[Benchmark dose estimation of polycyclic aromatic hydrocarbons exposure base on Bayesian kernel machine regression].

Objective: To explore benchmark dose (BMD) estimations of polycyclic aromatic hydrocarbons (PAHs) based on Bayesian kernel machine regression (BKMR) . Methods: A total of 155 adult residents of a coking plant in Shanxi Province who were surveyed in summer (June to August) from 2014 to 2019 were selected as the research objects. Fasting elbow vein blood of the subjects was collected in the morning for automatic analysis and detection of blood routine. Morning urine samples were collected for automatic analysis and detection of urine routine and urine creatinine detection. BKMR model combined with BMD method was used to calculate the acceptable doses of PAHs exposure on red blood cell damage in non-occupational population. Results: The concentration of hydroxylpolycyclic aromatic hydrocarbons (OH-PAHs) in the red blood cells abnormal group (n=117) was significantly higher than that in the normal group (n=38) (P<0.01). In the combined effect of OH-PAHs, 2-hydrol-naphthalene contributed the most, and the posterior inclusion probability (PIP) value was 0.9354. When OH-PAHs ≥P(55) concentration, the joint effect on the risk of red blood cell abnormalities increased as the concentration of the OH-PAHs mixture increased. When OH-PAHs were at P(65) and P(75) concentrations, respectively, the risk of red blood cell abnormalities in adults were 3.09 and 4.98 times that of OH-PAHs at P(50) concentrations, respectively. Compared with high concentration, low concentration of OH-PAHs exposure was more sensitive to red blood cell darmage. The acceptable doses of 8 kinds of OH-PAHs were 1.010 µmol/mol Cr (2-hydrol-naphthalene), 0.743 µmol/mol Cr (1-hydrol-naphthalene), 0.901 µmol/mol Cr (2-hydroxy-fluorene) and 0.775 µmol/mol Cr (1-hydroxy-phenanthrene), 0.737 µmol/mol Cr (1-hydroxy-pyrene), 0.607 µmol/mol Cr (9-hydroxy-fluorene), 0.713 µmol/mol Cr (2-hydroxy-phenanthrene) and 0.628 µmol/mol Cr (3-hydroxybenzo[a] pyrene), respectively. Conclusion: OH-PAHs mixture has positive combined effect on red blood cell damage in non-occupational population, and low concentration of OH-PAHs exposure is more sensitive to red blood cell damage. It is recommended that the exposure dose of PAHs should be controlled within 1 µmol/mol Cr.

Biomarkers for polycyclic aromatic hydrocarbons in human excreta: recent advances in analytical techniques-a review.

Polycyclic aromatic hydrocarbons (PAHs) are widespread environmental pollutants that are generated by the incomplete combustion of organic materials. The main anthropogenic sources of PAHs are the combustion of solid fuels for heating purposes, illegal waste incineration, road transport and industries based on fossil fuels. PAHs can easily enter the body because they are present in all elements of the environment, including water, soil, air, and food. Due to their ubiquitous presence, PAHs, may exert a harmful effect on human health. Assessing PAH exposure through biomonitoring mostly involve techniques to measure the concentration of 1-hydroxypyrene in human urine. Nevertheless, through recent progress in analytical techniques, other common metabolites of PAHs in human biospecimens can be detected. A scientific literature search was conducted to determine which hydroxy derivatives of PAHs are markers of PAHs exposure and to reveal the leading sources of these compounds. Techniques for analyzing biological samples to identify OH-PAHs are also discussed. The most frequently determined OH-PAH in human urine is 1-hydroxypyrene, the concentration of which reaches up to a dozen ng/L in urine. Apart from this compound, the most frequently determined biomarkers were naphthalene and fluorene metabolites. The highest concentrations of 1- and 2-hydroxynaphthalene, as well as 2-hydroxyfluorene, are associated with occupational exposure and reach approximately 30 ng/L in urine. High molecular weight PAH metabolites have been identified in only a few studies. To date, PAH metabolites in feces have been analyzed only in animal models for PAH exposure. The most frequently used analytical method is HPLC-FLD. However, compared to liquid chromatography, the LOD for gas chromatography methods is at least one order of magnitude lower. The hydroxy derivatives naphthalene and fluorene may also serve as indicators of PAH exposure.

