Urinary Monohydroxylated Polycyclic Aromatic Hydrocarbons Research Articles

Association of occupational exposure to polycyclic aromatic hydrocarbons in workers with hypertension from a northeastern Chinese petrochemical industrial area

Elevated urinary polycyclic aromatic hydrocarbon metabolites have been linked to an increased risk of cardiovascular diseases (CVDs). However, for petrochemical workers with potentially high PAH exposure, it remains largely unknown whether the link will be amplified. Thus, this work aimed to investigate 14 urinary mono-hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in 746 petrochemical workers working in a Chinese petrochemical industrial area and their association with the risk of hypertension using the binary logistic regression. Metabolites of naphthalene, fluorene, phenanthrene, and pyrene were frequently detected in the 746 urine samples analyzed (>98%), with Σ10OH-PAH concentration in the range of 0.906–358 ng/mL. 2-hydroxynaphthalene accounted for the largest proportion of ten detected OH-PAHs (60.8% of Σ10OH-PAHs). There were significant correlations between these metabolites and other factors, including gender, age, and body mass index. Diastolic blood pressure, not systolic blood pressure, was significant positively associated with the urinary Σ10OH-PAH concentrations of the petrochemical workers. Elevated urinary 2/3-OH-Flu was significantly associated with an increased risk of hypertension (adjusted odds ratio: 1.96, 95% confidence interval: 1.20–3.18, p = 0.007), suggesting that PAH exposure in petrochemical workers was a driving factor of hypertension. In the stratified analysis, the association was more pronounced in those who were overweight with older age. Although the PAH exposure risk in petrochemical workers based on the estimated daily intakes was relatively low. Given the long-term impact, we call attention to CVDs of petrochemical workers.

Associations between urinary monohydroxylated polycyclic aromatic hydrocarbons and unexplained recurrent spontaneous abortion and health risk assessment in a large case-control study in China

Polycyclic aromatic hydrocarbons (PAHs) are a group of environmental endocrine disruptors with known carcinogenic, reproductive, and developmental toxicity. Important knowledge gaps remain regarding the relationship between PAH exposure and unexplained recurrent spontaneous abortion (URSA). In the present study, twelve monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) were measured in the urine of 413 URSA cases and 434 controls. The main OH-PAHs measured in this study were monohydroxy metabolites of naphthalene, followed by fluorene and phenanthrene. After the creatinine correction, the median concentration of urinary OH-PAHs in the control group (17.4 μg/g Creatinine) was higher than that in the case group (14.2 μg/g Creatinine). There was no positive relationship between PAH exposure and URSA using binary logistic regression analysis. Among 847 Chinese women of childbearing age, residential environment, type of drinking water, and education level were the influencing factors of PAH exposure. The health risk assessment showed that over 98% of women had a carcinogenic risk with carcinogenic risk values above the acceptable level (10−6). Although this large-scale case-control study did not observe an association between PAH exposure and URSA, more attention should be paid to the high carcinogenic risk due to PAH exposure in women of reproductive age.

Improvement on recovery and reproducibility for quantifying urinary mono-hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs)

Efficient and reproducible measurements of multiple polycyclic aromatic hydrocarbon (PAH) metabolites in urinary samples are required to evaluate the complex health effects of PAH exposure. Here, we demonstrate a highly practical, automated off-line solid-phase extraction (SPE) of deconjugated hydroxylated PAHs followed by LC-MS/MS to simultaneously measure eight mono-hydroxylated PAH compounds: 1-hydroxynaphthalene, 2-hydroxynaphthalene, 2-hydroxyfluorene, 1-hydroxyphenanthrene, 2&3-hydroxyphenanthrene, 4-hydroxyphenanthrene and 1-hydroxypyrene. Initially, we observed low recovery rates (e.g., 16% for 1-hydroxypyrene) when using previously published methods. We optimized the procedure by choosing polymeric absorbent-based cartridges, automating the sample loading step by diluting samples with 15% methanol/sodium acetate, and most importantly, replacing acetonitrile with methanol as the eluting solvent. Optimized sample preparation has improved the recovery rates to more than 69% for analytes of interest. This improvement led to higher method sensitivity and detection frequency, especially for 1-hydroxypyrene, in all of 100 urine samples collected in the New York City site of the Legacy Girls Study. The limits of detection ranged from 7.6 pg/mL to 20.3 pg/mL using 1 mL of urine, compared to the 2 mL required in CDC, method 09-OD. The average coefficients of variance of quality control samples (n = 60) ranged between 7 and 21%; variance of repeated measurements (n = 45) was less than 10%. This efficient and reliable method for measuring PAH metabolites will greatly benefit epidemiology studies and biomonitoring programs.

