Determinants of urinary dialkyl phosphate metabolites in midlife women: the Study of Women's Health Across the Nation Multi-Pollutant Study (SWAN-MPS).

BACKGROUND: Biomonitoring data and determinants of urinary dialkylphosphate (DAP) metabolites, markers of organophosphate pesticides, in racially diverse, non-occupationally exposed populations are scarce. OBJECTIVE: This study evaluated urinary concentrations and potential determinants of DAP metabolites of organophosphate pesticides in a multi-site, multi-racial/ethnic cohort of women aged 45-56 years, the Study of Women's Health Across the Nation Multi-Pollutant Study (SWAN-MPS). METHODS: We analyzed 963 urine samples collected in 1999-2000, the baseline of SWAN-MPS for longitudinal studies, and quantified DAP metabolites, including dimethyl alkylphosphates (DMAPs): dimethylphosphate (DMP), dimethylthiophosphate (DMTP), dimethyldithiophosphate (DMDTP); and diethyl alkylphosphates (DEAPs): diethylphosphate (DEP), diethylthiophosphate (DETP), diethyldithiophosphate (DEDTP), using gas chromatography and triple quadrupole mass spectroscopy. Adjusted least squared geometric means (LSGMs) and 95% confidence intervals (CIs) were computed to compare DAP concentrations by socio-demographic, behavioral and dietary factors. RESULTS: The geometric means (geometric standard deviations) of total DAPs, DMAPs, and DEAPs were 141 (2.63) nmol/L, 102 (2.99) nmol/L, and 26.8 (2.46) nmol/L, respectively. Body mass index (BMI) was inversely associated with DMAPs and DEAPs: LSGM (95% CI) = 68.8 (55.7-84.9) and 21.0 (17.7-25.0) nmol/L for women with obesity vs. 102 (84.7-123) and 30.1 (25.7-35.1) nmol/L for women with normal/underweight, respectively. Fruit consumption was positively (74.9 (62.1-90.2) for less than 5-6 servings/week vs. 105 (84.8-130) nmol/L for 1 serving/day and more) whereas meat consumption was inversely associated with DMAPs (110 (95.0-128) for seldom vs. 82.3 (59.5-114) nmol/L for often consumption). Fresh apple consumption appears to be attributed to the DMAP differences. Alcohol consumption was positively associated with DEAPs (27.5 (23.1-32.7) for 2 drinks/week and more vs. 23.0 (20.0-26.6) nmol/L for less than 1 drink/month). Black women had higher concentrations of DEAPs compared with White women (27.3 (21.2-35.2) vs. 23.2 (20.2-26.7) nmol/L). IMPACT STATEMENT: Organophosphate pesticides (OPs) are synthetic chemicals and currently the most widely used type of insecticides. We examined multi-site, multi-ethnic cohort of midlife women in the U.S. that offers a unique opportunity to evaluate major determinants of OP exposure. We improved OP metabolite detection rates and obtained accurate concentrations using an improved analytical technique. Our findings suggest that consumptions of fruit, meat and alcohol are important determinants of OP exposure for midlife women. Higher concentrations of diethyl OP metabolites in Black women compared to White women, even after accounting for dietary intake, suggests additional, but unknown racial-ethnic differences that affect exposure.

Low level exposure to hydrogen sulfide: a review of emissions, community exposure, health effects, and exposure guidelines.

Hydrogen sulfide (H2S) is a toxic gas that is well-known for its acute health risks in occupational settings, but less is known about effects of chronic and low-level exposures. This critical review investigates toxicological and experimental studies, exposure sources, standards, and epidemiological studies pertaining to chronic exposure to H2S from both natural and anthropogenic sources. H2S releases, while poorly documented, appear to have increased in recent years from oil and gas and possibly other facilities. Chronic exposures below 10 ppm have long been associated with odor aversion, ocular, nasal, respiratory and neurological effects. However, exposure to much lower levels, below 0.03 ppm (30 ppb), has been associated with increased prevalence of neurological effects, and increments below 0.001 ppm (1 ppb) in H2S concentrations have been associated with ocular, nasal, and respiratory effects. Many of the studies in the epidemiological literature are limited by exposure measurement error, co-pollutant exposures and potential confounding, small sample size, and concerns of representativeness, and studies have yet to consider vulnerable populations. Long-term community-based studies are needed to confirm the low concentration findings and to refine exposure guidelines. Revised guidelines that incorporate both short- and long-term limits are needed to protect communities, especially sensitive populations living near H2S sources.

