Assessment of PAH exposure and health risks among South Korean firefighters based on urinary PAH metabolites.

Polycyclic aromatic hydrocarbons (PAHs) comprise a group of compounds resulting from the incomplete combustion of organic matter. Firefighters engaged in fire suppression are highly exposed to PAHs. This study centered on evaluating the exposure levels and health risks of PAHs in South Korean firefighters involved in firefighting activities. The concentrations of 10 PAH metabolites in the urine of firefighters were measured immediately after, and two weeks post their engagement in extinguishing a large tire factory fire. The levels of OH-PAHs in urine samples immediately after fire suppression were elevated by a factor of 1.01-1.84 compared to urine samples from non-exposed period. The median concentration of total PAH metabolites (OH-PAHs) was higher in urine samples immediately after fire suppression (5910 ng/g creatinine) than in urine samples from non-exposed periods (5020 ng/g creatinine). However, the ∑OH-PAH levels in firefighters' urine were related to personal habits such as smoking. The concentrations of all individual OH-PAHs in the urine samples of nonsmokers exhibited a substantial increase, ranging from 1.37 to 2.3 times, clearly demonstrating that firefighting activities were a substantial source of PAH exposure. The calculated values associated with the health risks stemming from exposure to PAHs, including carcinogenic risk, total estimated daily intake (TEDI), and hazard quotients/index (HQs/HI), all fell within acceptable limits, indicating negligible risk. However, the HQ/HI values and TEDI for individual and total PAH exposures, except those for naphthalene, were 1.36-2.00 times higher in firefighters' samples taken after firefighting operations compared to those during regular duty. This underscores the need for more comprehensive investigations to comprehend the singular impact of firefighting activities due to the diverse sources of PAH emissions in the environment.

Identification of organic chemical indicators for tracking pollution sources in groundwater by machine learning from GC-HRMS-based suspect and non-target screening data.

In this study, the strong analytical power of gas chromatography coupled to a high resolution mass spectrometry (GC-HRMS) in suspect and non-target screening (SNTS) of organic micropollutants was combined with machine learning tools for proposing a novel and robust systematic environmental forensics workflow, focusing on groundwater contamination. Groundwater samples were collected from four different regions with diverse contamination histories (namely oil [OC], agricultural [AGR], industrial [IND], and landfill [LF]), and a total of 252 organic micropollutants were identified, including pharmaceuticals, personal care products, pesticides, polycyclic aromatic hydrocarbons, plasticizers, phenols, organophosphate flame retardants, transformation products, and others, with detection frequencies ranging from 3 % to 100 %. Amongst the SNTS identified compounds, a total of 51 chemical indicators (i.e., OC: 13, LF: 12, AGR: 19, IND: 7) which included level 1 and 2 SNTS identified chemicals were pinpointed across all sampling regions by integrating a bootstrapped feature selection method involving the bootfs algorithm and a partial least squares discriminant analysis (PLS-DA) model to determine potential prevalent contamination sources. The proposed workflow showed good predictive ability (Q2) of 0.897, and the suggested contamination sources were gasoline, diesel, and/or other light petroleum products for the OC region, anthropogenic activities for the LF region, agricultural and human activities for the AGR region, and industrial/human activities for the IND region. These results suggest that the proposed workflow can select a subset of the most diagnostic features in the chemical space that can best distinguish a specific contamination source class.

Human exposure to short-chain chlorinated paraffins and organophosphate flame retardants in relation to paired multiple sources.

In this study, the levels and distributions of short chain chlorinated paraffins (SCCPs) and organophosphate flame retardants (OPFRs) were determined in 10-88 aged human serum/hair and their paired multiple exposure sources, including one-day composite food, drinking water, and house dust. The average concentration of SCCPs and OPFRs were respectively 6313 and 176 ng/g lipid weight (lw) in serum, 1008 and 108 ng/g dry weight (dw) in hair, 1131 and 27.2 ng/g dw in food, not detected and 45.1 ng/L in drinking water, and 2405 and 864 ng/g in house dust. The levels of SCCPs in serum of adults were significantly higher than those of juvenile (Mann-Whitney U test, p < 0.05), whereas gender showed no statistically significant difference in SCCPs and OPFRs levels. In addition, there were significant relationships of OPFR concentrations between serum and drinking water as well as hair and food using the multiple linear regression analysis, whereas no correlation was observed for SCCPs. Based on the estimated daily intake, the major exposure pathway for SCCPs was food, while for OPFRs, it was food and drinking water with three order magnitude safety margin.

