Accumulation of polycyclic aromatic hydrocarbons (PAHs) in surface sediment residues of Mahanadi River Estuary: Abundance, source, and risk assessment.

In this study, we examined the distribution of polycyclic aromatic hydrocarbons (PAHs) in sediments from the Mahanadi River Estuary (MRE), identified sources, and evaluated the ecological toxicity. The PAHs distributions in MRE ranged from 13.1 to 685.4 ng g-1 (dry weight), with a mean value of 192.91 ± 177.56 ng g-1 (dry weight). Sediments at sites S11, S8, and S13 have the highest 3-rings, 4-rings, and 5-rings PAHs, respectively. In MRE, pyrene has a significantly higher concentration with a mean value of 30.51 ng g-1, followed by Fluoranthene (86.2 ng g-1), Chrysene (67.4 ng g-1), and Benzo(k)fluoranthene (54.2 ng g-1). Site S8 had a higher total PAH concentration than sites S11, S13, and S1. The diagnostic and principal component analysis suggests that PAHs originated from petroleum, oil, biomass, and coal combustion. Higher toxic and mutagenic equivalent quotients indicate potential aquatic toxicity and a need for continuous monitoring of MRE for PAHs pollution.

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.

A Mesocosm Assessment of the Effect of Bioturbation by the Ghost Shrimp (Lepidophthalmus louisianensis) on the Fate of Petroleum Hydrocarbons in the Intertidal Zone.

To fully assess the long-term impacts of oil spills like the 2010 Deepwater Horizon incident in the northern Gulf of Mexico, the potential for organisms other than microbes to affect the fate and distribution of the oil may have to be considered. This influence could be substantial for abundant bioturbating benthic animals like the ghost shrimp Lepidophthalmus louisianensis. An assessment of the influence of these ghost shrimp on petroleum hydrocarbons was conducted in laboratory micro- and mesocosms containing coastal Gulf of Mexico sediment, seawater, and oil or the polynuclear aromatic hydrocarbon (PAH) pyrene. In an experiment with pyrene added to the water column, the ghost shrimp presence lowered water-column pyrene concentrations. In an experiment with oil added to the sediment surface, the ghost shrimp presence decreased PAH concentrations in the sediment surface layer but increased these in the water column and subsurface sediment. A companion study and a mass-balance analysis indicated a net loss of PAHs through an enhancement of microbial degradation. In an experiment in which oil was added as a narrow subsurface layer in the sediment, the ghost shrimp presence appeared to broaden the oil's depth distribution. Taken together, these results demonstrate that ghost shrimp can significantly influence the biodegradation and distribution of spilled oil in coastal ecosystems. Environ Toxicol Chem 2020;39:637-647. © 2019 SETAC.

Status, sources, and risk assessment of polycyclic aromatic hydrocarbons in urban soils of Xi'an, China.

To identify status, source of polycyclic aromatic hydrocarbons (PAHs) in urban soils and to assess soil environmental quality in Xi'an City, China, total 45 soil samples were collected from surface layer (0-10 cm) in different functional areas. Total concentrations of 16 US EPA priority PAHs ranged from 149.9 to 5770 µg kg-1, with a mean of 1246 µg kg-1. High molecular weight (HMW) PAHs accounted for the majority (42.4-72.2%) of the total PAHs in the urban soils, and phenanthrene (Phe), fluorene (Flo), pyrene (Pyr), benzo(b)fluoranthene (BbF), and chrysene (Chr) were the major compounds. Concentrations of PAHs varied among different functional areas. High level of PAHs was particularly apparent in industrial zones and city road overpass, while low level was recorded in scenic spots and campus. The integration of isomer ratios, principal component analysis (PCA), and positive matrix factor (PMF) indicated that the sources of PAHs in Xi'an urban soils were mainly derived from vehicle emissions and coal combustion. Based on incremental lifetime cancer risks (ILCR) model, the urban soils from the three functional areas (industrial zone, urban road, and city road overpass) posed potential cancer risk, and the cancer risks of direct ingestion for children were apparently higher than that for adolescence and for adult, respectively. Therefore, attention should be paid to the health risk for children exposed to PAHs in the urban soils.