Biomonitoring of polycyclic aromatic hydrocarbons in Brazilian pregnant women: Urinary levels and health risk assessment.

Over the years, humans have been continuously exposed to several compounds directly generated by industrial processes and/or present in consumed products. Polycyclic aromatic hydrocarbons (PAHs) are legacy pollutants ubiquitous in the environment and represent the main chemical pollutants in urban areas. Worldwide, studies that aim to understand the impacts of exposure to these chemicals have gained increasing prominence due to their potential toxicity profile, mainly concerning genotoxicity and carcinogenicity. Human biomonitoring (HB) is an analytical approach to monitoring population exposure to chemicals; however, these studies are still limited in Brazil. Thus, this work aimed to evaluate the exposure of Brazilian pregnant women to PAHs through HB studies. Besides, the risk characterization of this exposure was performed. For this purpose, urine samples from 358 Brazilian pregnant women were used to evaluate 11 hydroxylated metabolites of PAHs employing gas chromatography coupled to mass spectrometry. The 1OH-naphthol and 2OH-naphthol were detected in 100% of the samples and showed high levels, corresponding to 16.99 and 3.62 µg/g of creatinine, respectively. 2OH-fluorene (8.12 µg/g of creatinine) and 9OH-fluorene (1.26 µg/g of creatinine) were detected in 91% and 66% of the samples, respectively. Benzo(a)pyrene (BaP) metabolites were detected in more than 50% of the samples (0.58-1.26 µg/g of creatinine). A hazard index of 1.4 and a carcinogenic risk above 10-4 were found for BaP metabolites in the risk characterization. Therefore, our findings may indicate that exposure to PAHs poses a potential risk to pregnant women's health and a high probability of carcinogenic risk due to their exposure to BaP. Finally, this work shows the need for more in-depth studies to determine the sources of exposure and the implementation of health protection measures regarding the exposure of the Brazilian population to PAHs.

Comparative assessment of soil microbial community in crude oil contaminated sites.

Petroleum refineries generate oily sludge that contains hazardous polycyclic aromatic hydrocarbons (PAH), and hence, its proper disposal is of foremost concern. Analysis of the physicochemical properties and functions of indigenous microbes of the contaminated sites are essential in deciding the strategy for bioremediation. This study analyses both parameters at two geographically distant sites, with different crude oil sources, and compares the metabolic capability of soil bacteria with reference to different contamination sources and the age of the contaminated site. The results indicate that organic carbon and total nitrogen derived from petroleum hydrocarbon negatively affect microbial diversity. Contamination levels vary widely on site, with levels of PAHs ranging from 5.04 to 1.66 × 103 µg kg-1 and 6.20 to 5.64 × 103 µg kg-1 in Assam and Gujarat sites respectively, covering a higher proportion of low molecular weight (LMW) PAHs (fluorene, phenanthrene, pyrene, and anthracene). Functional diversity values were observed to be positively correlated (p < 0.05) with acenaphthylene, fluorene, anthracene, and phenanthrene. Microbial diversity was the highest in fresh oily sludge which decreased upon storage, indicating that immediate bioremediation, soon after its generation, would be beneficial. Improvement in the bio-accessibility of hydrocarbon compounds by the treatment of biosurfactant produced by a (soil isolate/isolate) was demonstrated., with respect to substrate utilization.

Seasonal assessment of the distribution, source apportionment, and risk of water-contaminated polycyclic aromatic hydrocarbons (PAHs).

