0.02), and phthalate concentrations were 63% higher in participants who had reported using hair products during the sample period (p = 0.05). Our results suggest that gas stoves can reduce HAP exposures among adolescents who are not primary cooks at home. Biomarkers of plastic exposure were not associated with intervention status, but some were elevated compared to age- and sex-matched participants of the National Health and Nutrition Examination Survey (NHANES).

The effect of polycyclic aromatic hydrocarbon biomarkers on cardiovascular diseases.

Polycyclic aromatic hydrocarbon (PAHs) are part of particulate matter (PM), which is produced from incomplete combustion of organic matter. Biomarkers mean biological indicators, molecules that indicate a normal or abnormal process in the body and may be a signof a condition or disease. Studies show that PAHs increase the risk of cardiovascular diseases through processes such as oxidative stress, inflammation andatherosclerosis. The present study focused on the evaluation of health effects PAHs biomarkers on cardiovascular diseases (CVD). In this narrative study, data werecollected from databases such as Scopus, PubMed, Web of science and Google Scholar in the period 1975-2023. After screening, duplicate and irrelevant articles were removed. Finally, 68 articles related to the effect of PAHs on CVD were included in the study. In addition to the articles found through the search in databases, another 18 articles from the references of the selected articles were included. According to the finding in during the biotransformation of PAH, a number of metabolites are made, such as phenols, diols, quinones, and epoxides. Phenolic isomers have the highest percentage and biomarkers used for their detection include 2-OHNAP used totrace naphthalene from heating processed food, 3-OHPHEN used to trace phenanthrene fromdiesel, 2-OHFLU used to trace fluorene and 1-OHPYR used to trace pyrene from cigarette and hookah smoke. According to the result, increasing blood pressure and heart rate and causing atherosclerosis are the main complications due to exposure to PAH metabolite on cardiovascular system. The most important agents that causes this affects including increased homocysteine, cholesterol, high-density lipoprotein (HDL), low-density lipoprotein (LDL), serum biomarkers of C-reactive protein, and triglycerides. Result this study showed that cardiovascular diseases riskis increased by exposure to PAH biomarkers from smoking, car emissions, occupational exposure, and incinerators. Therefore, strict controls should be implemented for sources of PAH production and exposure.

Application of Ion Mobility Spectrometry-Mass Spectrometry for Compositional Characterization and Fingerprinting of a Library of Diverse Crude Oil Samples.

Exposure characterization of crude oils, especially in time-sensitive circumstances such as spills and disasters, is a well-known analytical chemistry challenge. Gas chromatography-mass spectrometry is commonly used for "fingerprinting" and origin tracing in oil spills; however, this method is both time-consuming and lacks the resolving power to separate co-eluting compounds. Recent advances in methodologies to analyze petroleum substances using high-resolution analytical techniques have demonstrated both improved resolving power and higher throughput. One such method, ion mobility spectrometry-mass spectrometry (IMS-MS), is especially promising because it is both rapid and high-throughput, with the ability to discern among highly homologous hydrocarbon molecules. Previous applications of IMS-MS to crude oil analyses included a limited number of samples and did not provide detailed characterization of chemical constituents. We analyzed a diverse library of 195 crude oil samples using IMS-MS and applied a computational workflow to assign molecular formulas to individual features. The oils were from 12 groups based on geographical and geological origins: non-US (1 group), US onshore (3), and US Gulf of Mexico offshore (8). We hypothesized that information acquired through IMS-MS data would provide a more confident grouping and yield additional fingerprint information. Chemical composition data from IMS-MS was used for unsupervised hierarchical clustering, as well as machine learning-based supervised analysis to predict geographic and source rock categories for each sample; the latter also yielded several novel prospective biomarkers for fingerprinting of crude oils. We found that IMS-MS data have complementary advantages for fingerprinting and characterization of diverse crude oils and that proposed polycyclic aromatic hydrocarbon biomarkers can be used for rapid exposure characterization. Environ Toxicol Chem 2023;42:2336-2349. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

External Quality Assurance Schemes (EQUASs) and Inter-laboratory Comparison Investigations (ICIs) for human biomonitoring of polycyclic aromatic hydrocarbon (PAH) biomarkers in urine as part of the quality assurance programme under HBM4EU