Assessment of Pb and pyrene accumulation in Scirpus triqueter assisted by combined alkyl polyglucoside and nitrilotriacetic acid application.

To understand the accumulation and uptake of polycyclic aromatic hydrocarbons (PAHs) and heavy metals by plants is an important part of the assessment of phytoremediation for PAHs and heavy metals co-contaminated soil. This study was an investigation of the accumulation and uptake of pyrene and lead (Pb) by Scirpus triqueter under the condition of alkyl polyglucoside (APG) and nitrilotriacetic acid (NTA) combined application. The results indicated that the accumulation of Pb by S. triqueter was significantly improved by NTA and APG addition into the soil. The pyrene accumulation in plant was also increased after application of APG when compared to the control treatment. However, the pyrene accumulation was decreased when APG was applied together with NTA. SEM and TEM images of root surface suggested that more Pb in the soil transferred to the plant by combined application of APG and NTA. More importantly, TEM images of xylem cells of S.triqueter root showed that permeability of cell membrane was improved by application of APG.

PAH determination based on a rapid and novel gas purge-microsyringe extraction (GP-MSE) technique in road dust of Shanghai, China: Characterization, source apportionment, and health risk assessment.

A novel cleanup technique termed as gas purge-microsyringe extraction (GP-MSE) was evaluated and applied for polycyclic aromatic hydrocarbon (PAH) determination in road dust samples. A total of 68 road dust samples covering almost the entire Shanghai area were analyzed for 16 priority PAHs using gas chromatography-mass spectrometry. The results indicate that the total PAH concentrations over the investigated sites ranged from 1.04µg/g to 134.02µg/g dw with an average of 13.84µg/g. High-molecular-weight compounds (4-6 rings PAHs) were significantly dominant in the total mass of PAHs, and accounted for 77.85% to 93.62%. Diagnostic ratio analysis showed that the road dust PAHs were mainly from the mixture of petroleum and biomass/coal combustions. Principal component analysis in conjunction with multiple linear regression indicated that the two major origins of road dust PAHs were vehicular emissions and biomass/fossil fuel combustions, which contributed 66.7% and 18.8% to the total road dust PAH burden, respectively. The concentration of benzo[a]pyrene equivalent (BaPeq) varied from 0.16µg/g to 24.47µg/g. The six highly carcinogenic PAH species (benz(a)anthracene, benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, dibenz(a,h)anthracene, and indeno(1,2,3-cd)pyrene) accounted for 98.57% of the total BaPeq concentration. Thus, the toxicity of PAHs in road dust was highly associated with high-molecular-weight compounds.

Sources appointment and ecological risk assessment of polycyclic aromatic hydrocarbons (PAHs) in sediments of Erhai Lake, a low-latitude and high-altitude lake in southwest China.

Sixteen polycyclic aromatic hydrocarbons (PAHs) were analyzed from the surficial sediments in Erhai Lake, a plateau lake in China. The results showed that except for acenaphthylene (Ace) Ace and Dibenz(a,h)anthracene (DBA), the central region contained individual PAHs at concentrations lower than those in other lake regions. Total concentration of the PAHs (ΣPAHs) in the sediments from Erhai Lake ranged from 32.42 to 558.53 mg/kg with a mean value of 256.70 mg/kg. The maximum value of ΣPAHs was observed in the north region of the lake and more than 10-fold higher than the minimum values. Moreover, high molecular weight (HMW) PAHs, especially 5-ring PAHs, accounted for higher ratios up to 76 % relative to other PAHs compound in almost all sampling sites. Molecular diagnostic ratios including anthtacene (Ant)/(Ant + phenanthrene (Phe)), fluoranthene (Flt)/(Flt + pyrene (Pyr)), benz(a)anthracene (BaA)/(BaA + chrysene (Chr)), and indeno(1,2,3-cd)pyrene (IPY)/(IPY + benz(g,h,i)perylene (BPE)) were recorded at all sampling sites and indicated that the origin of PAHs in Erhai Lake was predominately pyrolytic. Furthermore, principal component analysis with component dominating by HMW PAHs showed that combustion origins were the primary contamination sources of PAHs in the sediments of Erhai Lake. Finally, ecological risk assessment indicated that the sediments from Erhai Lake are exposed to potential low risk for ΣPAHs, and the ecological risk decreases in the order of northern region > southern region > central region.