The research aims to evaluate the seasonal differences in the distribution, source, and risks of water-contaminated PAHs. The PAHs were extracted by the liquid-liquid method and analyzed with GC-MS, and a total of eight PAHs were detected. There was a percentage increase in the average concentration of the PAHs from the wet to the dry season in the range of 20 (Anthracene)-350 (Pyrene)%. Total PAHs (∑PAHs) range from 0.31 to 1.23 mg/l in the wet period and from 0.42 to 1.96 mg/l in the dry period. The distribution of the average PAHs in mg/l showed that Fluoranthene ≤ Pyrene < Acenaphthene < Fluorene < Phenanthrene < Acenaphthylene < Anthracene < Naphthalene in wet period and while Fluoranthene < Acenaphthene < Pyrene < Fluorene < Phenanthrene < Acenaphthylene < Anthracene < Naphthalene in the dry period. The children were exposed to non-carcinogenic risk through non-dietary ingestion due to the accumulative effect (HI) of the PAHs in the dry period. Furthermore, the naphthalene was responsible for ecological and carcinogenic risk in the wet period, while the fluorene, phenanthrene, and anthracene were responsible for ecological and carcinogenic risk in the dry period. However, while adults and children are both susceptible to carcinogenic risk through the oral channel during the dry period, only children are susceptible to non-carcinogenic risk through this pathway. The multivariate statistical analysis revealed the influence of physicochemical parameters on the detected PAHs and also showed the PAHs' sources to be mainly combustion, pyrolysis, and vehicular emission.

Photodegradation of hydroxyfluorenes in ice and water: A comparison of kinetics, effects of water constituents, and phototransformation by-products.

The photochemical behavior of organic pollutants in ice is poorly studied in comparison to aqueous photochemistry. Here we report a detailed comparison of ice and aqueous photodegradation of two representative OH-PAHs, 2-hydroxyfluorene (2-OHFL) and 9-hydroxyfluorene (9-OHFL), which are newly recognized contaminants in the wider environment including colder regions. Interestingly, their photodegradation kinetics were clearly influenced by whether they reside in ice or water. Under the same simulated solar irradiation (λ > 290 nm), OHFLs photodegraded faster in ice than in equivalent aqueous solutions and this was attributed to the specific concentration effect caused by freezing. Furthermore, the presence of dissolved constituents in ice also influenced photodegradation with 2-OHFL phototransforming the fastest in 'seawater' ice (k = (11.4 ± 1.0) × 10-2 min-1) followed by 'pure-water' ice ((8.7 ± 0.4) × 10-2 min-1) and 'freshwater' ice ((8.0 ± 0.7) × 10-2 min-1). The presence of dissolved constituents (specifically Cl-, NO3-, Fe(III) and humic acid) influences the phototransformation kinetics, either enhancing or suppressing phototransformation, but this is based on the quantity of the constituent present in the matrixes, the specific OHFL isomer and the matrix type (e.g., ice or aqueous solution). Careful derivation of key photointermediates was undertaken in both ice and water samples using tandem mass spectrometry. Ice phototransformation exhibited fewer by-products and 'simpler' pathways giving rise to a range of hydroxylated fluorenes and hydroxylated fluorenones in ice. These results are of importance when considering the fate of PAHs and OH-PAHs in cold regions and their persistence in sunlit ice.

Hydrophobic microporous extraction on polyurethane sponges for convenient and sensitive analysis of organic molecules in water.

RATIONALE: Various solvent supports have been developed to overcome solvent instability during liquid-phase microextraction. The hydrophobic polyurethane sponge (PS) possesses numerous cross-linked internal microchannels and terminal micropores that can facilitate steady solvent storage capacity, high extraction efficiency, extractant loading, and recycling convenience. METHODS: In this study, an easy, convenient, and efficient PS-supported liquid-phase microextraction (PS-LPME) coupled with gas chromatography-mass spectrometry (GC-MS) method was developed for the trace analysis of different organic compounds in aqueous solutions. Different extraction solvents, PS dosages, stirring speeds, and extraction times were first investigated by extracting eight polycyclic aromatic hydrocarbons (PAHs: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, and pyrene), and then applied for the analysis of triazines, amides, chloroacetamides, and organophosphorus compounds. RESULTS: High enrichment factors (approximately 208-439) were observed for the monitored PAHs. Good linearities, with determination coefficients (r2 ) greater than 0.9992, were achieved in the concentration range of 0.01-50 µg L-1 . Low limits of detection and quantification were found in the ranges of 0.3-3 ng L-1 and 1-10 ng L-1 , respectively. At three spiked concentrations (0.1, 1, and 10 µg L-1 ), good recoveries were obtained in the range of 91.6-118.5% with intra- and inter-day relative standard deviations of less than 6.4% and 11.7%, respectively. CONCLUSIONS: The developed PS-LPME method coupled with GC-MS was successfully applied in the analysis of different organic compounds in aqueous solutions and has shown great convenience and satisfactory enrichment performance in microextraction analysis.

