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.

Assessment of environmental forensic indicator for anthropogenic groundwater contamination via target/suspect/nontarget analysis using HRMS techniques.

This study compared target/suspect/nontarget analysis via liquid chromatography-high-resolution mass spectrometry (LC-HRMS) with traditional environmental forensic methods, specifically nitrate and its stable N isotope, in assessing groundwater pollution from livestock manure and agriculture. Using an in-house database of 1471 target and suspects, 35 contaminants (pesticides, veterinary drugs, surfactants) were identified, some uniquely linked to specific pollution sources, such as sulfamethazine and 4-formylaminoantipyrine in manure-affected areas. Pesticides were widespread, typically showing higher intensity in agricultural zones. On the other hand, the results of stable N isotope analysis (δ15N-NO3: 4.8 to 16.4‰) indicated the influence of human activities such as fertilizers, sewage, and manure in all sampling sites, including the control site far from the pollution sources and cannot differentiate the specific sources. The study underscores LC-HRMS's efficacy in different pollution sources, surpassing the limitations of stable N isotope analysis, and provides valuable insights for polluted groundwater source tracking strategies.

Distribution and ecological risk assessment of priority water pollutants in surface river sediments with emphasis on industrially affected areas.

Priority water pollutants comprising six plasticizers, 18 volatile organic compounds (VOCs), total petroleum hydrocarbon (TPH), 1,4-dioxane, epichlorohydrin, formaldehyde, acrylamide, and cyanides were determined in surface river sediments to assess their distribution patterns and ecological risks. Among these, di (2-ethylhexyl) phthalate (DEHP), toluene, TPH, and acrylamide were frequently found in sediments. The industrial sites had higher concentrations of ∑plasticizers (median 628 ng/g dry weight (dw)), ∑VOCs (median 3.35 ng/g dw), acrylamide (median 0.966 ng/g dw), and TPH (median 152 µg/g dw) in sediments than the mixed and non-industrial areas. The other pollutants did not show the significant differences in levels according to site types because of their relatively low detection frequencies. Volatile and soluble substances as well as hydrophobic pollutants were predominantly detected in surface sediments from industrial areas. Sediment contamination patterns were affected by the size and composition of the industrial zones around the sampling sites. The ecological risks determined using the sediment quality guidelines (DEHP, VOCs, and TPH) and the mean probable effect level quotients (DEHP) were mostly acceptable. However, the two most representative industrial regions (the largest industrial area and the first industrial city) showed risks of concern for DEHP and TPH.

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.

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.

Assessment of individual-based perfluoroalkly substances exposure by multiple human exposure sources.

Individual exposure of perfluoroalkyl substances (PFASs) was assessed by analyzing serum, food, dust, drinking water, and hand wipes from 50 individuals. The PFASs concentrations in serum were correlated most strongly with exposure to PFASs through the (direct and indirect) ingestion of dust (p < 0.01). Daily PFOA intakes were estimated to be 2.07 ng/kg/day from food, 0.003 ng/kg/day from dust, 0.053 ng/kg/day from hand-to-mouth activity, and 0.020 ng/kg/day from drinking water. Daily perfluorooctanesulfonic acid (PFOS) intakes were estimated to be 0.689 ng/kg/day from food, 0.001 ng/kg/day from dust, 0.018 ng/kg/day from hand-to-mouth activity, and 0.005 ng/kg/day from drinking water. The daily PFOA and PFOS intakes calculated for individuals in this study and in group/scenario based exposure assessment of previous studies were compared. The estimated PFOS intake on individual basis (0.695 ng/kg/day) was a little bit higher than the intake on group/scenario basis (0.652 ng/kg/day). However, the estimated daily PFOA intake on individual basis (1.41 ng/kg/day) was about four times higher than the intake on group/scenario basis (0.339 ng/kg/day). Among the exposure pathways, food ingestion was major contributor to the total daily PFOA and PFOS intakes on individuals (99% of total intake) and group/scenario basis (64% of total intake).