Quantitative Assessment of Parametric Uncertainty in Northern Hemisphere PAH Concentrations.

We quantitatively examine the relative importance of uncertainty in emissions and physicochemical properties (including reaction rate constants) to Northern Hemisphere (NH) and Arctic polycyclic aromatic hydrocarbon (PAH) concentrations, using a computationally efficient numerical uncertainty technique applied to the global-scale chemical transport model GEOS-Chem. Using polynomial chaos (PC) methods, we propagate uncertainties in physicochemical properties and emissions for the PAHs benzo[a]pyrene, pyrene and phenanthrene to simulated spatially resolved concentration uncertainties. We find that the leading contributors to parametric uncertainty in simulated concentrations are the black carbon-air partition coefficient and oxidation rate constant for benzo[a]pyrene, and the oxidation rate constants for phenanthrene and pyrene. NH geometric average concentrations are more sensitive to uncertainty in the atmospheric lifetime than to emissions rate. We use the PC expansions and measurement data to constrain parameter uncertainty distributions to observations. This narrows a priori parameter uncertainty distributions for phenanthrene and pyrene, and leads to higher values for OH oxidation rate constants and lower values for European PHE emission rates.

Sources and ecological risk assessment of PAHs in surface sediments from Bohai Sea and northern part of the Yellow Sea, China.

Sources and ecological risk of sixteen priority PAHs in surface sediments from Bohai Sea (BS) and northern part of the Yellow Sea (NPYS) were investigated. The total concentrations of PAHs varied in ranges 149.24-1211.81 and 148.28-907.47 ng/g for BS and NPYS, respectively. Principal component analysis-multiple linear regression (PCA-MLR) suggested that coal combustion, vehicular emission and coke oven could be the primary PAH contributors, accounting for 56.6%, 29.2% and 14.2% of PAH concentrations, respectively. Analysis with sediment quality guidelines (SQGs) indicated that acenaphthylene, fluorene, phenanthrene, fluoranthene, pyrene and dibenzo(a,h)anthracene may occasionally cause adverse biological effects in some stations. Organic carbon (OC)-normalized analysis and mean effects range-median quotient (M-ERM-Q) suggested that the combined ecological risk of PAHs was generally low. The toxic equivalent concentrations of carcinogenic PAHs were 12.87-64.6 ng/g-BaP(eq) and 5.95-68.80 ng/g-BaP(eq) in BS and NPYS, respectively, suggesting low carcinogenic risk for both BS and NPYS.

Assessment of nitro-polycyclic aromatic hydrocarbons in PM1 near an area of heavy-duty traffic.

The objective of this research was to evaluate nitro-polycyclic aromatic hydrocarbons (NPAHs) associated with ultrafine airborne particles (PM1) in areas affected by vehicles in the metropolitan area of Porto Alegre (MAPA), RS, Brazil. Extraction, isolation/derivatization, and subsequently gas chromatography with electron capture detection (GC/ECD) were the techniques used to extract and determine NPAHs (1-nitronaphthalene, 2-nitrofluorene,3-nitrofluoranthene,1-nitropyrene, and 6-nitrochrysene) associated with PM1 Airborne particles (PM1) were collected using PTFE filters in a PM162M automatic sampler. The analytical method was validated by the Standard Reference Material - SRM 1649 b - from the National Institute of Standards and Technology (NIST, USA). The results were consistent with the certified values. 3-NFlt and 6-NChr reached highest concentrations of 0.047 ng·m(-3) and 0.0284 ng·m(-3), respectively, in Sapucaia do Sul and Canoas. Seasonal variation showed higher NPAH concentrations in cold days. The NPAHs associated with PM1 were correlated with the pollutants nitrogen oxides and NPAHs with meteorological variables: temperature and wind speed. The results indicated that vehicles with diesel engines were influential. This was confirmed by the study of the ratios NPAHs/PAHs, 1-NPyr/Pyr, and 6-NChr/Chr.