Health risk assessment of exposure to organochlorine pesticides in the general population in Seoul, Korea over 12 years: A cross-sectional epidemiological study.

This study evaluated the 12-year trends in serum levels of 28 organochlorine pesticides (OCPs) in 880 adults living in Seoul, Korea. The OCP levels decreased from 2006 to 2017, and p,p'-dichlorodiphenyldichloroethylene was a predominant compound. OCP levels were higher in females than in males, and showed positive associations with BMI and age. The OCP concentrations had inverted U-shaped associations with low-density lipoprotein cholesterol and total cholesterol. Concentrations of ß-hexachlorocyclohexane were significantly higher in patients with hypertension than in participants that were normotensive. OCP levels showed positive associations with uric acid, creatinine, and thyroid-stimulating hormone, but negative associations with free thyroxine. Participants with diabetes had significantly higher OCP levels than those without it. Principal component analysis suggested possible differences in disease manifestation depending on the composition of OCPs. These results suggest that OCPs might disturb renal transport and thyroid homeostasis. To our knowledge, the inverted U-shaped associations of heptachlor epoxide and endosulfan with cholesterol, the epidemiological associations of trans-nonachlor and endosulfan with thyroid hormones, and the association of p,p'-DDE with hyperuricemia have not been previously reported in general population. This is the first long-term study to show trends of 28 OCPs in serum and associations with various health indicators in Korea.

Twenty-year trends and exposure assessment of polychlorinated dibenzodioxins and dibenzofurans in human serum from the Seoul citizens.

This study investigated polychlorinated dibenzodioxins and dibenzofurans (PCDD/Fs) in air (n = 108) and human serum (n = 1802) samples collected over 20 years to evaluate the long-term exposure to PCDD/Fs and health effects on the Korean general population. The serum PCDD/F levels were higher in males than in females and were significantly correlated with age, body mass index, and manifestation of diabetes mellitus. From 2000 to 2019, the PCDD/F levels declined by 96% in the air, but only by 36% in the serum, because PCDD/Fs are relatively stable in the human body and are exposed to humans after PCDD/Fs are distributed and migrated in various environmental matrices. The PCDD/F levels in other environmental matrices have also decreased at rates that differed among the matrices due to the different retention times and changes in continuous input of contaminants. As PCDD/Fs migrate from environmental matrices to the human body, the fraction of PCDDs increased whereas that of PCDFs decreased because of their relatively short half-lives. This study provides a concrete evidence that PCDD/F emissions by national regulations can achieve long-term reduction in human exposure. To the best of our knowledge, this is the longest and largest study to evaluate the long-term trends and annual changes of PCDD/Fs in the atmosphere and human serum, simultaneously.

Contamination characteristics of polycyclic aromatic hydrocarbons in river and coastal sediments collected from the multi-industrial city of Ulsan, South Korea.

River and coastal sediments were collected at 17 stations in Ulsan, the largest industrial city in South Korea, to evaluate the levels, profiles, emission sources, and spatial distribution of polycyclic aromatic hydrocarbons (PAHs). The mean concentration of Σ16 PAHs was 722 ng/g, and fluoranthene was a predominant compound. PAHs with 4-6 rings showed higher proportions than PAHs with 2-3 rings. The stations located near industrial complexes showed elevated levels of indicator compounds for petroleum, coal, coke, and fuel combustion. Therefore, petrochemical industries, coal pier, non-ferrous industries, and vehicles were identified as the emission sources. As industrialization and urbanization progressed, an increase in PAH levels and profile changes were observed as a result of the increasing industrial fuel consumption and the increasing number of vehicles. This is the first study that confirmed the change of PAHs in sediment caused by the change of emission sources over time in Ulsan.

Internal distribution and fate of persistent organic contaminants (PCDD/Fs, DL-PCBs, HBCDs, TBBPA, and PFASs) in a Bos Taurus.