Polycyclic aromatic hydrocarbons (PAHs) were included as priority substances for human biomonitoring (HBM) in the European Human Biomonitoring Initiative (HBM4EU), which intended to harmonise and advance HBM across Europe. For this project, a specific Quality Assurance and Quality Control (QA/QC) programme applying Inter-laboratory Comparison Investigations (ICIs) and External Quality Assurance Schemes (EQUASs) was developed to ensure the comparability and accuracy of participating analytical laboratories. This paper presents the results of four ICI/EQUAS rounds for the determination of 13 PAH metabolites in urine, i.e. 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 2-, 3- and 9-hydroxyfluorene, 1-, 2-, 3-, 4- and 9-hydroxyphenanthrene, 1-hydroxypyrene and 3-hydroxybenzo(a)pyrene. However, 4 PAH metabolites could not be evaluated as the analytical capacity of participating laboratories was too low. Across all rounds and biomarkers, 86% of the participants achieved satisfactory results, although low limits of quantification were required to quantify the urinary metabolites at exposure levels of the general population. Using high-performance liquid or gas chromatography coupled with mass spectrometry (HPLC-MS; GC-MS) and isotope dilution for calibration as well as performing an enzymatic deconjugation step proved to be favourable for the accurate determination of PAHs in urine. Finally, the HBM4EU QA/QC programme identified an international network of laboratories providing comparable results in the analysis of urinary PAH biomarkers, although covering all parameters initially selected was still too challenging.

Association between urinary biomarkers of polycyclic aromatic hydrocarbons and severe abdominal aortic calcification in adults: data from the National Health and Examination Nutrition Survey

ObjectiveRecent studies have found that polycyclic aromatic hydrocarbons (PAHs) exposure may increase the risk of cardiovascular disease. The present study aimed to explore the association between PAHs exposure and severe abdominal aortic calcification (AAC) in adults.MethodsData were collected from the 2013–2014 National Health and Nutrition Examination Survey. PAHs exposure was analyzed from urinary mono hydroxylated metabolites of PAHs. Logistic regression models and subgroup analysis were performed to explore the association of PAHs exposure with severe AAC prevalence.ResultsA total of 1,005 eligible individuals were recruited into the study. After adjusting for confounding factors, those with the highest quartiles of 1-hydroxynaphthalene (1-NAP: OR 2.19, 95% CI 1.03–4.68, Pfor trend < 0.001), 2-hydroxynaphthalene (2-NAP: OR 2.22, 95% CI 1.04–4.64, Pfor trend < 0.001) and 1-hydroxypyrene (1-PYR: OR 2.15, 95% CI 1.06–4.33, Pfor trend < 0.001) were associated with an increased prevalence of severe AAC in the adults compared to those who in the lowest quartile.ConclusionThis study found that urinary 1-NAP, 2-NAP and 1-PYR were positively associated with severe AAC prevalence in adults.

Association of human cohorts exposed to blood and urinary biomarkers of PAHs with adult asthma in a South Asian metropolitan city.

Semi-volatile organic compounds (SVOCs) are a major global problem that causes the greatest impact on urban settings and have been linked to bronchial asthma in both children and adults in Pakistan. The association between exposure of polycyclic aromatic hydrocarbons (PAHs) and asthma in the adult population is less clear. The current study aimed to assess the clinico-chemical parameters and blood levels of naphthalene phenanthrene, pyrene, and 1,2-benzanthracene and urinary levels of 1-OH pyrene and 1-OH phenanthrene as well as asthma-related biomarkers immunoglobulin E (IgE), resistin, and superoxide dismutase (SOD) of oxidative stress and other hematologic parameters in adults and their relationship with bronchial asthma. The GC/MS analysis showed higher mean concentrations of blood PAHs in asthma respondents (4.48 ± 1.34, 3.46 ± 1.04, 0.10 ± 0.03, and 0.29 ± 0.09) (ng/mL) as compared to controls (3.07 ± 0.92, 1.71 ± 0.51, 0.06 ± 0.02, and 0.11 ± 0.03) (ng/mL), with p = .006, p = .001, p = .050, and p = .001. Similarly, urinary levels of 1-OHpyr and 1-OHphe were significantly increased in adults with bronchial asthma (0.54 ± 0.16; 0.13 ± 0.04) (μmol/mol-Cr) than in controls (0.30 ± 0.09; 0.05 ± 0.02) (μmol/mol-Cr), with p = .002 and p = .0001, respectively, with a significant positive correlation to asthma severity. The asthma-related biomarkers IgE, resistin, and SOD were significantly higher (p 0.0001, 0.0001, and 0.0001) in people with asthma than in control persons. The findings showed that higher blood and urine PAHs levels were linked to higher asthma risk in adults and significant interaction with participants who smoked, had allergies, had a family history of asthma, and were exposed to dust. The current study's findings will be useful to local regulatory agencies in Lahore in terms of managing exposure and advocating efforts to minimize PAH pollution and manage health.

