Assessment of Dust, Chemical, Microbiological Pollutions and Microclimatic Parameters of Indoor Air in Sports Facilities.

The aim of this study was to analyse the quality of indoor air in sport facilities in one of the sport centres in Poland with respect to microclimatic parameters (temperature, humidity, and air flow velocity), particulate matter concentrations (PM10, PM4, PM2.5, and PM1), gas concentrations (oxygen, ozone, hydrogen sulphide, sulphur dioxide, volatile organic compounds, and benzopyrene), and microbial contamination (the total number of bacteria, specifically staphylococci, including Staphylococcus aureus, haemolytic bacteria, Enterobacteriaceae, Pseudomonas fluorescens, actinomycetes, and the total number of fungi and xerophilic fungi). Measurements were made three times in May 2022 at 28 sampling points in 5 different sporting areas (the climbing wall, swimming pool, swimming pool changing room, and basketball and badminton courts) depending on the time of day (morning or afternoon) and on the outside building. The obtained results were compared with the standards for air quality in sports facilities. The air temperature (21−31 °C) was at the upper limit of thermal comfort, while the air humidity (RH < 40%) in the sports halls in most of the locations was below demanded values. The values for dust pollution in all rooms, except the swimming pool, exceeded the permissible limits, especially in the afternoons. Climatic conditions correlated with a high concentration of dust in the indoor air. Particulate matter concentrations of all fractions exceeded the WHO guidelines in all researched premises; the largest exceedances of standards occurred for PM2.5 (five-fold) and for PM10 (two-fold). There were no exceedances of gaseous pollutant concentrations in the air, except for benzopyrene, which resulted from the influence of the outside air. The total number of bacteria (5.1 × 101−2.0 × 104 CFU m−3) and fungi (3.0 × 101−3.75 × 102 CFU m−3) was exceeded in the changing room and the climbing wall hall. An increased number of staphylococci in the afternoon was associated with a large number of people training. The increased concentration of xerophilic fungi in the air correlated with the high dust content and low air humidity. Along with the increase in the number of users in the afternoon and their activities, the concentration of dust (several times) and microorganisms (1−2 log) in the air increased by several times and 1−2 log, respectively. The present study indicates which air quality parameters should be monitored and provides guidelines on how to increase the comfort of those who practice sports and work in sports facilities.

Impacts of dibenzopyrenes on bacterial community isolated from Gulf of Mexico sediment.

The presence of polycyclic aromatic hydrocarbons (PAHs) in marine environments as a result of contamination is an environmental concern, especially in regions where oil spills such as the Deepwater Horizon have occurred. While numerous PAHs have been studied for their effects on microbes, the family of dibenzopyrenes has yet to be investigated. In this preliminary study, the impacts of these molecules on the community structure of a bacterial consortium isolated from oil-impacted Gulf of Mexico sediment were examined using high-throughput sequencing, demonstrating intriguing negative impacts on species diversity and abundance. While no measurable degradation of the dibenzopyrenes was observed after 28-day incubation, the abundance of known oil-degrading bacteria from orders such as Oceanospirillales, Caulobacterales, Sphingomonadales, and Nitrosococcales were shown to be enhanced. Of the five isomers of dibenzopyrene studied, dibenzo[a,h]pyrene supported the fewer number of microbial species suggesting the isomer was more toxic compared to the other isomers.

2D Graphene Oxide/Fe-MOF Nanozyme Nest with Superior Peroxidase-Like Activity and Its Application for Detection of Woodsmoke Exposure Biomarker.

Emerging nanomaterials such as nanozymes have recently been applied for the immunoassay-based detection of biomarkers. However, the inferior catalytic activity and low water solubility of nanozymes remain as the major limitations compared to natural enzymes. To overcome these limitations, we successfully synthesized a superior nanozyme with a structure of enriched 2D catalytic interface, namely Nanozyme Nest, which was composed of Fe-based metal-organic frameworks (Fe-MOF) and graphene oxide (GO). Then, we applied it in an ultrasensitive enzyme-linked immunosorbent assay (ELISA) for the detection of benzo[a]pyrene-7,8-diol 9,10-epoxide-DNA adduct (BPDE-DNA), which is a metabolite of benzo[a]pyrene (BP) and used as a typical biomarker of woodsmoke exposure in human blood. The Nanozyme Nest features amplified peroxidase-like catalytic ability from graphene and Fe-MOF due to their large surface area and abundant active sites. By using the proposed Nanozyme Nest-based ultrasensitive ELISA, the BPDE-DNA could be detected at a level as low as 0.268 ng/mL, and the obtained sensitivity was much higher than most of the widely used methods. Our work provides a novel strategy to design ultrasensitive immunosensors with advantages of amplified catalytic activity and improved water solubility compared to classic nanozymes. This illustrates the promising applications of the Nanozyme Nest-based immunosensors in point-of-care settings to conveniently detect exposures and diagnose diseases.