Assessment of biological community in riparian zone contaminated by PAHs: Linking source apportionment to biodiversity.

Riparian zone, an important land-water interface, plays an essential role in maintaining the ecological health of rivers, whereas the effects of Polycyclic aromatic hydrocarbons (PAHs) on the health of biological communities in riparian groundwater remain undetermined. To understand the responses of multiple communities to environmental variables, the distribution and ecosystem risk of 16 PAHs have been investigated in the Beiluo River, China. The distribution of multiple communities in riparian groundwater was investigated by environmental DNA metabarcoding, including 16S rRNA, 18S rRNA, and COI gene sequencing for bacteria, microbial eukaryotes (including algae, fungi, and protozoa), and metazoan, respectively, followed by correlation analysis between multiple communities and PAH contamination levels. The concentration of PAHs in the Beiluo River ranged largely from 35.32 to 728.59 ng/L. Here, the Shannon's diversity index of bacteria (Firmicutes) decreased possibly due to the occurrence of Pyrene, which mainly derives from coal and biomass combustion. Furthermore, the reduced richness of fungi (Ascomycota, Basidiomycota) and algae (Chlorophyta, Chrysophyceae) can be attributed to the presence of medium molecular weight (MMW) PAHs (Pyrene, Benz(a)anthracene, Chrysene), and low molecular weight (LMW) PAHs (Naphthalene, Fluorene, Phenanthrene). The richness and Shannon's diversity index of metazoan (Arthropoda) were promoted owing to MMW PAHs (Chrysene, Fluoranthene) generated from coal and biomass combustion and traffic emission. The ecological risk of PAHs in the groundwater environment of the Beiluo River was characterized as low to medium, where LMW and MMW PAHs posed higher risk than the high molecular weight (HMW) compounds. Overall, this study provides insights into the structures of riparian multi-biological communities altered by PAHs.

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

BACKGROUND: 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. OBJECTIVES: 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. METHODS: 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. RESULTS: PAH levels in the worker breathing zones were highest for naphthalene, acenaphthene, and phenanthrene, with geometric means of 52.1, 11.4, and 9.8 µg/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 5.5 µg/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. CONCLUSIONS: 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 2.5 µg/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.

Occupational exposure and markers of genetic damage, systemic inflammation and lung function: a Danish cross-sectional study among air force personnel.

Air force ground crew personnel are potentially exposed to fuels and lubricants, as raw materials, vapours and combustion exhaust emissions, during operation and maintenance of aircrafts. This study investigated exposure levels and biomarkers of effects for employees at a Danish air force military base. We enrolled self-reported healthy and non-smoking employees (n = 79) and grouped them by exposure based on job function, considered to be potentially exposed (aircraft engineers, crew chiefs, fuel operators and munition specialists) or as reference group with minimal occupational exposure (avionics and office workers). We measured exposure levels to polycyclic aromatic hydrocarbons (PAHs) and organophosphate esters (OPEs) by silicone bands and skin wipes (PAHs only) as well as urinary excretion of PAH metabolites (OH-PAHs). Additionally, we assessed exposure levels of ultrafine particles (UFPs) in the breathing zone for specific job functions. As biomarkers of effect, we assessed lung function, plasma levels of acute phase inflammatory markers, and genetic damage levels in peripheral blood cells. Exposure levels of total PAHs, OPEs and OH-PAHs did not differ between exposure groups or job functions, with low correlations between PAHs in different matrices. Among the measured job functions, the UFP levels were higher for the crew chiefs. The exposure level of the PAH fluorene was significantly higher for the exposed group than the reference group (15.9 ± 23.7 ng/g per 24 h vs 5.28 ± 7.87 ng/g per 24 h, p = 0.007), as was the OPE triphenyl phosphate (305 ± 606 vs 19.7 ± 33.8 ng/g per 24 h, p = 0.011). The OPE tris(1,3-dichlor-2-propyl)phosphate had a higher mean in the exposed group (60.7 ± 135 ng/g per 24 h) compared to the reference group (8.89 ± 15.7 ng/g per 24 h) but did not reach significance. No evidence of effects for biomarkers of systemic inflammation, genetic damage or lung function was found. Overall, our biomonitoring study show limited evidence of occupational exposure of air force ground crew personnel to UFPs, PAHs and OPEs. Furthermore, the OH-PAHs and the assessed biomarkers of early biological effects did not differ between exposed and reference groups.