Sedimentary PAH and oxidative stress biomarkers responses on Namalycastis abiuma (Polychaeta: Nereididae) from an urbanized Amazon estuary

Contamination by polycyclic aromatic hydrocarbons (PAH) in sediments and oxidative stress biomarkers responses (glutathione-S-transferase activity—GST and lipoperoxidation—LPO) on the polychaetes Namalycastis abiuma were screened along the urbanized margin of the Guajará Estuary, Brazilian Amazon coast, during dry and rainy seasons. Total 16 priority PAH concentrations ranged from 17 to 386 ng g−1 dry sediment, with higher values during the dry season. High molecular weight PAHs predominated during dry season and were probably originated from fossil fuel burning. Increased naphthalene and anthracene concentrations were noted when the maximum river flow was recorded and suggest diffuse sources from drainage of contaminated surfaces. Ecotoxicological PAH risks were low according to international sediment quality indices. Nevertheless, PAH toxicity equivalency was around 10-fold higher nearer the oil terminal than alongside the estuary. Highest GST activities at the oil terminal and industrial sites coincided with the rainy season, and combined with hydrochemical and sedimentary conditions thought to promote PAH bioavailability and a prolonged toxicant exposure. LPO approached similar levels in both seasons, suggesting that enzymatic activities were sufficient to uphold the prooxidants exposure. This result indicates that the overall estuarine condition exerts subtle oxidative stress on a keystone species and matches the low PAH ecotoxicological risks. Depositional margins within the mangrove areas and port operation are susceptible to an enhanced PAH accumulation and need special surveillance.

Abstract B005: Polycyclic aromatic hydrocarbons and pancreatic cancer: An analysis of blood biomarker PheT as an exposure identifier

Abstract Exposure to polycyclic aromatic hydrocarbons (PAHs), a byproduct of incomplete combustion, and its effects on the development of cancer needs further evaluation. Recent studies have analyzed the relationship between PAHs and tobacco or dietary intake in the form of processed foods and smoked/well-done meats. This study aims to assess the association of a blood biomarker and metabolite of PAHs, r-1-,t-2,3,c-4-tetrahydroxy-1,2,3,4-tetrahydrophenanthrene (PheT), selected metabolism SNPs, and pancreatic cancer. Demographics, food-frequency data, SNPs, treatment history and levels of PheT in plasma were collected from 400 participants (202 cases and 198 control) and evaluated based on pancreatic adenocarcinoma diagnosis. A two-stage analysis was completed to identify 1) SNPs that were significantly associated with pancreatic cancer and 2) Dietary intake and PheT variables significantly associated with pancreatic cancer. A univariate analysis for variables with OR≠1 and p-value &amp;lt; 0.05 suggests significant relationship with pancreatic cancer and were carried forward to a multiple regression model for either food items or SNPs. Backward stepwise selection was used to eliminate non-significant variables. A collection of 5 SNPs were observed to form several of the most significant (adjusted p-value &amp;lt;0.05) interaction pairs across different SNP models. These were rs566979 (gene: CAT), rs28540420 (gene: PTGER4), rs12029406 (gene: none), rs730368 (gene: PTGER4), and rs3181077 (gene: CCR1). A final multiple regression model combined the significant food items and SNPs. Final significant factors associated with pancreatic cancer after backward selection included: Type 2 Diabetes [7.66 (3.46, 17.76)], corrected percent recovered version of the PAH (cPheT) [1.03 (1.02, 1.05)], very well done red meat [0.90 (0.84, 0.96)], recessive(rs12203582) [3.58 (1.50, 8.83)], recessive(rs56679) [0.25 (0.06, 0.80)], overdominant(rs3784605) [3.42 (1.81, 6.66)], overdominant(rs721430) [0.42 (0.21, 0.83)]. Of note by design, the level of smoking did not differ between our cases and controls. This study provides evidence that a metabolite PheT could be a biomarker of pancreatic cancer independent of dietary intake, smoking, and select metabolism SNPs. Citation Format: Sierra Nguyen, Heather Carlson, Andrea Yoder, William R. Bamlet, Ann L. Oberg, Gloria M. Peterson, Steven Hecht, Rick Jansen. Polycyclic aromatic hydrocarbons and pancreatic cancer: An analysis of blood biomarker PheT as an exposure identifier [abstract]. In: Proceedings of the AACR Special Conference on Pancreatic Cancer; 2022 Sep 13-16; Boston, MA. Philadelphia (PA): AACR; Cancer Res 2022;82(22 Suppl):Abstract nr B005.