Determination of 3-Hydroxybenzo[a]pyrene Glucuronide/Sulfate Conjugates in Human Urine and Their Association with 8-Hydroxydeoxyguanosine.

While 3-hydroxybenzo[a]pyrene (3-OHBaP) is a preferable biomarker to assess human exposure to benzo[a]pyrene (BaP), a sensitive and simple method is lacking. In this study, a specific and sensitive method based on liquid chromatography coupled with electrospray tandem mass spectrometry (LC-ESI-MS/MS) was developed for direct analysis of 3-OHBaP glucuronide and sulfate conjugates in human urine samples without enzymatic hydrolysis. The limits of detection (LODs) were 0.06 ng L-1 for BaP-3-sulfate (BaP-3-S) and 0.16 ng L-1 for BaP-3-glucuronide (BaP-3-G), which showed high sensitivity. Both compounds showed excellent linearity (r2 > 0.99) in the range of 0.01-10 µg L-1 in the instrumental calibration. The absolute recoveries of the target analytes spiked in human urine for the entire analytical procedure were 68.3 ± 4.96% (mean ± SD) and 63.7 ± 5.47% for BaP-3-S and BaP-3-G, respectively. This method was applied to quantify BaP-3-G and BaP-3-S in 150 urine samples collected from healthy volunteers. The mean concentration of BaP-3-S was 0.67 ng g-1 creatinine (98% of 3-OHBaP is excreted mainly in these two conjugated forms in human urine. A statistically significant positive association was observed between urinary 3-OHBaP conjugates and urinary 8-OHdG levels (p < 0.001) in the general population. This study developed a sensitive and simple method to determine urinary glucuronide/sulfate conjugated BaP metabolites and for the first time found that BaP exposure associated with 8-OHdG levels in the general population.

Ultra-high sensitive analysis of 3-hydroxybenzo[a]pyrene in human urine using GC-APLI-MS.

Urinary 3-hydroxybenzo[a]pyrene (3-OH-BaP) is a known biomarker for human exposure to carcinogenic polycyclic aromatic hydrocarbons (PAH). In this work, a new method for the ultra-sensitive quantification of this biomarker has been developed using the hyphenation of gas chromatography and atmospheric pressure laser ionization-mass spectrometry (GC-APLI-MS). In combination with an advanced sample preparation, a limit of detection (LOD) of 0.6 pg/L was achieved which is an improvement by a factor of at least 28 compared with existing methods. The limit of quantification (LOQ) is 1.8 pg/L. With this set-up 3-OH-BaP could be analyzed in urine samples of 7 smokers and 7 non-smokers. Concentrations ranged from 37 to 270 pg/L for non-smokers and from 374 to 1171 pg/L for smokers. For the first time, 3-OH-BaP was quantifiable in all non-smoker samples as no value was below the LOQ. Correlation of the urinary 3-OH-BaP values with the number of daily smoked cigarettes and with urinary cotinine values shows a clear relationship between 3-OH-BaP content and smoking habits. This innovative analytical method enables monitoring of low levels of the biomarker 3-OH-BaP in urine of non-occupationally exposed individuals including smokers, the general population with background PAH exposure and cohorts of low exposition such as newborns and children.

Toxicant inhalation among singleton waterpipe tobacco users in natural settings.