Probabilistic ecological risk assessment of polycyclic aromatic hydrocarbons in southwestern catchments of the Bohai Sea, China.

A probability risk assessment was undertaken to study the individual and combined ecological risks induced by six polycyclic aromatic hydrocarbons (PAHs) both in surface water and sediment from southwestern catchments of the Bohai Sea, China. The actual measured PAH concentrations in water and sediment were compared with toxicity effect data (the 10th percentile of predicted no effect concentration) to calculate the risk quotients (RQs) for an individual PAH. The equilibrium partitioning method was applied to estimate toxicity data in sediment. A method based on the equivalent concentration concept was proposed and applied to assess the combined ecological risk of multiple PAHs. Monte Carlo simulation and bootstrap technique were utilized to calculate the distribution of RQs and associated uncertainties. The ecological safety level was defined by RQ ≤ 1. Results indicated that both in water and sediment, fluoranthene and pyrene posed the highest risks, whereas acenaphthene and fluorene posed negligible risks. Naphthalene and phenanthrene did not pose risks to the ecological community in surface water but had relatively higher risks in sediment. The median RQs of combined risk in surface water and sediment were 0.934 and 2.42, and the probabilities of RQ > 1 were up to 0.473 and 0.599, respectively, which were much higher than the individual compound acting alone. The risk level in sediment was quite higher than in surface water probably owing to the non-equilibrium distribution between two phases, which suggested that local authorities should focus more on sediment quality management.

Risk assessment of polycyclic aromatic hydrocarbons in aquatic ecosystems.

A probability risk assessment of anthracene, benzo(a)pyrene, chrysene, fluorene, phenanthrene and pyrene was carried out to examine the ecological risk of these six polycyclic aromatic hydrocarbons (PAHs) in aquatic ecosystems in China. The literature on PAH concentrations in surface water in China was collected to evaluate the environmental exposure concentrations (EEC). The 10th percentile of predicted no observed effect concentration (PNEC(10%)) of PAHs, calculated according to the data from the USEPA AQUIRE database and regulatory reviews, was applied as the toxicity assessment endpoint. The ratio of EEC and PNEC(10%), expressed as a risk quotient (RQ), was used to characterize the risk value. Bootstrapping method and Monte Carlo simulation were utilized to calculate the distribution of EEC, PNEC(10%), RQ and associated uncertainties. Risk assessment showed that reliable maximum RQs of anthracene, benzo(a)pyrene, chrysene, fluorene and phenanthrene were in the range of 0.064-0.755, lower than the acceptable value of 1. However, the reliable maximum RQ of pyrene was 1.39, indicating its potential ecological risk. Notwithstanding the uncertainty, these results suggest that the aquatic ecosystems with high PAH concentrations might pose potential ecological risks, and concerted efforts are required to ensure that surface water is protected.

Assessment of pyrene bioavailability in soil by mild hydroxypropyl-ß-cyclodextrin extraction.

Bioavailability of organic pollutants in soil is currently a much-debated issue in risk assessment of contaminated sites. Ecorisk of an organic pollutant in soil is strongly influenced by the properties of the soil and its contamination history. To evaluate the effect of aging on the availability of pyrene, earthworm (Eisenia fetida) accumulation and chemical extraction by exhaustive and nonexhaustive techniques in soil spiked with a range of pyrene levels (1.07, 9.72, 88.4, 152, and 429 µg g⁻¹ dry soil) were measured in this study using both unaged (i.e., 0 days) and aged (i.e., 69, 150, and 222 days) soil samples. The results showed that the amount of pyrene accumulated by earthworms did not change greatly with aging time under different high-dose contamination levels, but changed significantly at lower concentrations. Moreover, aging (after 222 days) significantly decreased biological and chemical availability of pyrene. Furthermore, the relationship between earthworm bioaccumulation, hydroxypropyl-ß-cyclodextrin (HPCD), and organic solvent extraction was investigated in order to find a suitable and rapid method to predict pyrene bioavailability. Results showed that, at different levels of pyrene, the mean values of earthworm uptake and HPCD extractability were 10-40% and 10-65%, respectively. Correlation (r² = 0.985) and extraction results for pyrene suggested that mild HPCD extraction was a better method to predict bioavailability of pyrene in soil compared with organic solvent extraction.