Associations between urinary biomarkers of oxidative stress and biomarkers of tobacco smoke exposure in smokers

Oxidative stress can contribute to the development of diseases, and may originate from exposures to toxicants commonly found in air pollution and cigarette smoke such as polycyclic aromatic hydrocarbons (PAHs) and volatile organic compounds (VOCs). Yet, associations between these exposures and oxidative stress biomarkers are poorly characterized. We report here novel associations between 14 exposure biomarkers of PAHs and VOCs, and two oxidative stress biomarkers; 8-oxo-7,8-dihydro-2′-deoxyguanosine (8-oxodG) and 8-isoprostaglandin F2α (8-isoprostane) in urine obtained from smokers participating in an ongoing clinical study (ESTxENDS, NCT03589989). We also assessed associations between six biomarkers of tobacco smoke exposure (metabolites of nicotine and tobacco-specific nitrosamines (TSNAs)) and both oxidative stress biomarkers. We then quantified the relative importance of each family of the 20 exposure biomarkers on oxidative stress. Participating smokers (153 men and 117 women, median age 44 years) had on average smoked 25 [2–62] years and smoked about 17 [5–40] cigarettes per day at the time of the study. Multiple linear regression results showed an association between 8-oxodG concentrations and the following metabolites in decreasing relative importance: PAHs (beta coefficient β = 0.105, p-value <0.001, partial R2 = 0.15) > VOCs (β = 0.028, p < 0.001, partial R2 = 0.09) > nicotine (β = 0.226, p < 0.001, partial R2 = 0.08); and between 8-isoprostane concentrations and metabolites of PAHs (β = 0.117, p < 0.001, partial R2 = 0.14) > VOCs (β = 0.040, p < 0.001, partial R2 = 0.14) > TSNAs (β = 0.202, p = 0.003, partial R2 = 0.09) > nicotine (β = 0.266, p < 0.001, partial R2 = 0.08). Behavioral factors known to contribute to oxidative stress, including sleep quality, physical activity, and alcohol consumption, did not play a significant role. Exposures to PAHs and VOCs among smokers were significantly associated with oxidative stress.

Assessment of the exposure to polycyclic aromatic hydrocarbons in users of various tobacco/nicotine products by suitable urinary biomarkers.

Polycyclic aromatic hydrocarbons (PAHs) occur naturally (bitumen and oils) and are formed during all incomplete combustions of organic materials. PAH exposure sources are manifold and include specific workplaces, ambient air, various foodstuffs, tobacco smoke and some medications. At least four members of this class of chemicals have been classified as proven or probable human carcinogens. Assessment of the exposure to PAHs with suitable methods is of importance, particularly in users of new-generation tobacco/nicotine products, which are intended to replace combustible cigarettes (CCs), a major source of non-occupational exposure to PAHs. In a clinical study comprising a period of 74h under confinement, we investigated the exposure to naphthalene (Nap), fluorene (Flu), phenanthrene (Phe), pyrene (Pyr) and benzo[a]pyrene (BaP) by measuring urinary monohydroxy-PAH (OH-PAH) derived from these parent compounds in habitual users of CCs, electronic cigarettes (ECs), heated tobacco products (HTPs), oral tobacco (OT), and nicotine replacement therapy products (NRTs). Non-users (NU) of any tobacco/nicotine products served as (negative) control group. Smokers exhibited the highest levels for all PAH biomarkers measured, almost all of which were significantly different from the NU and user groups of all other products investigated. CC smokers were the only group which showed a significant relationship between almost all PAH biomarkers and dose markers such as daily consumption, urinary nicotine equivalents (Nequ) and plasma cotinine (CotP). The ratios in urinary OH-PAH between CC and all other groups were dependent on the biomarker and range from < 2 to > 10. These ratios could at least partly be explained by the enzymes involved, their region-selectivity and inducibility by smoking. In conclusion, cigarette smokers (CC) were the only group, which showed product use dependent exposure to PAHs, whereas users of EC, HTP, NRT and OT were not distinguishable from NU of any tobacco/nicotine products.