BACKGROUND: Studies that assess waterpipe tobacco smoking behaviour and toxicant exposure generally use controlled laboratory environments with small samples that may not fully capture real-world variability in human behaviour and waterpipe products. This study aimed to conduct real-time sampling of waterpipe tobacco use in natural environments using an in situ device. METHODS: We used the REALTIME sampling instrument: a validated, portable, self-powered device designed to sample automatically a fixed percentage of the aerosol flowing through the waterpipe mouthpiece during every puff. We recruited participants at café and home settings in Jordan and measured puffing behaviour in addition to inhalation exposure of total particulate matter (TPM), carbon monoxide (CO), nicotine, polycyclic aromatic hydrocarbons and volatile aldehydes. We correlated total inhaled volume with five selected toxicants and calculated the regression line of this relationship. RESULTS: Averaged across 79 singleton sessions (52% male, mean age 27.0, 95% home sessions), sessions lasted 46.9 min and participants drew 290 puffs and inhaled 214 L per session. Mean quantities of inhaled toxicants per session were 1910 mg TPM, 259 mg CO, 5.0 mg nicotine, 117 ng benzo[a]pyrene and 198 ng formaldehyde. We found positive correlations between total inhaled volume and TPM (r=0.472; p<0.001), CO (r=0.751; p<0.001), nicotine (r=0.301, p=0.035) and formaldehyde (r=0.526; p<0.001), but a non-significant correlation for benzo[a]pyrene (r=0.289; p=0.056). CONCLUSIONS: In the natural environment, waterpipe tobacco users inhale large quantities of toxicants that induce tobacco-related disease, including cancer. Toxicant content per waterpipe session is at least equal, but for many toxicants several magnitudes of order higher, than that of a cigarette. Health warnings based on early controlled laboratory studies were well founded; if anything our findings suggest a greater exposure risk.

French firefighters exposure to Benzo[a]pyrene after simulated structure fires.

INTRODUCTION: Firefighters have occupational exposure to toxic compounds during firefighting, but not only. Surface contamination of equipment has never been studied in French firefighters. MATERIALS AND METHODS: This study measured the surface load in benzo [a]pyrene (BaP), a carcinogenic polycyclic aromatic hydrocarbon, on the outer surface of fire jackets, personal protective equipment and tools used by firefighters after a live fire training in a closed environment. The effectiveness of a standard jacket washing procedure on BaP contamination was assessed. RESULTS: A single training session was responsible for a BaP deposit of 113.75 ±â€¯45.03µg/m2 on exposed fire jacket material. After a single session, the deposit of BaP found on PPE and tools was measured on different surfaces ranged from 12 to 157 µg/m2. After multiple training sessions, a cumulative effect was suspected. The current PPE cleaning and maintenance procedures does not appear to effectively reduce contamination. CONCLUSION: French firefighters' exposure during in a live-fire training session in fire simulator is responsible for exposure to BaP. The estimated load of BaP on the outer surface of fire jackets could potentially have acute and chronic effects if absorbed in one's body. Further studies are needed to better understand individual French firefighters' exposure and determine appropriate measures to prevent contamination. It will be also be necessary find maintenance procedures that significantly reduce the BaP load.

Sedimentary archive of Polycyclic Aromatic Hydrocarbons and perylene sources in the northern part of Taihu Lake, China.

In the present work, we analyzed the concentration patterns of 20 Polycyclic Aromatic Hydrocarbons (PAHs) in 25 surface sediments and 11 sediment cores from the northern part of Taihu Lake, China. Three of the cores were dated based on 137Cs activity for the deposition age of the sediment. The spatial distributions of the PAH concentrations show that the inflow rivers into Zhushan Bay and Meiliang Bay were the main pathway for PAHs and sediment input to the northern part of the lake. This results in substantially higher PAH concentrations (up to 5000 ng/g) and sedimentation rates (higher than the average of 3-4 mm/a) in the area close to the river outlets. In addition, results also show that PAH concentrations in the sediments considerably increased from the early 1960s, but the decreasing concentrations in the upper layers of the sediment could be attributed to the introduction of measures on environmental improvement from ca. 2000. There were both anthropogenic and biogenic origins of perylene in the lake sediments, which were distinguished based on spatial distribution patterns and also the concentration proportions of perylene to the sum of the 20 PAHs. In the cores collected close to river outlets, the concentration proportions of perylene typically range from 0.02 to 0.18 and there are significant positive linear correlations between the concentration of perylene and three anthropogenic PAHs (Benzo[a]pyrene, Benzo[e]pyrene, Pyrene), suggesting that perylene was dominated by anthropogenic input. However, the cores collected further away from the river outlets show the concentration proportions between 0.13 and 0.96, and present significant negative correlations or no correlations between perylene and the three PAHs, suggesting that perylene was mainly formed by biogenic activities. Furthermore, the different perylene sources accompanied with the location distributions imply that anthropogenic activities could inhibit its biogenic formation.

Hair analysis for the biomonitoring of polycyclic aromatic hydrocarbon exposure: comparison with urinary metabolites and DNA adducts in a rat model.