Exposure and Risk Assessment of Korean Firefighters to PBDEs and PAHs via Fire Vehicle Dust and Personal Protective Equipment.

In this study, the levels of polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers (PBDEs) were characterized in firefighters' personal protective equipment (PPE) (i.e., jackets, pants, hoods, and gloves) and vehicle dust wipe samples to assess the exposure and potential risk of firefighters to these combustion-related toxic pollutants. The mean levels of ∑PBDEs in the fire vehicle dust samples (778 and 449 pg/cm2 for pump trucks and command cars, respectively) were significantly higher than those in the private vehicles (31.2 pg/cm2) (Kruskal-Wallis test, p < 0.05), which was similar to the ∑PAH levels (521, 185, and 46.8 pg/cm2 for pump trucks, command cars, and private vehicles, respectively). In the case of firefighters' PPE, the levels of ∑PBDEs and ∑PAHs in used jackets and pants were found to be, respectively, 70- to 2242-folds and 11- to 265-folds higher than those in their unused counterparts. Biomass/petroleum combustion was found to be the main source of PAH contamination in fire vehicle dust and used PPE in the present study. Both carcinogenic and noncarcinogenic risks via vehicle dust ingestion and dermal absorption from wearing of PPE were within permissible limits, although the relative risk evaluation showed that PAH/PBDE absorption via wearing of PPE could pose a higher likelihood of carcinogenic and noncarcinogenic risks than the ingestion of pollutants via fire vehicle dust, warranting the need for appropriate management of firefighters' personal protective ensembles.

Long-term degradation of toluene and phenol in soil: Identification of transformation products and pathways via HRMS-based suspect and non-target screening.

In this study, the long-term fate of toluene and phenol in the soil was investigated, and the transformation products (TPs) and pathways of these compounds were studied by a high resolution mass spectrometry (HRMS)-based suspect and non-target screening approach for the first time, and 9 and 12 transformation products were identified for toluene and phenol, respectively in the lab-exposed soil samples. Salicylaldehyde, 4-hydroxybenzaldehyde, and benzaldehyde were identified in toluene-contaminated field soil samples for the first time, and the main mechanisms involved in the biodegradation and detoxification of toluene and phenol in soil were oxidation, carboxylation, dehydroxylation, and ring fission amongst others. 2-oxoglutarate, TP165-A, TP165-B, TP172, and TP195 were identified as novel phenol transformation products, while salicylaldehyde, 2-oxoglutarate, TP165-A, and TP165-B were identified as novel toluene transformation products, providing new possible evidence for additional degradation pathways, which could give new insights into the fate of toluene and phenol during the natural attenuation process in the environment. Finally, salicylaldehyde, 4-OH-benzaldehyde, and 4-OH-benzoic acid which were detected at Level 1 identification confidence were suggested as indicator chemicals of toluene and phenol exposure in the contaminated field.

Temporal and spatial trends of chlorinated paraffins and organophosphate flame retardants in black-tailed gull (Larus crassirostris) eggs.