Urinary Biomarkers of Polycyclic Aromatic Hydrocarbons and Timing of Pubertal Development: The California PAH Study.

Polycyclic aromatic hydrocarbons (PAHs) are endocrine-disrupting chemicals. Few studies have evaluated the association between pubertal development in girls and PAH exposures quantified by urinary biomarkers. We examined associations of urinary PAH metabolites with pubertal development in 358 girls 6-16 years of age from the San Francisco Bay Area enrolled in a prospective cohort from 2011 to 2013 and followed until 2020. Using baseline data, we assessed associations of urinary PAH metabolites with pubertal development stage. In prospective analyses limited to girls who at baseline had not yet started breast (N = 176) or pubic hair (N = 179) development or menstruation (N = 267), we used multivariable Cox proportional hazards regression to assess associations of urinary PAH metabolites with the onset of breast and pubic hair development, menstruation, and pubertal tempo (interval between the onset of breast development and menstruation). We detected PAH metabolites in >98% of girls. In cross-sectional analyses using baseline data, PAH metabolites were not associated with the pubertal development stage. In prospective analyses, higher concentrations (≥ median) of some PAH metabolites were associated with two-fold higher odds of earlier breast development (2-hydroxy naphthalene, 1-hydroxy phenanthrene, summed hydroxy phenanthrenes) or pubic hair development (1-hydroxy naphthalene) among girls overweight at baseline (body mass index-for-age percentile ≥85) compared with nonoverweight girls with lower metabolites concentrations. PAH metabolites were not associated with age at menarche or pubertal tempo. PAH exposures were widespread in our sample. Our results support the hypothesis that, in overweight girls, PAHs impact the timing of pubertal development, an important risk factor for breast cancer.

Spatial and temporal trends of polycyclic aromatic hydrocarbons in sediment cores of Brunei Bay, East Malaysia

The spatial and temporal distribution of polycyclic aromatic hydrocarbons (PAHs) in three sediment cores from Brunei Bay, Southern South China Sea was investigated. The total concentrations of 16 priority PAHs (∑PAH16) and their alkyl-substituted derivatives ranged from 10.4 to 376 ng g−1 and 30.7 to 2263 ng g−1, respectively. PAH biomarker diagnostic ratios and principal component analysis (PCA) combined with absolute principal component score (APCS) and multiple linear regression (MLR) were performed to apportion the source contribution. The results revealed mixed inputs of fuel combustion residues and uncombusted petrogenic products. The downcore PAH profile revealed that the highest peaks could be related to past human activities using biofuel and coal during the industrialization/agriculture revolution period. The 1,7/(2,6+1,7)-dimethylphenanthrene ratio also highlighted wood combustion during forest fire outbreaks, which appeared to coincide with the past climate events.

Internal exposure of Flemish teenagers to environmental pollutants: Results of the Flemish Environment and Health Study 2016-2020 (FLEHS IV).