Alongside the analysis of urinary metabolites which are traditional biomarkers of polycyclic aromatic hydrocarbons (PAH) exposure, the possibility of detecting PAH as well as their metabolites in hair has also recently been demonstrated. As the concentration of pollutants detected in hair is not impacted by short-term variations in exposure as can be observed with urine, it accurately represents an individual's average level of exposure, which is the most relevant information when investigating possible linkages with biological effects. In the current study, based on a rat model exposed to a mixture of PAHs for a 90-day period, the linkage between the PAH exposure level and the resulting concentration of their metabolites in hair was then investigated. The linkage between exposure levels and the concentrations of OH-PAH in hair collected at the end of the experiment were compared to those obtained using urinary concentration of OH-PAH collected from the same animals. Linear relationship between levels of exposure and the concentration of OH-PAH in the rats' hair (R2 0.722-0.965, p < 0.001) was observed for 28 OH-PAH out of the 54 investigated. The difference in PAH concentration between the different groups of exposure and the possibility to back determine the animals' level of exposure on the basis of PAH-metabolite concentrations in both hair and urine was also demonstrated. In addition to the strong linear relation observed between the doses of exposure and the levels of concentration of hydroxylated metabolites in hair (p < 0.001), the analysis of a subset of animals demonstrated a linkage between 3-OH-benzo[a]pyrene concentration levels in hair and the levels of B[a]P-DNA adduct formed (p < 0.05), thereby suggesting the potential of their analysis to predict genetic alteration.

Exporisq-HAP database: 20 years of monitoring French occupational exposure to polycyclic aromatic hydrocarbon mixtures and identification of exposure determinants.

BACKGROUND: Millions of workers are exposed to polycyclic aromatic hydrocarbons (PAHs), a well-known family of carcinogens, but occupational exposure data about PAH mixture compositions are scarce. OBJECTIVES: To provide a detailed picture of airborne PAH exposures encountered in the French industrial landscape over the previous 20 years and to identify determinants driving exposures. METHODS: Results from 1643 airborne samples of 16 gaseous and particulate PAHs implemented into the Exporisq HAP database from 1995 to 2014 were used to describe exposure levels and aerosol chemical composition in many industries and activities. Compliance of benzo[a]pyrene (BaP) levels with several existing occupational exposure limits for long-term exposure was assessed. RESULTS: BaP levels were lower than those reported in the literature, but the level and composition of PAH mixtures were highly variable between and within industries. Numerous exposure determinants (e.g., product composition, type and temperature of process, ventilation and confinement) were assumed to explain these differences. The highest levels were found in industries using products derived from coal (aluminum, silicon, and coke production, manufacturing of carbon products and foundries), with mean BaP levels up to 23 times higher than the French recommended value of 150 ng/m3. Forty-seven percent of the occupational activities exceeded this value. Conversely, exposures resulting from petroleum-derived products were relatively low. CONCLUSIONS: As health effects depend on PAH levels but also on the composition of the mixture, exposure assessments must characterize the entire mixtures and record specific determinants to define homogeneous exposure groups and to accurately assess health risks.

Urinary trans-anti-7,8,9,10-tetrahydroxy-7,8,9,10-tetrahydrobenzo(a)pyrene as the most relevant biomarker for assessing carcinogenic polycyclic aromatic hydrocarbons exposure.

Polycyclic aromatic hydrocarbons (PAH) are ubiquitous pollutants present as complex mixtures in the environment. Among them, benzo(a)pyrene (BaP) is classified as carcinogenic to humans by the International Agency of Research on Cancer. Taking into account all absorption ways, human biomonitoring allows PAH exposure assessment, but biomarkers both specific to carcinogenic effect and sufficiently sensitive are lacking. In this work, we proposed the urinary 7,8,9,10-tetrahydroxy-7,8,9,10-tetrahydrobenzo(a)pyrene (7,8,9,10-OHBaP) stemming from hydrolysis of BaP-7,8-diol-9,10-epoxide, the ultimate carcinogenic BaP metabolite, as biomarker of PAH exposure. A simple and highly sensitive analytical method, with a limit of quantification (LQ) reaching 0.06pmol/L (0.02ng/L), was described and validated. The relevance of urinary 7,8,9,10-OHBaP concentrations adjustment by creatinine was demonstrated. In a group of 24 non-occupationally PAH exposed subjects, only 15% of 7,8,9,10-OHBaP levels was below the LQ and the last daily void has been found as the best sampling time. Tobacco consumption had a significant positive effect on 7,8,9,10-OHBaP concentrations with a 90e percentile equal to 0.05nmole/mole creatinine (nmol/mol) and 0.03nmol/mol for smokers and non-smokers, respectively. In case of occupational PAH exposure, all the pre- and post-shift urinary 7,8,9,10-OHBaP levels of 7 non-smoking workers in a prebaked electrodes production plant were above the LQ. Concentrations ranged from 0.05 to 0.91nmol/mol and accumulation of 7,8,9,10-OHBaP into organism of workers during the working week was clearly observed. The best sampling time was the post-shift at the end of week but samples should also be collected at pre-shift the beginning of week to assess the background level. Finally, the urinary 7,8,9,10-OHBaP elimination kinetic through the weekend was studied using non-linear mixed effect modelling. Mean apparent urinary half-life was 31.5h with low inter-individual variability. Describing key characteristics of urinary 7,8,9,10-OHBaP as PAH exposure biomarker, this work should promote its use for future large-scale biomonitoring campaigns.