While terrestrial organisms such as livestock are consumed regularly, studies of internal distribution and bioaccumulation of persistent organic pollutants (POPs) have been focused more on aquatic organisms. In this study, we have assessed the internal distribution and fate of legacy (PCDD/Fs and PCBs) and emerging POPs (HBCDs and PFASs), and TBBPA in 42 tissues of a Bos Taurus. PCDD/Fs, DL-PCBs, and HBCDs were found 3, 4, and 4-fold higher in the lipid-rich organs (subcutaneous fat, visceral fat, large intestine) compared to the remaining organs and muscles, owing to their hydrophobic properties. The TBBPA concentration in the excrement was 36-fold higher compared to the average tissues, suggesting a short internal half-life of TBBPA. Among PFASs, PFUnDA displayed 98% contribution from all ionic PFASs in the tissues due to its strong binding affinity, high exposure via feed and water, and increasing emergence of PFUnDA and its precursors in the Southeast Asian countries. While our study suggests that, at the moment, there is no significant health risks to the general Korean population, the future changes in environmental exposure as well as the internal dynamics and fate of various POPs species should be kept in mind when consuming various parts of livestock.

Photosensitized diastereoisomer-specific degradation of hexabromocyclododecane (HBCD) in the presence of humic acid in aquatic systems.

Humic acids (HA) are the most important photosensitizers in the ocean and generate highly reactive oxygen species (ROS), known as photochemically produce reactive intermediates (PPRI), which degrade organic pollutants. Thus, to reveal the fate of organic pollutants in an aqueous environment, it is important to understand the natural photodegradation phenomenon caused by HA. Three ROS generated from HA, 1O2, O2-, and OH, were measured using different probe compounds and instrumental techniques. In this study, HBCD (hexabromocyclododecane), a newly listed one of persistent organic pollutants (POPs) under the Stockholm Convention, was studied to understand the phototransformation mechanism, which has not been sufficiently investigated in terms of its environmental fate and transport, despite the distinctive features of its diastereoisomers. The results showed that the diastereoisomer-specific distributions of α-, ß-, and γ-HBCD were related to the acceleration and retardation of photodegradation in the presence of AHA (Aldrich Humic Acid) under simulated solar light, and only α-HBCD was rapidly photodegraded as the amount of AHA increased relative to the absence of AHA. This study provides the first characterization of the behavior of photosensitized HBCD degradation in aquatic systems.

Matrix-specific distribution and compositional profiles of perfluoroalkyl substances (PFASs) in multimedia environments.

This study investigated perfluoroalkyl substances (PFASs) in multimedia environments to confirm the effects of emission sources of PFASs and to elucidate their spatial distribution. The highest PFAS levels were detected from the samples of air (272.30 pg/m3) and surface water (36.54 ng/L) in an industrial complex area, meanwhile high PFAS levels were found from the samples of soil (8.80 ng/g) and sediment (84.98 ng/g) in urban areas and near wastewater treatment plants (WWTPs). Perfluorobutane sulfonate (PFBS) was primarily detected in water, influent and effluent, whereas long chain perfluorocarboxylic acids (PFCAs) and perfluorooctane sulfonate (PFOS) were dominant in dust, soil, sediment and sludge. While PFBS and neutral PFASs were dominant in air, PFCAs were primarily detected in plant and fish. The specific distribution patterns of PFASs in each matrix showed the influences of surrounding environments and different physicochemical characteristics of each congener. These findings suggest that the industrial complex and WWTP might be major emission sources to air and aquatic environments, respectively. This is the first study in which 6 neutral and 13 ionic PFASs were investigated simultaneously for nine different matrices in multimedia environments, and also it would be a good model study for future assessment of PFASs.

Influence of exposure to perfluoroalkyl substances (PFASs) on the Korean general population: 10-year trend and health effects.