The Flemish Environment and Health Study (FLEHS) collects information on internal exposure to a broad range of environmental chemicals in the general population in Flanders, the Northern region of Belgium. The aim is to establish biomonitoring exposure distributions for the general population in support of public health and environmental policy, environmental risk assessment and risk management decisions. In 2017-2018, urine and blood samples were collected from 428 teenagers by a stratified clustered two stage randomized design. Samples were analyzed for a broad range of biomarkers related to exposure to chlorinated and newer pesticides, brominated and organophosphate flame retardants (BFR/OPFR), polychlorinated biphenyls (PCBs), bisphenols, phthalates and alternative plasticizers, per-and polyfluoroalkyl substances (PFAS), polycyclic aromatic hydrocarbons (PAHs), benzene, metals and trace elements. The geometric mean levels and percentiles of the distribution were estimated for each biomarker, for the whole study population and following stratification for sex, the household educational attainment and the residence area's urbanicity. Geometric means of biomarkers of lead, dichlorodiphenyltrichloroethane (DDT), PCBs, PAHs, regulated phthalates and bisphenol A (BPA) were lower than in the previous FLEHS cycles. Most biomarker levels were below health-based guidance values (HB-GVs). However, HB-GVs of urinary arsenic, blood lead, blood cadmium, sum of serum perfluorooctane sulfonate (PFOS) and perfluoro-1-hexanesulfonate (PFHxS) and the urinary pyrethroid metabolite (3-PBA) were exceeded in respectively 25%, 12%, 39.5%, 10% and 22% of the teenagers. These results suggest that the levels of exposure in the Flemish population to some environmental chemicals might be of concern. At the same time, we noticed that biomarkers for BPA substitutes, metabolites of OPFRs, an expanded list of PFAS, glyphosate and its metabolite could be measured in substantial proportions of participants. Interpretation of these levels in a health-risk context remains uncertain as HB-GVs are lacking. Household educational attainment and residential urbanicity were significant exposure determinants for many biomarkers and could influence specific biomarker levels up to 70% as shown by multiple regression analysis. The research consortium also took care of the broader external communication of results with participants, policy makers, professional groups and civil society organizations. Our study demonstrated that teenagers are exposed to a wide range of chemicals, it demonstrates the success of public policies to reduce exposure but also points to concern and further priorities and needs for follow up.

Exposure assessment of polycyclic aromatic hydrocarbons in refined coal tar sealant applications.

Refined coal tar sealant (RCTS) emulsions are used to seal the surface of asphalt pavement. Nine of the 22 polycyclic aromatic hydrocarbons (PAHs) evaluated in this study are classified as known, probable, or possible human carcinogens. Exposure assessment research for RCTS workers has not been published previously. The overall objective of this study was to develop a representative occupational exposure assessment of PAH exposure for RCTS workers based on worksite surveys. The specific aims were to: 1) quantify full-shift airborne occupational exposures to PAHs among RCTS workers; 2) quantify workers' dermal exposures to PAHs; 3) quantify biomarkers of PAH exposure in workers' urine; 4) identify specific job titles associated with RCTS exposure; and 5) apply these results to a biological exposure index to assess risk of potential genotoxicity from occupational exposures. A total of twenty-one RCTS workers were recruited from three companies. Personal and area air samples were collected using a modification of NIOSH Method 5515. Dermal exposure was assessed by hand and neck wipes before and after shifts. Twenty-two PAHs were quantified via gas chromatography-mass spectrometry selected ion monitoring. Internal dose was estimated by quantifying select PAH metabolites in pre- and post-shift urine samples using on-line solid phase extraction-high performance liquid chromatography-tandem mass spectrometry. PAH levels in the worker breathing zones were highest for naphthalene, acenaphthene, and phenanthrene, with geometric means of 52.1, 11.4, and 9.8μg/m3, respectively. Hand wipe levels of phenanthrene, fluoranthene and pyrene were the highest among the 22 PAHs with geometric means of 7.9, 7.7, and 5.5μg/cm2, respectively. Urinary PAH biomarkers for naphthalene, fluorene, phenanthrene, and pyrene were detected in all workers and were higher for post-shift samples than those collected pre-shift. Urinary concentrations of the metabolite 1-hydroxypyrene were greater than the American Conference of Governmental Industrial Hygienists (ACGIH) Biological Exposure Index (BEI) for this metabolite in 89 percent of post-shift samples collected on the final day of the work week or field survey. Statistically significances were found between concentrations of fluorene, naphthalene, and phenanthrene in the breathing zone of workers and their corresponding urinary PAH biomarkers. Workers were placed in two work place exposure groups: applicators and non-applicators. Applicators had higher total PAH concentrations in personal breathing zone (PBZ) air samples than non-applicators and were more likely to have post-shift hand wipe concentrations significantly higher than pre-shift concentrations. Concentrations of post-shift urinary biomarkers were higher, albeit not significantly, for applicators than non-applicators. The exposure results from RCTS worker samples cannot be explained by proximal factors such as nearby restaurants or construction. Air and skin concentration levels were substantially higher for RCTS workers than previously published levels among asphalt workers for all PAHs. PAH profiles on skin wipes were more consistent with RCTS sealant product than air samples. Last day post-shift urinary concentrations of 1-hydroxypyrene greatly exceeded the ACGIH BEI benchmark of 2.5μg/L in 25 of 26 samples, which suggests occupational exposure and risk of genotoxicity. When pyrene and benzo[a]pyrene were both detected, concentration ratios from personal exposure samples were used to calculate the adjusted BEI. Concentrations of 1-hydroxypyrene exceeded the adjusted BEIs for air, hand wipes, and neck wipes in most cases. These results indicate the need to increase safety controls and exposure mitigation for RCTS workers.