Quantification of 1-hydroxypyrene, 1- and 2-hydroxynaphthalene, 3-hydroxybenzo[a]pyrene and 6-hydroxynitropyrene by HPLC-MS/MS in human urine as exposure biomarkers for environmental and occupational surveys.

CONTEXT: Several urinary PAHs metabolites can be detected by HPLC-MS/MS for individual exposure assessment. OBJECTIVE: Quantitation of urinary metabolites of four PAHs, selected on the basis of their significance, with reduced costs and high sensitivity. MATERIALS AND METHODS: HPLC-MS/MS was used and pure standards and isotope-labeled internal analogs of the analytes. Two hundred samples were tested after enzymatic hydrolysis. RESULTS: Accuracy was higher than 90% and variability lower than 19%; LODs permit to measure 1-hydroxypyrene, 1 and 2-hydroxynaphthalene in all subjects, 6-hydroxynitropyrene in the 65% and 3-hydroxybenzo[a]pyrene in the 70%. DISCUSSION AND CONCLUSION: The method is suitable both for occupational and for environmental studies. This is the first paper reporting urinary levels of 6-hydroxynitropyrene in European subjects, nonoccupationally exposed to nitro-PAHs.

Human Microdosing with Carcinogenic Polycyclic Aromatic Hydrocarbons: In Vivo Pharmacokinetics of Dibenzo[def,p]chrysene and Metabolites by UPLC Accelerator Mass Spectrometry.

Metabolism is a key health risk factor following exposures to pro-carcinogenic polycyclic aromatic hydrocarbons (PAHs) such as dibenzo[def,p]chrysene (DBC), an IARC classified 2A probable human carcinogen. Human exposure to PAHs occurs primarily from the diet in nonsmokers. However, little data is available on the metabolism and pharmacokinetics in humans of high molecular weight PAHs (≥4 aromatic rings), including DBC. We previously determined the pharmacokinetics of DBC in human volunteers orally administered a microdose (29 ng; 5 nCi) of [14C]-DBC by accelerator mass spectrometry (AMS) analysis of total [14C] in plasma and urine. In the current study, we utilized a novel "moving wire" interface between ultraperformance liquid chromatography (UPLC) and AMS to detect and quantify parent DBC and its major metabolites. The major [14C] product identified in plasma was unmetabolized [14C]-DBC itself (Cmax = 18.5 ±15.9 fg/mL, Tmax= 2.1 ± 1.0 h), whereas the major metabolite was identified as [14C]-(+/-)-DBC-11,12-diol (Cmax= 2.5 ±1.3 fg/mL, Tmax= 1.8 h). Several minor species of [14C]-DBC metabolites were also detected for which no reference standards were available. Free and conjugated metabolites were detected in urine with [14C]-(+/-)-DBC-11,12,13,14-tetraol isomers identified as the major metabolites, 56.3% of which were conjugated (Cmax= 35.8 ± 23.0 pg/pool, Tmax = 6-12 h pool). [14C]-DBC-11,12-diol, of which 97.5% was conjugated, was also identified in urine (Cmax = 29.4 ± 11.6 pg/pool, Tmax = 6-12 h pool). Parent [14C]-DBC was not detected in urine. This is the first data set to assess metabolite profiles and associated pharmacokinetics of a carcinogenic PAH in human volunteers at an environmentally relevant dose, providing the data necessary for translation of high dose animal models to humans for translation of environmental health risk assessment.

Sensitive determination of trace urinary 3-hydroxybenzo[a]pyrene using ionic liquids-based dispersive liquid-liquid microextraction followed by chemical derivatization and high performance liquid chromatography-high resolution tandem mass spectrometry.