Assessment of organotin and tin-free antifouling paints contamination in the Korean coastal area.

Twelve organotins (methyl-, octyl-, butyl-, and phenyl-tin), and eight tin-free antifouling paints and their degradation products were measured in marine sediments from the Korean coastal area, and Busan and Ulsan bays, the largest harbor area in Korea. The total concentration of tin-free antifouling paints was two- to threefold higher than the total concentration of organotins. Principal component analysis was used to identify sites with relatively high levels of contamination in the inner bay area of Busan and Ulsan bays, which were separated from the coastal area. In Busan and Ulsan bays, chlorothalonil and DMSA were more dominant than in the coastal area. However, Sea-Nine 211 and total diurons, including their degradation products, were generally dominant in the Korean coastal area. The concentrations of tin and tin-free compounds were significantly different between the east and west coasts.

Assessment of impact of internal exposure to PBDEs on human thyroid function--comparison between congenital hypothyroidism and normal paired blood.

In this work, we investigated exposure levels, distribution patterns, and potential harmful impacts of polybrominated diphenyl ethers (PBDEs) on thyroid hormone activity in 26 children with congenital hypothyroidism and their mothers' pair and 12 normal control pairs. The average concentration of PBDEs in congenital hypothyroidism (median: 22.16 ng/g lipid) was higher than in normal controls (median: 14.76 ng/g lipid), but there was no statistical difference between the two groups. The BDE congeners were dominated by penta- to hepta-BDEs, but the greater brominated congeners (e.g., BDE 197, 196, 207, and 208) were relatively abundant in congenital hypothyroidism. BDE 138 was only observed in the congenital hypothyroidism cases. The maternal transfer and transport ratio of individual BDE congeners was shown for BDE 28 (0.588, p < 0.001), BDE 47 (0.564, p < 0.001), BDE 49 (0.712, p < 0.001) and BDE 119 (0.477, p = 0.002). The thyroid hormones were most obviously influenced by the internal exposure to PBDEs in normal mothers, showing a positive relationship with TSH (0.641 with BDE 154; 0.591 with BDE 153) and FT4 (0.584 with BDE 49; 0.572 with BDE 66) and a negative relationship with T3 (-0.577 with BDE 154) in the normal infants group. No significant correlations were observed in the congenital hypothyroidism cases.

Assessment of characteristic distribution of PCDD/Fs and BFRs in sludge generated at municipal and industrial wastewater treatment plants.

The presence of polychlorinated dibenzo-p-dioxins and furan (PCDD/Fs) and brominated flame retardants (BFRs) in sludge generated at municipal wastewater treatment plants (MWTPs) and industrial wastewater treatment plants (IWTPs) was investigated. The concentrations of these pollutants were in the following ranges: 5.38-7947ngkg(-1)dw (0.02-49.9ngWHO-TEQkg(-1) dw) for 17 PCDD/Fs, 17.5-66761µgkg(-1)dw for 27 polybrominated diphenyl ethers (PBDEs), 1.55-29604µgkg(-1)dw for hexabromocyclododecanes (HBCDs) (α-, ß-, and γ-diastereomers), and 4.01-618µgkg(-1)dw for tetrabromobisphenol A (TBBPA). Generally, the levels of each compound in the sewage-sludge samples were higher than those in the industrial-sludge samples with some exceptions. The characteristic distribution profiles of target compounds were observed for different types of sludge and different sources of wastewater. High-chlorinated PCDD/Fs were dominant in all samples except those from the textile industry. The distribution of the BFRs in industrial-sludge samples varied, whereas that of the BFRs in sewage-sludge samples was consistent. The proportion of penta-BDEs in sewage sludge was higher than that in industrial sludge, even though BDE-209 was the most dominant congener in all the samples. For HBCDs, the distribution of diastereomers (α-, ß-, and γ-HBCD) was similar across sludge samples that had the same source of wastewater and treatment processes.

Analysis and Exposure Assessment of Perchlorate in Korean Dairy Products with LC-MS/MS.