Exposure of children to polycyclic aromatic hydrocarbons in Mexico: assessment of multiple sources.

PURPOSE: Biological monitoring of polycyclic aromatic hydrocarbons (PAHs) has expanded rapidly since urinary 1-hydroxypyrene (1-OHP) was suggested as a biological index for pyrene. Taking into account that pyrene is often present in PAHs mixtures, 1-OHP has also been considered an indirect indicator of exposure to these mixtures. Sources of PAHs in developing countries are numerous; however, exposure of children to PAHs has not been studied in detail. Therefore, the aim of this study was to assess exposure of children to PAHs in different scenarios: (a) children living next to highways with heavy traffic; (b) sanitary landfill; (c) brick kiln communities and (d) children exposed to biomass combustion. METHODS: A total of 258 children (aged 3-13) participated in the study. The analyses were performed by HPLC with fluorescence detector. Urinary 1-OHP concentrations were then adjusted by urinary creatinine. RESULTS: The highest levels of 1-OHP in this study were found in children exposed to biomass combustion (mean value 3.25 micromol/mol creatinine), but exposure was also detected in children living in communities with brick kiln industry (mean 0.35 micromol/mol creatinine), or in a community next to a sanitary landfill (with waste combustion) (0.30 micromol/mol creatinine) and in children exposed to traffic (mean value 0.2 micromol/mol creatinine and 0.08 micromol/mol creatinine). CONCLUSIONS: Considering our results and taking into account that millions of children in Mexico are living in scenarios similar to those studied in this work, the assessment of health effects in children exposed to PAHs is urgently needed; furthermore, PAHs have to be declared contaminants of concern at a national level.

1-Hydroxypyrene--a biochemical marker for PAH pollution assessment of aquatic ecosystem.

The aim of the present study was to assess aquatic contamination by polycyclic aromatic hydrocarbons (PAH), using the 1-hydroxypyrene (1-OHP) content in fish bile as a biochemical marker. A total of 71 chub (Leuciscus cephalus L.) were collected from seven locations on the Svitava and Svratka rivers in and around the industrial city of Brno, Czech Republic. The levels of 1-OHP were determined by reverse phase HPLC with fluorescence detection after deconjugation. Normalising the molar concentration of the biliary 1-OHP to the biliary protein content reduced sample variation. The content of 1-OHP was correlated with the PAH level in bottom sediment and semi-permeable membrane devices (SPMD), which was analyzed by a combination of HPLC/FLD and GC/MS methods. The highest mean values of 1-OHP were found in fish caught at the Svratka River at locations Modrice (169.2 ± 99.7 ng · mg(-1) protein) and Rajhradice (152.2 ± 79.7 ng · mg(-1) protein), which are located downstream from Brno. These values were significantly (P < 0.05) higher than those obtained from localities Knínicky (98.4 ± 66.1 ng · mg(-1) protein) and Bílovice nad Svitavou (64.1 ± 31.4 ng · mg(-1) protein). The lowest contents of PAH in sediment and SPMD were found at location Knínicky (1.5 mg · kg(-1) dry mass and 19.4 ng · L(-1), respectively). The highest contents of PAH in sediment and SPMD were found in Rajhradice (26.0 mg · kg(-1) dry mass) and Svitava before junction (65.4 ng · L(-1)), respectively. A Spearman correlation test was applied to determine the relationship between biliary 1-OHP and the sum of PAH in sediment and SPMD. A positive, but no statistically significant correlation was found. The main impact sources of elevated level of PAHs in sites located downstream from Brno are most probably intensive industrial and agricultural activities and domestic waste.

[Assessment of exposure to polycyclic aromatic hydrocarbons in Japanese children].