3-Hydroxybenzo[a]pyrene (3-OHBaP) is widely used as a biomarker for assessing carcinogenic benzo[a]pyrene exposure risks. However, monitoring urinary 3-OHBaP suffers from an insufficient sensitivity due to the pg/mL level in urine excretion. In this study, a sensitive method for determination trace urinary 3-OHBaP was developed, involving enzymatic hydrolysis of the glucuronide and sulfate conjugates, ionic liquids dispersive liquid-liquid microextraction (IL-DLLME) enrichment, derivatization with dansyl chloride and HPLC-HRMS/MS analysis in the positive ion mode. Using IL-DLLME makes the enrichment of trace 3-OHBaP very simple, time-saving, efficiency and environmentally-friendly. To enhanced HPLC-HRMS/MS response, an MS-friendly dansyl group was introduced to increase the ionization and fragmentation efficiency. The optimal IL-DLLME extraction parameters and derivatization reaction conditions were investigated. Good linearity was obtained over a concentration range of 0.6-50.0pg/mL with correlation coefficients (r(2)) of 0.9918. The limit of detection (LOD) and limit of quantification (LOQ) values were 0.2pg/mL and 0.58pg/mL, respectively. The recoveries were 92.0±4.2% with the intra-day and inter-day RSD values ranged from 2.2% to 3.8% and from 3.3% to 6.8%, respectively. The proposed IL-DLLME-Dansylation-HPLC-HRMS/MS method was successfully applied to determine urinary 3-OHBaP of non-occupational exposed smokers and nonsmokers.

[THE LEVEL OF BENZ(A)PIREN IN TOBACCO SMOKE].

The medical problems of the environmental pollution with products of tobacco smoke are relatively known. The question of separate components of tobacco smoke, factors such a puff-volume, rate, distance, frequency, length of butt in the environment air is not well understand and should further be investigated. It is shown the dependence of the process on the following factors: physic-chemical parameters of atmospheric environment, brand of tobacco product, activity of smoking process. We aimed to determine the dependence of benz(a)pirene in the air samples of tobacco smoke in the distance of 2,0; 4,0 and 6,0m. from lighting cigarette after puff-by puff. Cigarettes were machine-smoked and the total particulate matter was collected (1,0m3) in room, having no air filtration and substances were analysed and identified by gashromatography. The condacted quantitative and qualitative analyses show, that distance of exposition from burning cigarette can change the volume of benz(a)pirene. In the result of pyrolitic and photochemical reactions in tobacco smoke at certain air space temperature new structures can be formed with high toxity and cancerogenity. The dominant transformation process is reaction with photochemically-produced radicals, which produced benz(a)piren as a minor product. Additional factors effecting indoor concentrations include location and ventilation condition time. Ultrafine particle and benz(a)piren deposition and smoking behavior were observed. The mainstream smoke was also monitored continuously in real time (3, 5 and 10 minute) on a puff-by-puff. Our data show that smoking pastime can change the structure and volume of component of tobacco smoke. The level of benz(a)piren in air samples was evaluated as the main background index of cigarette smoke toxity in relatively small room, having no air filtration system. This question still needs to be explained. It would be interesting to investigate of tobacco smoke components in lung tissue after the smoking process. The studies are necessary in different derection.

Studies on size distribution and health risk of 37 species of polycyclic aromatic hydrocarbons associated with fine particulate matter collected in the atmosphere of a suburban area of Shanghai city, China.

Polycyclic aromatic hydrocarbons (PAHs) in suspended particulate matter (SPM) contribute significantly to health risk. Our objectives were to assess the size distribution and sources of 26 PAHs and 11 polycyclic aromatic compounds (PACs) in SPM in the suburban area, Shanghai city, China. Air sampling was carried out on the rooftop of a five-stories building in the campus of Shanghai University. An Andersen high-volume air sampler was employed to collect ambient size-segregated particles from August to September 2015. The toxic particulate PAHs were determined by the gas chromatography mass spectrometry. The concentrations of total PAHs (TPAHs) in SPM and PM1.1 (suspended particulate matter below 1.1 µm) were in the ranges of 4.58-14.5 ng m(-3) and 1.82-8.56 ng m(-3), respectively. 1,8-naphthalic anhydride showed the highest concentrations among 37 species of PAHs and PACs ranging 7.76-47.9 ng m(-3) and 1.50-17.6 ng m(-3) in SPM and PM1.1, respectively. The concentrations of high molecular weight 5-6 ring PAHs followed a nearly unimodal size distribution with the highest peak in PM1.1, while other lower molecular weight PAHs were not dependent on particle sizes. The toxicity analysis indicated that the carcinogenic potency of particulate PAHs primarily existed in PM1.1. Regarding meteorological parameters and other pollutants, the positive effect of humidity and NO2 over PAHs was confirmed. Diagnostic ration indicated that the particulate PAHs in Shanghai were mainly derived from motor-vehicle or petroleum combustion. The highest benzo[a]pyrene equivalent (BaPeq) in SPM and PM1.1 were 2.15 ng m(-3) and 1.43 ng m(-3) calculated by the toxicity equivalency factor, and 69.31 ng m(-3) and 47.81 ng m(-3) estimated by the potency equivalency factors, respectively. The highest contributors in the total carcinogenicity of the particulate PAHs were dibenzo[a,h]pyrene (46.2% and 45.0%) and benz[j]aceanthrylene (80.2% and 83.1%), respectively while benzo[a]pyrene is lower contributor than other carcinogenic PAHs.