In this study, eggs of black-tailed gull (Larus crassirostris), a top trophic level predator of marine ecosystem were, for the first time, monitored to assess the temporal and spatial trends of emerging pollutants in South Korea. Two Island regions, namely, Baekryeong-do (Site A) and Hong-do (Site B) were investigated from 2012 to 2018, and the total levels of short chain chlorinated paraffins (SCCPs), medium chain CPs (MCCPs), and organophosphate flame retardants (OPFRs) for both Site A and B were 1180-2931 and 694-2023 ng/g lipid weight (lw), 1287-4898 and 1034-3075 ng/g lw, and 203-499 and 233-409 ng/g lw, respectively. The time-trends of the concentration of pollutants showed an increasing tendency from 2012 to 2018, with the levels predicted to be doubled within three years, following the results of regression analysis. A shift in temporal-trends from shorter to longer chain CPs was noted, suggesting the effect of industrial-related contamination. Especially, significantly high levels of CPs and OPFRs were found in the site adjacent to China, which is reasonable as China is the largest producer and consumer of FRs and plasticizers worldwide. This study is valuable to understand the temporal increment of emerging pollutants as the alternatives of phased-out FRs and plasticizers, while raising the need for continuous environmental management.

Assessment of Exposure of Korean Firefighters to Polybrominated Diphenyl Ethers and Polycyclic Aromatic Hydrocarbons via Their Measurement in Serum and Polycyclic Aromatic Hydrocarbon Metabolites in Urine.

This study investigated the occupational exposure of Korean firefighters to a suite of combustion-related pollutants. Exposure to polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs) was assessed by measurement of their levels in serum and metabolites in urine (i.e., monohydroxylated PAHs, OH-PAHs). The mean level of ∑PBDEs in the serum of firefighters (17.1 ng/g lipid weight (lw)) was significantly higher than that of the general population (1.39 ng/g lw) (Mann-Whitney U Test, p < 0.05), which is similar to the ∑PAH levels (1286 ng/g lw for firefighters and 1016 ng/g lw for the general population). Individual OH-PAH levels showed 2.1- to 4.2-fold increases in postfire urine samples compared to the control urine samples, with the mean ∑OH-PAHs being significantly higher in postfire urine samples (22,658 ng/g creatinine) than in the control urine samples (10,253 ng/g creatinine) (Mann-Whitney U test, p < 0.05). It was found that ∑PBDEs correlated with firefighters' length of service and years dedicated to on-site dispatch, while ∑OH-PAHs was strongly associated with firefighters' exposure duration, age, length of service, and years dedicated to on-site dispatch. Indeed, the results of the present study indicate that Korean firefighters are prone to elevated risk of exposure to toxic combustion-related pollutants compared with the general population.

Perfluoroalkyl substances and pharmaceuticals removal in full-scale drinking water treatment plants.

The concentrations of 14 perfluoroalkyl substances (PFASs) and 46 pharmaceuticals in raw water and drinking water from five drinking water treatment plants were determined to assess removal of the chemicals during treatment. 10 out of 14 PFASs were detected in the raw and drinking water samples. The mean perfluorohexane sulfonate concentrations in raw and drinking water were the highest with levels of 106 and 69.6 ng L-1, respectively and the other PFAS concentrations were lower. The ∑14PFAS and individual PFAS removal efficiencies for the treatment plants were -36.9% to 70.7% (mean 31.3%) but the granular activated carbon process removed >80% of the total amount of long-chain PFASs that was removed. The removal efficiency increased as the perfluorocarbon chain length increased. The removal efficiencies increased by 14.2% and 11.2% from the shortest to the longest perfluoroalkyl carboxylic acid and perfluoroalkyl sulfonic acid chain lengths, respectively. 20 out of 46 pharmaceuticals were detected in the raw water samples, but most were removed completely during treatment. Only caffeine, carbamazepine, crotamiton, fenbendazole, metformin, and sulfamethoxazole were detected in the drinking water samples. Oxidation processes contributed >90% of the overall treatment plant removal efficiency except for metformin.

Short-chain chlorinated paraffins in various foods from Republic of Korea: Levels, congener patterns, and human dietary exposure.