Innovative Thin-Layer Chromatography/Fluorescence Detection Approach for Sensitive and Specific Determination of Ledipasvir in Rats' Feces and Pharmaceutical Dosage Form.

An innovative thin-layer chromatography method coupled with the fluorescence detection was developed for a specific estimation of ledipasvir. The separation was achieved on plates of silica gel 60 F254 using ethylacetate: hexane: acetonitrile: triethylamine; (6: 3.5: 1.5: 0.5, $\mathrm{v}/\mathrm{v}/\mathrm{v}/\mathrm{v}$) as a mobile phase system. The method involved the exposure of the developed thin-layer chromatography plate of ledipasvir to strong ultraviolet irradiation, resulting in a great enhancement in the fluorescence properties of ledipasvir. The irradiated plates were scanned after the excitation at 315 $\mathrm{nm}$. The method provided a sufficient separation of ledipasvir from sofosbuvir with ${R}_F$values of 0.28 and 0.36 for ledipasvir and sofosbuvir, respectively. The developed procedures were validated based on guidelines from the International Conference on Harmonization and Food and Drug Administration guidelines. The calibration curve was linear over the range of 5-50 $\mathrm{ng}/\mathrm{band}$. The excellent analytical features of the proposed method allow to the specific determination of ledipasvir in pharmaceutical tablets without interference from sofosbuvir or excipients. As the main elimination route for ledipasvir is via the fecal excretion (86%), the method was applied for the estimation of ledipasvir in fecal specimens with adequate recovery. In addition, the proposed method was applied for testing the content uniformity of ledipasvir in the pharmaceutical tablets.

Biodegradation of fluorene by the newly isolated marine-derived fungus, Mucor irregularis strain bpo1 using response surface methodology.

Fluorene, a low molecular weight polycyclic aromatic hydrocarbon (PAH), is of immense environmental interest because of its carcinogenicity, teratogenicity, mutagenicity, toxicity and persistence to microbial degradation. Existentially, there is paucity of information on PAH degradation by fungi isolated from marine environment. Therefore, this study investigated fluorene degradation efficiency of marine derived filamentous fungus, Mucor irregularis strain bpo1 (GenBank Accession Number: MK373020). Response Surface Methodology (RSM) using Box-Behnken Design (BBD) was successfully deployed in the optimization of process parameters (pH-7, temperature-32.5 °C, substrate concentration-100 mg L-1 and dry weight-2 g) resulting in 81.50% fluorene degradation on 5th day. The design and regression model were found to be statistically significant, adequate and appropriate with p < 0.0001, F value= 202.39, and predicted coefficient of determination (R2 =0.9991). Optimization of the vital constituents of the mineral salt medium (MSM) used for the study using RSM-Central Composite Design (CCD) resulted in 79.80% fluorene degradation rate. Enhanced fluorene degradation efficiency (82.50%) was recorded when the optimized process variables were subjected to growth-linked validation experiments. The enzyme activities revealed 87%, 59% and 31% induction of laccase, manganese peroxidase and lignin peroxidase respectively. Four metabolites; 9H-fluoren-9-one, benzene-1,2-dicarboxylic acid, 2-hydroxybenzoic acid and phenol obtained after the experiment were characterized and confirmed with GC-MS analysis. The findings revealed the promising potentials of M. irregularis in PAH degradation and by extension green remediation technology.