Quantitative analysis of 3-OHB[a]P and (+)-anti-BPDE as biomarkers of B[a]P exposure in rats.

The aim of this study was to develop an analytical method for the determination the levels of metabolites of benzo[a]pyrene (B[a]P), 3-hydroxybenzo(a)pyrene (3-OHB[a]P) and (+)-anti-benzo(a)pyrene diol-epoxide [(+)-anti-BPDE, combined with DNA to form adducts], in rat blood and tissues exposed to B[a]P exposure by high-performance liquid chromatography with fluorescence detection (HPLC/FD), and to investigate the usefulness of 3-OHB[a]P and (+)-anti-BPDE as markers of intragastrical exposure to B[a]P in rats. The levels of 3-OH-B[a]P and B[a]P-tetrol I-1 released after acid hydrolysis of (+)-anti-BPDE in the samples were measured by HPLC/FD. The calibration curves were linear (r(2) > 0.9904), and the lower limit of quantification ranged from 0.34 to 0.45 ng/mL for 3-OHB[a]P and from 0.43 to 0.58 ng/mL for (+)-anti-BPDE. The intra- and inter-day stability assay data suggested that the method is accurate and precise. The recoveries of 3-OHB[a]P and (+)-anti-BPDE were in the ranges of 73.6 ± 5.0 to 116.5 ± 6.3% and 73.3 ± 8.5 to 141.2 ± 13.8%, respectively. A positive correlation was found between the concentration of intragastrical B[a]P and the concentrations of 3-OH-B[a]P and (+)-anti-BPDE in the blood and in most of the tissues studied, except for the brain and kidney, which showed no correlation between B[a]P and 3-OHB[a]P and between B[a]P and (+)-anti-BPDE, respectively. A sensitive, reliable and rapid HPLC/FD was developed and validated for analysis of 3-OHB[a]P and (+)-anti-BPDE in rat blood and tissues. There was a positive correlation between the concentration of 3-OHB[a]P or (+)-anti-BPDE in the blood and the concentration of 3-OHB[a]P or (+)-anti-BPDE in the most other tissues examined. The concentration of 3-OHB[a]P or (+)-anti-BPDE in the blood could be used as an indicator of the concentration of 3-OHB[a]P or (+)-anti-BPDE in the other tissues in response to B[a]P exposure. These results demonstrate that 3-OHB[a]P and (+)-anti-BPDE are potential biomarkers of B[a]P exposure, which would also be useful to assess the carcinogenic risks from B[a]P exposure.

Occupational exposure to polycyclic aromatic hydrocarbons: relations between atmospheric mixtures, urinary metabolites and sampling times.

PURPOSE: Occupational exposure to polycyclic aromatic hydrocarbons (PAHs) can be assessed by either air monitoring or biomonitoring using urinary 1-hydroxypyrene (1-OHP) or 3-hydroxybenzo(a)pyrene (3-OHBaP). The aim of this study was to understand the links between atmospheric PAHs and urinary metabolites, in order to improve the biomonitoring strategy for assessing carcinogenic risk. METHODS: Personal air sampling for pyrene and BaP measurements, and urines for 1-OHP and 3-OHBaP analyses of seven workers from electrode production plant were collected every day of the working week. RESULTS: High variability of atmospheric levels between activities and between days was observed, especially for gaseous pyrene. No correlation was found between urinary metabolites: 1-OHP maximum levels occurred for "electrode extrusion" activity; those of 3-OHBaP occurred for "raw materials dispatcher." Sixty percentage of 3-OHBaP maximum levels were observed in urines collected at the beginning of shift the last workday. Those of 1-OHP occurred at different sampling times, depending on the gaseous pyrene levels (not stopped by P3 respirators). Dermal absorption of PAHs was confirmed by significant effect of particulate pyrene on 1-OHP in the samples collected the morning of the following day (p < 0.02, n = 25). CONCLUSIONS: Lack of correlation between metabolites concentrations emphasizes the non-relevance of 1-OHP, from a non-carcinogenic gaseous and particulate compound, and the great interest of 3-OHBaP, from carcinogenic BaP. Its slower urinary elimination prevents the risk of exposure underestimation, and urinary analysis should be performed at the beginning of shift the end of working week, especially in case of high exposure variability.