Short-chain chlorinated paraffin (SCCP) concentrations in 419 food samples (from 59 species) from Republic of Korea were determined. The SCCP concentrations and lipid contents in whole foods positively correlated and the highest SCCP concentration (891 ng/g wet weight) was observed in fats and oils. The SCCP concentrations were higher in benthic fish/shellfish and demersal fish than other fish and shellfish. The SCCP concentrations were higher in duck meat and eggs than meat and eggs of other species. The chlorine-based congener group patterns were related to the lipid contents of the foods. SCCPs in eggs (high lipid content) were dominated by more-chlorinated SCCPs (particularly Cl8-SCCPs, which contributed 43% of the total) but SCCPs in seaweed (low lipid content) were dominated by less-chlorinated SCCPs (particularly Cl6-SCCPs, which contributed 46%). Dietary SCCP intakes were calculated using the median SCCP concentrations and estimated 888 and 781 ng/kg/d for male and female Korean adults, respectively. The predominant contributing foods to SCCP dietary exposure differed according to sex and age. Dairy products contributed most (about 50%) for infants/children (1-5 y old), but meat and dairy products contributed most for adult males and females, respectively. Grain contributed most for ≥65 y old.

Formation and distribution of phenanthrene and its metabolites (monohydroxy-phenanthrenes) in Korean rockfish (Sebastes schlegelii).

This study investigated the tissue distribution of phenanthrene (PHE) and the formation of monohydroxy-phenanthrene (OH-PHE) metabolites in Korean rockfish (Sebastes schlegelii). PHE was intragastrically administered to two groups of rockfish. The first group was exposed to PHE at a low dose (10 mg/kg body weight) and the second group was exposed at a high dose (30 mg/kg body weight). The rockfish were analyzed and the levels of PHE were higher in the liver, followed by muscle, and then bile. PHE concentrations in the liver, muscle, and bile were 1.4-26, 0.10-2.01, and not detected (ND)-0.13 µg/g wet weight, respectively. All five monohydroxylated PHE metabolites (1-OH-PHE, 2-OH-PHE, 3-OH-PHE, 4-OH-PHE, and 9-OH-PHE) were detected only in bile. Among these OH-PHE metabolites, 3-OH-PHE was found at the highest concentration from all fish bile samples in both PHE exposure groups, indicating that regioselective OH-PHE formation occurs in rockfish and 3-OH PHE could be a good biomarker of exposure of Korean rockfish to PHE. Suspect screening analysis of the rockfish bile was performed by LC-QTOF/MS, and the formation of two OH-PHE-DNA adducts (thymine-OH-PHE and cytosine-OH-PHE) were identified in the bile sample collected 6 h after rockfish were exposed to the high PHE dose, indicating that OH-PHE metabolites may be toxic to fish. This is the first report on the formation characteristics of OH-PHE metabolites in rockfish and their use as biomarkers of exposure of rockfish to parent PHE.

Field-scale evaluation of the uptake of Perfluoroalkyl substances from soil by rice in paddy fields in South Korea.

The concentrations of 17 perfluoroalkyl substances (PFASs) were investigated in paddy soil, void water, and brown rice collected from 30 paddy fields to examine the uptake of PFASs from soil by rice. The total concentrations of PFASs ranged from 7.76 to 3020 ng/L (average = 166 ng/L) in void water, 0.120 to 13.9 ng/g dry-weight (dw) (1.92 ng/g dw) in paddy soils, and from not-detected to 1.85 ng/g (0.403 ng/g) in brown rice samples. The highest PFAS concentrations were observed in brown rice cultivated in a paddy field where high levels of PFASs were observed in void water and paddy soil. Among target PFAS compounds, perfluorocarboxylic acids were dominant and detected in all matrices, and perfluorooctanoic acid (PFOA) was the most predominant compound in brown rice and void water. Significant positive correlations were examined for some detected PFASs between each matrix. PFOA in brown rice was positively correlated with PFOA in void water as well as perfluorodecanoic acid (PFDA) in paddy soil (p < 0.01). PFOA in void water also had correlated with PFDA in paddy soil. However, there was no correlation of other compounds between each matrix, except for correlations of perfluorononanoic acid (PFNA) and PFDA in paddy soil with those in void water, respectively (p < 0.05). Moreover, PFOA concentration in brown rice (0.093 ng/g) was much higher than one in white rice detected with a non-detectable level.