Effectiveness of predicting spatial contaminant distributions at industrial sites using partitioned interpolation method.

Soil pollution at industrial sites is an important issue in China and in most other regions of the world. The accurate prediction of the spatial distribution of pollutants at contaminated industrial sites is a requirement for the development of most soil remediation strategies, and is commonly performed using spatial interpolation methods. However, significant and abrupt variations in the spatial distribution of pollutants decrease prediction accuracy. During this study, the use of partition interpolation methods was applied to benzo fluoranthene in four soil layers at a contaminated site to determine their ability to improve prediction accuracy in comparison to unpartitioned methods. The examined methods for partitioned interpolation included inverse distance weighting (IDW), radial basis function (RBF), and ordinary kriging (OK). The prediction results of the three methods for partitioned interpolation were compared, and the applicability of partition interpolation was determined. The prediction error associated with the partitioned interpolation methods decreased by 70% compared to unpartitioned interpolation. The prediction accuracy of IDW-based partition interpolation was higher than that of RBF- and OK-based partition interpolation techniques, and it was suitable for identification of highly polluted areas. Partition interpolation is also applicable to 12 other PAHs controlled by USEPA that can be detected, and the prediction effects could also verify this interpolation choice. In addition, the results also demonstrated that the more the maximum concentration deviated from the "norm", the greater the prediction error was caused by the smoothing effects of the interpolation models. These results suggest that the partition interpolation with IDW method can be effectively used to obtain relatively accurate spatial contaminant distribution information, and to identify highly polluted areas.

Seasonal characteristic composition of inorganic elements and polycyclic aromatic hydrocarbons in atmospheric fine particulate matter and bronchoalveolar lavage fluid of COPD patients in Northeast China.

OBJECTIVE: To explore the composition characteristics of atmospheric fine particulate matter (PM2.5) and bronchoalveolar lavage fluid (BALF), and their impact on the development of chronic obstructive pulmonary disease (COPD). METHODS: The atmospheric PM2.5 samples and BALF samples from COPD patients were collected from June 2, 2017 to October 30, 2018, and allocated into a high-risk of PM2.5 inhalation group and a low-risk PM2.5 inhalation group according to the heating season in Harbin. Inorganic elements were detected by ICP-MS, and polycyclic aromatic hydrocarbons (PAHs) were detected by GC/MS. RESULTS: Twenty-six inorganic elements were found in 54 BALF specimens. There was a high correspondence in inorganic elements between BALF and atmospheric PM2.5. Trace elements Cr, Mn, V, and Co, and toxic trace elements Al, Pb, Cd, As, and Ag were above the upper limit of normal blood. There were significant higher K, Ti, Fe, Co, Cu, Se, Rb, Ag, and Sb in BALF of the high-risk PM2.5 inhalation group (p < 0.05). Sixteen PAHs were detected in 32 BALF samples. The main components of BALF and atmospheric PM2.5 were the high molecular weight PAHs, and the species and concentration of PAHs in BALF and atmospheric PM2.5 are highly consistent. CONCLUSION: The types and concentrations of inorganic elements and PAHs in BALF of COPD patients are highly consistent with those of atmospheric PM2.5. The sustained high concentrations of Benzo(a)anthracene, Chrysene, Benzo(b)Fluoranthene, Benzo(k)Fluoranthene, Indeno(123-c,d)Pyrene, and Benzo(a)Pyrene in BALF of COPD patients may have long-term adverse effects on COPD patients.

Polycyclic aromatic hydrocarbons (PAHs) in dry tea leaves and tea infusions in Vietnam: contamination levels and dietary risk assessment.