Relevance of urinary 3-hydroxybenzo(a)pyrene and 1-hydroxypyrene to assess exposure to carcinogenic polycyclic aromatic hydrocarbon mixtures in metallurgy workers.

OBJECTIVES: In metallurgy, workers are exposed to mixtures of polycyclic aromatic hydrocarbons (PAHs) in which some compounds are carcinogenic. Biomonitoring of PAH exposure has been performed by measuring urinary 1-hydroxypyrene (1-OHP), a metabolite of pyrene which is not carcinogenic. This study investigated the use of 3-hydroxybenzo(a)pyrene (3-OHBaP), a metabolite of benzo(a)pyrene (BaP) which is the main carcinogenic component in PAHs, to improve carcinogen exposure assessment. METHODS: We included 129 metallurgy workers routinely exposed to PAHs during working hours. Urinary samples were collected at three sampling times at the beginning and at the end of the working week for 1-OHP and 3-OHBaP analyses. RESULTS: Workers in anode production showed greater exposure to both biomarkers than those in cathode or silicon production, with respectively, 71, 40, and 30% of 3-OHBaP concentrations exceeding the value of 0.4 nmol mol(-1) creatinine. No difference was observed between the 3-OHBaP levels found at the end of the penultimate workday shift and those at the beginning of the last workday shift. Within these plants, the 1-OHP/3-OHBaP ratios varied greatly according to the workers' activity and emission sources. Using linear regression between these two metabolites, the 1-OHP level corresponding to the guidance value for 3-OHBaP ranged from 0.7 to 2.4 µmol mol(-1) creatinine, depending on the industrial sector. CONCLUSIONS: This study emphasizes the interest of monitoring urinary 3-OHBaP at the end of the last workday shift when working week exposure is relatively steady, and the irrelevance of a single guideline value for 1-OHP when assessing occupational health risk.

Increased IL-4 mRNA expression and poly-aromatic hydrocarbon concentrations from children with asthma.

BACKGROUND: Asthma is the most common chronic childhood disease. Imbalance of cytokines released from T helper cells and environmental factors, such as exposure to poly-aromatic hydrocarbon (PAH), play pivotal roles in the pathogenesis of asthma. The aim of this study was to compare the mRNA expression patterns of Interleukin (IL)-4, interferon (IFN)-γ and Acyl Co A long chain 3 (ACSL3) in peripheral blood leukocytes of children with and without asthma. To correlate the obtained mRNA data with serum IL-4, IFN-γ and PAH levels. Further, to determine the effect of in vivo exposure to PAH on mRNA expression of IL-4, IFN-γ and ACSL3 genes in a rat model. METHODS: A total of 170 children below 16 years (85 pediatric asthma patients and 85 matched healthy controls) were randomly selected from the Riyadh Cohort, Saudi Arabia. Gene expression analysis was performed using qRTPCR. Serum IL-4, IFN-γ and PAH were measured using LINCOplex (human multiplex immunoassay kit) and HPLC respectively. RESULTS: IL-4 mRNA expression was significantly increased (P < 0.05) in children with asthma compared to healthy control group whereas no differences were observed for either IFN-γ or ACSL3 mRNA. Similarly, serum IL- 4 and PAHs concentration was significantly higher as well in children with asthma in whom IFN-γ was also significantly lower. Results obtained in rats showed that exposure to the benzopyrene prototype PAH resulted in a 2.6 fold (P < 0.001) increased IL-4 mRNA expression in blood. CONCLUSION: Peripheral blood IL-4 mRNA levels, serum concentration of this cytokine are elevated in children with asthma. Also, elevated levels of PAH were observed in children with asthma. Additionally, PAH administration in rodents resulted in an increased IL-4 mRNA which is supposed to partly mediate the inflammatory response noted in asthma.