Exposure to polycyclic aromatic hydrocarbons and nicotine, and associations with sperm DNA fragmentation.

BackgroundTobacco smoking has been reported to cause DNA fragmentation and has been suggested to cause mutations in spermatozoa. These effects have been ascribed to the action of polycyclic aromatic hydrocarbons (PAH) present in the smoke. Simultaneously, DNA fragmentation has been associated with mutagenesis.ObjectiveThe aim of this study was to investigate whether levels of urinary biomarkers of PAH and nicotine exposure were associated with sperm DNA fragmentation.MethodsIn the urine of 381 men recruited from two cohorts of young men (17–21 years old) from the general Swedish population, the PAH metabolites 1‐hydroxypyrene and 2‐hydroxyphenanthrene, as well as the nicotine metabolite cotinine, were measured. The sperm DNA fragmentation index (DFI) was analysed using the sperm chromatin structure assay. Associations between the DFI, and PAH metabolite levels as continuous variables as well as in quartiles, were studied by general linear models adjusted for abstinence time. A similar analysis was carried out for cotinine levels, according to which the men were categorised as “non‐smoking” (n = 216) and “smoking” (n = 165).ResultsNo association was found between levels of any of the three biomarkers and DFI, either as a continuous variable (p = 0.87–0.99), or when comparing the lowest and the highest quartiles (p = 0.11–0.61). The same was true for comparison of men categorised as non‐smoking or smoking (DFI 11.1% vs. 11.8%, p = 0.31).DiscussionWe found no evidence of PAH or nicotine exposure to be associated with DFI, which does not exclude that these exposures may have other effects on sperm DNA.ConclusionIn these young men, levels of biomarkers of nicotine and PAH exposure were not associated with DFI.

Unearth the Luminescence Potential of Metal-Organic Frameworks: Adopting a Feasible Strategy to Fabricate One Ratiometric Fluorescence Sensor for Monitoring Both 1-Hydroxypyrene and Cu2.

In this work, a novel luminescent hybrid material with double emission centers (Eu(TTA)0.2@9-1-UMOF) is successfully prepared, adopting a feasible design strategy. Initially, the second ligand 1,2,4-benzenetricarboxylic acid (H3BTC) is encapsulated based on a solid solution approach, which effectively improves the ligand-based emission intensity of the original LMOF and provides functional sites for introducing the second luminescent center; then, Eu3+ as the red emission source is loaded into the frameworks through a coordination post-synthetic modification method; finally, to balance the emission intensity at 613 nm (Eu3+) and 465 nm (1,4-naphthalenedicarboxylic acid (H2NDC)), 2-thenoyltrifluoroacetone (TTA) as a powerful antenna is introduced. Given the outstanding luminescence properties and structural stability of Eu(TTA)0.2@9-1-UMOF, it is further developed as a ratiometric sensor for detecting 1-hydroxypyrene (1-HP, the biomarker of polycyclic aromatic hydrocarbons (PAHs)) and Cu2+, which promotes the pre-diagnosis of human health. Notably, Eu(TTA)0.2@9-1-UMOF exhibits excellent selective recognition ability for both 1-HP and Cu2+ with high sensitivity (LOD = 4.06 × 10-6 mg/mL, 3.85 × 10-7 mol/L, respectively) and fast response speed. In addition, Eu(TTA)0.2@9-1-UMOF as a fluorescent probe shows great potential for the determination of 1-HP and Cu2+ in actual samples. More importantly, this work widens the road for the development of dual/multiple LMOF-based sensors for analytical applications.