This study demonstrated the 10-year trend of 13 perfluoroalkyl substances (PFASs) serum levels among 786 adults living in Seoul, Korea. PFAS levels gradually increased from 2006 to 2013, decreasing thereafter. We found that PFAS levels were higher in male than in female participants and were positively correlated with age. PFASs were not significantly correlated with body mass index, although we observed positive correlations with total cholesterol, low-density lipoprotein cholesterol, and triglycerides and negative correlations with high-density lipoprotein cholesterol. Uric acid and free thyroxine (fT4) also showed positive correlations with major congeners while correlations between thyroid stimulating hormone and PFASs were inconsistent. We demonstrated significant correlations between fT4 and perfluorononanoic acid (PFNA), perfluorohexane sulfonate (PFHxS), and perfluorodecanoic acid (PFDA). There were significant differences in PFHxS and perfluorododecanoic acid (PFDoDA) levels between participants with and without diabetes. Furthermore, principal component analysis suggested possible differences in disease manifestation based on the congener distribution of PFASs. This study is the first study of temporal trends of 13 PFAS congeners in serum samples obtained from the Korean general population; it is currently longest and largest scale study of this type.

Matrix-specific distribution and diastereomeric profiles of hexabromocyclododecane (HBCD) in a multimedia environment: Air, soil, sludge, sediment, and fish.

Hexabromocyclododecane (HBCD) contamination and its diastereomeric profile were investigated in a multi-media environment along a river at the local scale in air, soil, sludge, sediment, and fish samples. The spatial distribution of HBCD in each matrix showed a different result. The highest concentrations of HBCD in air and soil were detected near a general industrial complex; in the sediment and sludge samples, they were detected in the down-stream region (i.e., urban area). Each matrix showed the specific distribution patterns of HBCD diastereomers, suggesting continuous inputs of contaminants, different physicochemical properties, or isomerizations. The particle phases in air, sludge, and fish matrices were dominated by α-HBCD, owing to HBCD's various isomerization processes and different degradation rate in the environment, and metabolic capabilities of the fish; in contrast, the sediment and soil matrices were dominated by γ-HBCD because of the major composition of the technical mixtures and the strong adsorption onto solid particles. Based on these results, the prevalent and matrix-specific distribution of HBCD diastereomers suggested that more careful consideration should be given to the characteristics of the matrices and their effects on the potential influence of HBCD at the diastereomeric level.

Diastereoisomer- and species-specific distribution of hexabromocyclododecane (HBCD) in fish and marine invertebrates.

The levels and distributional characteristics of hexabromocyclododecane (HBCD) diastereoisomers have been largely reported for various fish and select shellfish. In this study, we reclassified a number and variety of marine invertebrates, including shellfish, to further contribute to the comprehensive understanding of the effects and assessment of human exposure to HBCD. Overall, 30 marine invertebrate species (n=188) were investigated and the following order of ∑2HBCD (α- and γ-HBCD) was observed: fish>chordata>cephalopoda>echinodermata>bivalve>crustacea. The marine invertebrates that were reclassified into nektonic and benthic organisms showed similar concentration of ∑2HBCD. The feeding habits and modes of the marine organisms were considered to compare the degree of bioaccumulation and diastereoisomer-specific distribution of HBCD due to the effects of the environment in and around pollution sources, as well as the organisms' metabolic capacities. To the best of our knowledge, this is the first study to examine the species-specific distribution patterns of HBCD for both fish and marine invertebrates. We expect to significantly expand the understanding of the environmental fate of HBCD for marine organisms.

Degradation of malic acid by Issatchenkia orientalis KMBL 5774, an acidophilic yeast strain isolated from Korean grape wine pomace.

Several yeast strains degrading malic acid as a sole carbon and energy source were isolated from Korean wine pomace after enrichment culture in the presence of malic acid. Among them, the strain designated as KMBL 5774 showed the highest malic acid degrading ability. It was identified as Issatchenkia orientalis based on its morphological and physiological characteristics as well as the nucleotide sequences of the internal transcribed spacer (ITS) I-5.8S rDNA-ITS II region. Phylogenetic analysis of the ITS I-5.8S rDNAITS II sequences showed that the KMBL 5774 is the closest to I. orientalis zhuan 192. Identity of the sequences of the KMBL 5774 was 99.5% with those of I. orientalis zhuan 192. The optimal pH of the media for the growth and malic acid degradation by the yeast was between 2.0 and 3.0, suggesting that the strain is an acidophile. Under the optimized conditions, the yeast could degrade 95.5% of the malic acid after 24 h of incubation at 30 degrees in YNB media containing 2% malic acid as a sole carbon and energy source.