C-Reactive Protein Gene Polymorphisms Correlated with Serum CRP Levels of Diesel Engine Exhaust-Exposed Workers

Objective: To assess the association between circulating C-reactive protein (CRP), and CRP polymorphisms in the diesel engine exhaust (DEE)-exposed workers. Methods: In 137 DEE-exposed workers and 127 unexposed comparable control workers, six urinary mono-hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) and serum CRP levels were assayed. Genotyping of four CRP single-nucleotide polymorphisms (SNPs) was measured. Results: Serum CRP levels increased in exposed versus control workers (all p < 0.001). In the DEE-exposed workers, two CRP polymorphisms were associated with serum CRP levels, the subjects of rs1205 TT genotype had lower serum CRP levels (p < 0.05 compared to TC or CC). Conclusions: Our findings suggest that polymorphisms in CRP and circulating CRP involved in the inflammatory process may play significant roles in human sensitivity to lung function injury caused by DEE exposure. This study will help investigate the underlying mechanisms of adverse respiratory effects induced by DEE.

Urinary monohydroxylated polycyclic aromatic hydrocarbons in primiparas from Shenzhen, South China: Levels, risk factors, and oxidative stress

The main objectives of the present study were to investigate urinary monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in 77 primiparas who live in Shenzhen, Guangdong Province, China, and their association with 8-hydroxy-2′-deoxyguanosine (8-OHdG) and human health risks. High detection frequencies of OH-PAHs demonstrated the wide occurrence of chemicals in the human exposure to PAHs. The urinary concentrations of Σ7OH-PAHs ranged from 1.37 to 45.5 ng/mL, and the median concentrations of 1-hydroxynaphthalene (1-OHN), 2-hydroxynaphthalene (2-OHN), 2-hydoxyfluorene (2-OHF), ΣOHPhe (the sum of 1-, 2+ 3-hydroxyphenanthrene), and 1-hydroxypyrene (1-OHP) were 3.00, 2.58, 0.31, 0.44, and 0.51 ng/mL, respectively. In the sum concentration of seven OH-PAHs, 1-OHN accounted for the largest proportion (43.7% of Σ7OH-PAHs), followed by 2-OHN (37.1%), 2-OHF (4.94%), 1-OHP (8.01%), 1-OHPhe (4.79%), and 2+3-OHPhe (1.46%). The present results showed that vehicle exhaust and petrochemical emission are the main sources of PAHs in primiparas in Shenzhen, and inhalation is the most important exposure route. The living conditions have a significant influence on human exposure to PAHs. The concentrations of 8-OHdG were positively correlated with OH-PAH concentrations in urine because evidence suggested that urinary 8-OHdG levels can be considered as a biomarker of oxidative DNA damage. Hazard quotient was used to assess the human health risks from exposure to single compound, and hazard index was used to assess the cumulative risks of the compounds, which demonstrated that the exposure risks from PAHs in primiparas were relatively low.

Determination of Ten Kinds of Monohydroxylated Polycyclic Aromatic Hydrocarbons in Human Urine by Supported Liquid Extraction Followed by Liquid Chromatography-Tandem Mass Spectrometry

Abstract The monitoring of urinary monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) can be used for risk assessment of human exposure to polycyclic aromatic hydrocarbons (PAHs). In this work, we developed a novel pretreatment method based on supported liquid extraction (SLE) for determination of 10 kinds of OH-PAHs by liquid chromatography- tandem mass spectrometry (LC-MS/MS). Urine samples were extracted with a mixed solvent of dichloromethane/n-hexane (3:7, V/V) by an SLE clean-up using a diatomaceous earth minicartridge. The results indicated that the developed pretreatment procedure gave good recoveries, while also significantly reducing the interference of the biological matrix. At three concentration levels (10, 50 and 100 μg L−1), the recoveries of 10 kinds of OH-PAHs ranged from 88.5% to 120.9%, and the repeatability ranged from 1.6% to 8.1%. The limits of detection ranged from 0.06 μg L−1 to 0.30 μg L−1, and the limits of quantification were between 0.2 μg L−1 and 1.0 μg L−1. This method was finally successfully applied for the determination of OH-PAHs in urine samples collected from primary school students in Guangdong. The results showed that 2-hydroxynaphthalene was the dominant compound, with a highest concentration of 4.83 μg L−1.