OBJECTIVES: Perchlorate is an emerging contaminant that is found everywhere, including various foods. Perchlorate is known to disturb the production of thyroid hormones and leads to mental disorders in fetuses and infants, as well as metabolic problems in adults. In this study, we attempted to establish an LC-MS/MS method for measuring perchlorate in dairy products and used this developed method to investigate perchlorate levels in Korean milk and yogurt samples. METHODS: The developed method of perchlorate analysis requires a shaker and 1% acetic acid/acetonitrile as the extracting solvent. Briefly, the samples were extracted and then centrifuged (4000 rpm, 1hour), and the supernatant was then passed through a Envi™ Carb SPE cartridge that had been prewashed sequentially with 6 mL of acetonitrile and 6 mL of 1% acetic acid in water. The final volume of the sample extract was adjusted to 40 mL with reagent water and the final sample was filtered through a 0.20-µm pore size PTFE (Polytetrafluoroethylene) syringe filter prior to LC-MS/MS. RESULTS: The average levels of perchlorate in milk and yogurt samples were 5.63 ± 3.49 µg/L and 3.65 ± 2.42 µg/L, respectively. The perchlorate levels observed in milk samples in this study were similar to those reported from China, Japan, and the United States. CONCLUSIONS: The exposure of Koreans to perchlorate through the consumption of dairy products was calculated based on the results of this study. For all age groups, the calculated exposure to perchlorate was below the reference of dose (0.7 µg/kg-day) proposed by the National Academy of Science, USA, but the perchlorate exposure of children was higher than that of adults. Therefore, further investigation of perchlorate in other food samples is needed to enable a more exact assessment of exposure of children to perchlorate.

Assessment of fates of estrogens in wastewater and sludge from various types of wastewater treatment plants.

We measured five estrogens in the wastewater samples from the municipal wastewater treatment plants (M-WWTPs), livestock wastewater treatment plants (L-WWTPs), hospital WWTPs (H-WWTPs) and pharmaceutical manufacture WWTPs (P-WWTPs) in Korea. The L-WWTPs showed the highest total concentration (0.195-10.4 µg L(-1)) of estrogens in the influents, followed by the M-WWTPs (0.028-1.15 µg L(-1)), H-WWTPs (0.068-0.130 µg L(-1)) and P-WWTPs (0.015-0.070 µg L(-1)). Like the influents, the L-WWTPs (0.003-0.729 µg L(-1)) and the M-WWTPs (0.001-0.299µgL(-1)) also showed higher total concentration of estrogens in the effluents than the H-WWTPs (0.002-0.021 µg L(-1)) and P-WWTPs (0.011 µg L(-1) in one sample). The L-WWTPs (37.5-543 µg kg(-1), dry weight) showed higher total concentrations in sludge than the M-WWTPs (3.16-444 µg kg(-1), dry weight) like the wastewater. The distribution of estrogens in the WWTPs may be affected by their metabolism in the human body, their transition through biological treatment processes, and their usage for livestock growth. Unlike the concentration results, the daily loads of estrogens from the M-WWTPs were the highest, which is related to the high capacities of WWTPs.

Occurrence and distribution of pharmaceuticals in wastewater from households, livestock farms, hospitals and pharmaceutical manufactures.

Twenty-four pharmaceuticals were measured in wastewater from 12 municipal wastewater treatment plants (M-WWTPs), four livestock WWTPs (L-WWTPs), four hospital WWTPs (H-WWTPs) and four pharmaceutical manufacture WWTPs (P-WWTPs). The total concentration of pharmaceuticals in the influent samples was highest in the L-WWTPs followed by the P-WWTPs, H-WWTPs and M-WWTPs. The effluents had different patterns of pharmaceuticals than their corresponding influents because of the different fate of each compound in the WWTPs. Non-steroidal anti-inflammatory drugs (NSAIDs) were the most dominant in the influents from the M-WWTPs and P-WWTPs, while antibiotics were dominantly detected in the L-WWTP. In the H-WWTP influents, NSAIDs, caffeine and carbamazepine were dominant. In the P-WWTPs, the distribution of pharmaceuticals in the effluents varied with sampling sites and periods. The M-WWTP influents had the highest daily loads, while the effluents showed somewhat similar levels in all source types.