OBJECTIVES: To estimate the level of exposure to polycyclic aromatic hydrocarbons (PAHs) in Japanese children by urinary metabolite analysis and the possible contribution of soil ingestion and environmental tobacco smoke (ETS) to PAHs exposure. METHODS: Spot urine samples and questionnaire data were collected from 107 kindergarten children (3-6 yrs) and their mother. The urinary concentration of 1-hydroxypyrene (1-OHP), a biomarker of PAHs exposure, was measured using a high performance liquid chromatography-fluorescence detector. RESULTS: The geometric mean (GM) of urinary 1-OHP concentrations in children was 0.065 mumol/mol-cre (geometric standard deviation=1.88). Parental smoking and time of playing outside (surrogate of soil exposure level) did not increase urinary 1-OHP level. Maternal urinary 1-OHP concentration correlated with, whereas GM (0.038 mumol/mol-cre) was significantly lower than, the urinary 1-OHP concentration in children. The latter might be attributable to greater amount of food intake per body weight for children than for adult. CONCLUSIONS: The contribution of ETS and soil ingestion to PAHs exposure seemed to be small and thus they cannot be the major source of PAHs in Japanese children.

Site contamination health risk assessment case study involving tenant relocation from a former gasworks site.

An Adelaide suburban public-housing residential site with 16 apartments was investigated after complaints of odor in some yard areas. A distinct 0.5-m layer of dark, odorous (tarry), contaminant material, which in some areas had been covered with plastic sheeting, was subsequently found beneath the topsoil across most of the site. This material appeared to extend beneath the apartments. Analysis indicated high levels of cyanide and polycyclic aromatic hydrocarbons (PAHs), consistent with gasworks waste. Historical investigation revealed that the site was originally owned by a gas company and that a large gasometer (gas-storage tank) existed in one corner of the site. This finding of significant soil contamination precipitated a decision by the health and housing authorities to notify tenants immediately and to plan for their relocation. In addition to tending to the consequent personal disruption and logistical difficulties this posed, a detailed risk assessment process was developed. Urine samples were collected before and after relocation and analyzed for 1-hydroxypyrene (1-OHP), a biomarker for polycyclic aromatic hydrocarbon (PAH) exposure. In addition, samples of tap water, indoor and outdoor air, indoor and ceiling dust, carpets, and soil from tillage areas were analyzed for PAHs. Data indicated a low health risk associated with tenancy on the site. This report presents details of the health risk assessment process undertaken and discusses vindicative reasons for tenant relocation.

1,2-Dimethylimidazole-4-sulfonyl chloride, a novel derivatization reagent for the analysis of phenolic compounds by liquid chromatography electrospray tandem mass spectrometry: application to 1-hydroxypyrene in human urine.

A novel derivatization method employing 1,2-dimethylimidazole-4-sulfonyl chloride (DMISC) to improve the mass spectrometric response for phenolic compounds in liquid chromatography electrospray ionization mass spectrometry (LC-ESI-MS) and tandem mass spectrometry (LC-ESI-MS/MS) is described. Several environmentally relevant compounds, including chloro-, aryl- and alkylphenols, steroidal estrogens, and hydroxy-polycyclic aromatic hydrocarbons (OHPAHs), were selected to evaluate this technique. A facile derivatization procedure employing DMISC results in dimethylimidazolesulfonyl (DMIS) derivatives that are stable in aqueous solution. These DMIS derivatives produced intense [M+H](+) ions in positive-ion LC-ESI-MS. The product ion spectra of the [M+H](+) ions of simple phenols were dominated by ions representing the DMIS and dimethylimidazole moieties, whereas product ion spectra of the DMIS derivatives of OHPAHs with three or more fused aromatic rings showed prominent ArO(+) ions, the relative intensity of which increased with the number of rings. The DMIS derivatives of the selected phenolic compounds showed excellent chromatographic properties. To substantiate the utility of derivatization with DMISC, an analytical method employing enzyme hydrolysis, solid phase extraction, derivatization with DMISC, and analysis by LC-ESI-MS/MS with multiple reaction monitoring for determination in human urine of 1-hydroxypyrene, a widely used biomarker for the assessment of human exposure to PAHs, was developed and validated.

1-hydroxypyrene as a biomarker of PAH exposure among subjects living in two separate regions from a steel mill.