Combined effect of urinary monohydroxylated polycyclic aromatic hydrocarbons and impaired lung function on diabetes

Associations of type 2 diabetes with exposure to polycyclic aromatic hydrocarbons and reduced lung function have been reported. The aim of the present study was to investigate effect of reduced lung function and exposure to background PAHs on diabetes. A total of 2730 individuals were drawn from the Wuhan-Zhuhai (WHZH) Cohort Study (n=3053). Participants completed physical examination, measurement of lung function and urinary monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs). Risk factors for type 2 diabetes were identified by multiple logistic regression analysis, and the presence of additive interaction between levels of urinary OH-PAHs and lower lung function was evaluated by calculation of the relative excess risk due to interaction (RERI) and attributable proportion due to interaction (AP). Urinary OH-PAHs levels was positively associated with type 2 diabetes among individuals with impaired lung function (p<0.05). Forced expiratory volume in one second (FEV1, odd ratio (OR): 0.664, 95% confidence interval (CI): 0.491–0.900) and forced vital capacity (FVC, OR: 0.693, 95% CI: 0.537–0.893) were negatively associated with diabetes among individuals. Additive interaction of higher urinary levels of OH-PAHs and lower FVC (RERI: 0.679, 95% CI: 0.120–1.238); AP: 0.427, 95% CI: 0.072–0.782) was associated with diabetes. Exposure to background PAHs was related to diabetes among individuals with lower lung function. Urinary levels of OH-PAHs and reduced lung function had an additive effect on diabetes.

Increased levels of etheno-DNA adducts and genotoxicity biomarkers of long-term exposure to pure diesel engine exhaust

Etheno-DNA adducts are biomarkers for assessing oxidative stress. In this study, the aim was to detect the level of etheno-DNA adducts and explore the relationship between the etheno-DNA adducts and genotoxicity biomarkers of the diesel engine exhaust (DEE)-exposed workers. We recruited 86 diesel engine testing workers with long-term exposure to DEE and 99 non-DEE-exposed workers. The urinary mono-hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) and etheno-DNA adducts (εdA and εdC) were detected by HPLC–MS/MS and UPLC–MS/MS, respectively. Genotoxicity biomarkers were also evaluated by comet assay and cytokinesis-block micronucleus assay. The results showed that urinary εdA was significantly higher in the DEE-exposed workers (p<0.001), exhibited 2.1-fold increase compared with the non-DEE-exposed workers. The levels of urinary OH-PAHs were positively correlated with the level of εdA among all the study subjects (p<0.001). Moreover, we found that the increasing level of εdA was significantly associated with the increased olive tail moment, percentage of tail DNA, or frequency of micronucleus in the study subjects (p<0.01). No significant association was observed between the εdC level and any measured genotoxicity biomarkers. In summary, εdA could serve as an indicator for DEE exposure in the human population.

Determination of ten monohydroxylated polycyclic aromatic hydrocarbons by liquid–liquid extraction and liquid chromatography/tandem mass spectrometry

The aim of this study is to develop and validate an analytical method for the quantitation of ten urinary monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) through high pressure liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). After enzymatic deconjugation, urine samples were extracted by liquid–liquid extraction (LLE) and OH-PAHs were analyzed by HPLC/MS/MS operated in negative electrospray ionization (ESI) and multiple reaction monitoring (MRM) mode. LLE was conducted with the solvent mixture of pentane and toluene, which reduced the matrix interferences and enhanced the method sensitivity significantly. Deuterated and 13C-labeled analogs are used as internal standards. Calibration curves of all target analytes shows favorable linearity within the concentration range of 5.9–15,000.0ng/L for different OH-PAHs with the regression coefficients above 0.993. The limits of detection (LODs) in pooled urine ranged from 1.72 to 17.47ng/L, which were much lower than those obtained by a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. The method shows satisfactory accuracy and precision when analyzing three different levels of OH-PAHs spiked in pooled urine. Except for 1-hydroxynaphthalene, recoveries of other OH-PAHs were in the range of 100±20% with a variation coefficient of less than 13%. The measurement of OH-PAHs from a QC sample of the Centers for Disease Control and Prevention (CDC) generated results close to the values measured by CDC. This method has been successfully employed in the California Biomonitoring Program.