Characteristic occurrence patterns of micropollutants and their removal efficiencies in industrial wastewater treatment plants.

The concentrations and removal efficiencies of various kinds of micropollutants were investigated and the relationships between the input sources of industrial wastewater and occurrence patterns of each micropollutant were identified at nine on-site industrial wastewater treatment plants (WWTPs). The distribution pattern of each compound varied according to the WWTP type and several micropollutants were significantly related with specific industries: chlorinated phenols (ClPhs) with paper and metal industries, polycyclic aromatic hydrocarbons (PAHs) with petrogenic- and pyrogenic-related industries, polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) with the paper industry, and chlorinated benzenes (ClBzs) with dye-related industries. The activated sludge (AS) process was very efficient in the removal of ClPhs and PAHs, and the filtration process in the removal of PCDD/Fs and 1,4-dioxane. Generally, the removal efficiencies of each micropollutant varied according to the WWTP type.

Perchlorate assessment of the Nakdong and Yeongsan watersheds, Republic of Korea.

The objective of the present study was to conduct a preliminary assessment for perchlorate in surface water, drinking water, and wastewater treatment plant effluent samples obtained from the Nakdong and Yeongsan watersheds in the Republic of Korea. Samples were analyzed for perchlorate using ion chromatography with suppressed conductivity detection (IC-CD) and/or liquid chromatography with tandem mass spectrometry detection (LC-MS/MS). Method reporting limits were 5.0 microg/L for IC-CD and 0.05 microg/L for LC-MS/MS analysis. At perchlorate levels above 5.0 microg/L, IC-CD and LC-MS/MS provided comparable results. The levels of perchlorate detected in the samples procured from the Yeongsan watershed were < 5.0 microg/L in each case. However, Nakdong watershed samples contained perchlorate at levels up to 60 microg/L. The highest concentrations of perchlorate were found in surface water samples, although drinking water contained perchlorate at concentrations up to 35 microg/L. In a subset of samples analyzed by LC-MS/MS, chlorate and bromate also were detected at concentrations ranging from < 0.10 to 44 microg/L and < 0.10 to 2.6 microg/L, respectively. To the best of the authors' knowledge, this is the first perchlorate assessment reported for water sources in the Republic of Korea.

Assessment of PCDD/F risk after implementation of emission reduction at a MSWI.

Municipal solid waste incinerators (MSWIs) have been shown to be important sources of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs). The emission of PCDD/Fs by MSWIs is a controversial subject in human health risk assessment. In this study the effect of a MSWI on a residential area was assessed before and after the installation of an additional treatment system for flue gas. This additional treatment system resulted in a dramatic decrease in PCDD/F concentrations in stack flue gas samples by 99.98%, while the concentrations in air decreased by approximately 50% (36,500 and 0.75 pg I-TEQ m(-3) for air in 1999; 3.5 and 0.38 pg I-TEQ m(-3) in 2002; 1.6 and 0.076 pg I-TEQ m(-3) in 2005 for stack gas and air, respectively). Considering the congener distributions of PCDD/Fs between stack flue gas and air samples, the study area seemed to have been contaminated by other urban sources as well as the MSWI. ISC3 model results support the conclusion that this incinerator became only a minor contributor to the study area after installation of the supplementary systems. This resulted from both proper MSWI operation using modern technology and additional sources of contaminants in this region. Finally, PCDD/F uptake by humans through inhalation of contaminated air was estimated. Assuming that inhalation exposure contributes 10% of total exposure, total exposure was lower than WHO guidelines. These results confirm that proper operation and maintenance of the incinerator led to a reduction in emissions and potential health impacts of PCDD/Fs.