OBJECTIVE: Steel mills are known to be a source of ambient polycyclic aromatic hydrocarbons (PAHs), and increased cancer risk has been reported among neighborhoods previously. In this study, we tried to assess the exposure to PAHs among residents nearby to a large steel mill in Korea by measuring urinary 1-hydroxypyrene (1-OHP). METHODS: Two separate areas at different distances from a steel mill but on the same wind direction were chosen to evaluate the environmental exposures to polycyclic aromatic hydrocarbons. Three-hundred and fifty children living in the vicinity of steel plant ("nearby" group) and 606 children residing much farther from the factory ("remote" group) participated. Urine was collected on three consecutive days, and questionnaires about exposure to passive smoking and food consumption as well as demographics were obtained. Routine monitoring data of ambient pollutants were obtained and particulate matter less than 10 microm (PM10) was analyzed with multiple regressions to assess the associations with urinary 1-OHP. RESULTS: The geometric mean concentration of urinary 1-OHP among nearby group (0.048+/-1.878 micromol/mol creatinine, GM+/-GSD) was approximately 1.3 times higher than that among remote group (0.036+/-2.425 micromol/mol creatinine, GM+/-GSD), and using multiple regression techniques, the difference was significant (P<0.0001) after adjusting for confounding variables. When different periods before the sampling of urine were examined, PM10 averages over 2 days, 3 days, and 1 week prior to urine sampling showed significant associations with urinary 1-OHP levels. CONCLUSION: Our findings are consistent with the interpretation that residents nearby to a steel mill are exposed to PAHs through ambient exposures.

An assessment of occupational exposure to polycyclic aromatic hydrocarbons in the UK.

A cross-industry occupational hygiene survey was commissioned by the Health and Safety Executive (HSE) to determine the levels of polycyclic aromatic hydrocarbon (PAH) exposure in UK industry and to determine if one or more target analytes were suitable as markers for assessing total exposure to PAHs. There were no broadly applicable UK exposure standards for assessing total exposure to PAHs. Until 1993 a guidance value for assessing exposure in coke ovens only, where PAH exposure is known to be the highest, was based on gravimetric analysis of cyclohexane-soluble material. Biological monitoring based on urinary 1-hydroxypyrene (1-OHP) is widely reported to be an effective indicator of exposure by both dermal and inhalation routes but there was no UK guidance value. The survey involved an occupational hygiene study of 25 sites using both airborne monitoring of a total of 17 individual PAHs and biological monitoring. The results showed 8 h TWA levels of total PAH in air ranged from 0.4 to 1912.6 microg m(-3) with a GM of 15.8 microg m(-3). The profile of PAHs was dominated by naphthalene, the most volatile 2-ring PAH. Airborne benzo(a)pyrene (BaP) correlated well (r(2) = 0.971) with levels of carcinogenic 4-6 ring PAHs and was an effective marker of exposure for all industries where significant particle bound PAH levels were found and, in particular, for CTPV exposure. The 8 h TWA levels of BaP ranged from <0.01 to 6.21 microg m(-3) with a GM of 0.036 microg m(-3); 90% were <0.75 microg m(-3) and 95% were <2.0 microg m(-3). Two hundred and eighteen urine samples collected from different workers at the end of shift and 213 samples collected pre-shift next day were analysed for 1-OHP. Levels of 1-OHP in end-of-shift samples were generally higher than those in pre-shift-next-day samples and showed a good correlation (r(2) = 0.768) to airborne BaP levels if samples from workers using respiratory protection or with significant dermal exposure were excluded. Urinary 1-OHP in end-of-shift samples ranged from the limit of detection (0.5 micromol mol(-1) creatinine) to 60 micromol mol(-1) creatinine with a mean of 2.49 micromol mol(-1) and a 90th percentile value of 6.7 micromol mol(-1) creatinine. The highest 1-OHP levels were found in samples from workers impregnating timber with creosote where exposure was dominated by naphthalene. If the 11 samples from these workers were excluded from the dataset, the 90% value for end-of-shift urine samples was 4 micromol mol(-1) creatinine (n = 207) and this value has since been adopted by the HSE as a biological monitoring benchmark value.