The total mean ∑[Formula: see text] in samples were from 75.3 to 387.0 ng/g dry weight (d.w) and showed high value in black dry tea, followed by herbal, oolong, and green tea. The mean ∑[Formula: see text] (a combination of benz[a]anthracene, chrysene, benzo[b]fluoranthene, and benzo[a]pyrene) values were 54.3 ng/g, 16.4 ng/g, 14.2 ng/g, and 6.6 ng/g for black, herbal, green, and oolong teas, respectively. Concentration for benzo[a]pyrene (BaP) was from 0.4 to 35.8 ng/g, and the BaP equivalent concentration values ranged from 0.3 to 48.1 ng/g. There was only 1 black tea sample that BaP concentration exceeded the maximum level according to European Union (EU) standards. Tea samples marketed in Vietnam showed insignificant difference with the samples from other origins by same analytical method. Black teas showed high PAHs contents in dry tea samples but the released percentage of sum of PAHs from tea-to-tea infusion was lower than that in other tea type samples. The released percentages of PAH4 from tea-to-tea infusion were 40.7, 15.4, and 1.9 for green, herbal, and black tea. High temperature in black tea manufacturing processes might reduce essential oil content in tea that might effect on the PAHs partially release into the infusion. Indeed, based on EU regulations, we may conclude that tea consumers are safe in risk of exposure to PAHs obtained from teas.

SERS-Based Molecularly Imprinted Plasmonic Sensor for Highly Sensitive PAH Detection.

A novel hybrid plasmonic platform based on the synergetic combination of a molecularly imprinted polymer (MIP) thin film with Au nanoparticle (NPs) assemblies, noted as Au@MIP, was developed for surface-enhanced Raman scattering (SERS) spectroscopy recognition of polycyclic aromatic hydrocarbons (PAHs). While the MIP trapped the PAH close to the Au surface, the plasmonic NPs enhanced the molecule's Raman signal. The Au@MIP fabrication comprises a two-step procedure, first, the layer-by-layer deposition of Au NPs on glass and their further coating with a uniform MIP thin film. Profilometry analysis demonstrated that the thickness and homogeneity of the MIP film could be finely tailored by tuning different parameters such as prepolymerization time or spin-coating rate. Two different PAH molecules, pyrene or fluoranthene, were used as templates for the fabrication of pyrene- or fluoranthene-based Au@MIP substrates. The use of pyrene or fluoranthene, as the template molecule to fabricate the Au@MIP thin films, enabled its ultradetection in the nM regime with a 100-fold improvement compared with the nonimprinted plasmonic sensors (Au@NIPs). The SERS data analysis allowed to estimate the binding constant of the template molecule to the MIP. The selectivity of both pyrene- and fluoranthene-based Au@MIPs was analyzed against three PAHs of different sizes. The results displayed the important role of the template molecule used for the Au@MIPs fabrication in the selectivity of the system. Finally, the practical applicability of pyrene-based Au@MIPs was shown by performing the detection of pyrene in two real samples: creek water and seawater. The design and optimization of this type of plasmonic platform will pave the way for the detection of other relevant (bio)molecules in a broad range of fields such as environmental control, food safety, or biomedicine.

Polycyclic aromatic hydrocarbons in traditionally smoked Slavonska kobasica.

The traditional smoking procedure, which is the use of open fire, can lead to the formation of PAHs in sausages. The aim of this paper was to assess the types and concentrations of 16 PAHs in 30 samples of Slavonska kobasica, a traditional smoked sausage. In general, some samples showed high values of anthracene and acenaphthylene. In one sample, acenaphthylene reached the value of 1050 µg/kg and in another 1491 µg/kg anthracene was measured. Cancerogenic benzo(a)pyrene content was little above the maximum limit of 5 µg/kg in four samples, but mainly remained below the limit of quantification. PAH4 (i.c. benzo(a)anthracene, chrysene, benzo(b)fluoranthene and benzo(a)pyrene) were above the maximum limit of 30 µg/kg in three samples. Generally, it can be noted from the results that samples with high PAH4 and benzo(a)pyrene concentrations also have high PAH16 concentrations.

Effects of smoke flavoring using different wood chips and barbecuing on the formation of polycyclic aromatic hydrocarbons and heterocyclic aromatic amines in salmon fillets.

Herein, the concentrations of food toxicants, polycyclic aromatic hydrocarbons (PAHs) and heterocyclic aromatic amines (HAAs), in salmon fillets smoke flavored with different smoking wood chips (oak, apple, bourbon soaked oak, cherry and hickory) and barbecuing were determined. Benzo[a]anthracene (up to 0.24 ng/g) and chrysene (0.22 ng/g) were determined in the raw salmon fillets. While ∑PAH8 (benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[k]fluoranthene, benzo[a]pyrene, dibenzo[a,h]anthracene, benzo[g,h,i]perylene, indeno[1,2,3-cd]pyrene) in the raw samples ranged between 0.44 and 0.46 ng/g, smoke flavoring increased the amount of ∑PAH8 and the amount varied between 0.47 and 0.73 ng/g. Salmon smoked flavored with bourbon soaked oak, cherry and hickory wood chips and barbecued showed significantly (P <0.05) lower contents of ∑PAH4 (benzo[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[a]pyrene) and ∑PAH8 compared to non-smoke flavored barbecued samples. Additionally, smoke flavoring with apple, bourbon soaked oak, and cherry wood chips significantly (P <0.05) reduced the total HAA contents in barbecued salmon. A remarkable result was that the bourbon-soaked oak and cherry wood chips had inhibitory effects on both PAH and HAA contents. In sum, barbecued non-smoke flavored and smoke flavored salmon with different wood chips could be considered safe from the perspective of the detected amounts of PAHs and HAAs in salmon fillets.

The Degradation of Phenanthrene, Pyrene, and Fluoranthene and Its Conversion into Medium-Chain-Length Polyhydroxyalkanoate by Novel Polycyclic Aromatic Hydrocarbon-Degrading Bacteria.

Screening of high-efficient polycyclic aromatic hydrocarbon (PAH)-degrading bacteria is important due to environmental contamination by PAHs. In this study, sediment contaminated with phenanthrene (Phe), pyrene (Pyr), and fluoranthene (Fluo) was used as a source of bacteria. The ability of these isolated bacteria to convert PAHs into valuable products was determined. Based on a primary screening, 20 bacterial isolates were obtained; however, only three strains showed a good PAH-degrading ability, and were identified as Pseudomonas aeruginosa, Pseudomonas sp., and Ralstonia sp. PAH-degrading genes were detected in all isolates. Notably, all selected strains could degrade PAHs using the ortho or meta cleavage pathways due to the presence of catechol dioxygenase genes. The ability of isolated strains to convert PAHs into polyhydroxyalkanoate (PHA) was also evaluated in both single and mixed cultures. Single cultures of P. aeruginosa PAH-P02 showed 100% degradation of PAHs, with the highest biomass (1.27 ± 0.02 g l-1) and PHA content (38.20 ± 1.92% dry cell weight). However, degradative ability and PHA production were decreased when mixtures of PAHs were used. This study showed that P. aeruginosa, Pseudomonas sp., and Ralstonia sp. were able to degrade PAHs and convert them into medium-chain-length (mcl)-PHA. A high content of 3-hydroxydecanoate (3HD, C10) was observed in this study. The formation of mcl-PHA with high 3HD content from Pyr and Fluo, and the assessment of mixed cultures converting PAHs to mcl-PHA, were novel contributions.

Investigation of geospatial distribution of PAH compounds in soil phase and determination of soil-air exchange direction in a megacity.

In this study, determination of possible sources, soil-air exchange direction, and spatial distribution of PAH concentrations was aimed. In this scope, soil samples were collected from 35 different points, which have the urban and rural characteristics, from European and Asian Sides in Istanbul. The average ∑16PAH concentrations were found as 22.11 ng/g dw for urban site and 19.53 ng/g dw for rural site, respectively. The highest concentration was 279.5 ng/g dw. PAH concentrations were higher in urban site than rural site. Acenaphthene and benzo[k]fluoranthene were observed as the dominant species. PAH concentrations are observed higher mostly in north and west parts of European Side and south and east parts of Asian Side. There was net evaporation from soil to air for lower molecular weight PAHs with 2, 3 rings, while high molecular weight PAHs with 4, 5, 6 rings accumulated in the soil at both urban and rural sites. PAHs were mostly originated from coal burning and the use of diesel engine vehicles.