Application of diffusive gradient in thin films probes to monitor trace levels of labile methylmercury in freshwaters.

This study aimed to optimize the methods for sampling and analyzing methylmercury (MeHg) concentrated within diffusive gradients in thin films (DGT) and its application to different water bodies. We explored the elution solution for MeHg, comprised of 1.13 mM thiourea and 0.1M HCl, optimizing its volume to 50 mL. In addition, we found that it is necessary to analyze the entire extraction solution after adjusting its pH, to ensure completion of the ethylation reaction. The DGT samplers were deployed in two distinct aquatic environments (i.e., Okjeong Lake and Nakdong River) for up to 6 weeks, and this study demonstrated to predict the time-weighted average concentration with a diffusion coefficient of 7.65 × 10-6 cm2 s-1 for MeHg in the diffusive gel. To assess the diffusive boundary layer (DBL) effects, the DGT samplers with different agarose diffusive gel thickness were deployed. The mass of MeHg accumulated in the DGT resin at a given time decreased with increasing diffusive gel thickness, because of creating longer diffusion pathways within thicker gels. The labile MeHg concentration estimated by the DGT in Okjeong Lake and Nakdong River are found in the range of 61-111 and 55-105 pg L-1, respectively, which were found to be similar to the grab sampling data. Additionally, this study evaluated depth-dependent MeHg in Okjeong Lake. The vertical profile results showed that the concentration of MeHg at the depth of 2.3 and 15.7 m are about 1.5 and 4.6 times of the DGT installed at 0.3 m of the surface layer, respectively, suggesting potential mercury methylation in deep waters. These findings have practical implications for predicting bioavailability, assessing risks, and formulating strategies for water body management and contamination remediation.

The performance of diffusive gradient in thin film probes for the long-term monitoring of trace level total mercury in water.

The potential of diffusive gradient in thin film (DGT) as a long-term monitoring tool to assess trace level mercury (Hg) in surface waters was evaluated. A piston type DGT sampler and a plate-type device that could hold 15 DGTs were designed. The device contained piston type DGT samplers with varying diffusive gel thicknesses, that is, 0.5, 0.75, and 1.0 mm, respectively. Three DGT devices were deployed in a lake for 5 weeks, and two were deployed in a stream for 3 weeks. In the lake, the total Hg (THg) mass accumulated in the DGT varied between 0.05 and 0.15 ng, which increased with an increase in deployment time and decreased with an increase in agarose diffusion gel thickness. The DGT concentration in the lake water for a 2 week period was estimated to be about 0.8-1.0 ng/L, which was close to the measured value of 1.1 (± 0.13) ng/L, using the grab sampling technique. However, the DGT estimated at 4 and 6 weeks showed a concentration of about 0.5-0.7 ng/L, which is about twice as small as that measured by grab sampling. This underestimation of the THg levels in water appear to be caused by additional thicknesses of the physical diffusive boundary layer (0.15, 0.5, 1.29 mm) and biofilm, outside the DGT filter. The predicted DGT concentration in the upper stream of the Nakdong River was estimated to be about 0.8-1.4 ng/L, which is similar to the value of 1.22 (± 0.29) ng/L measured in the field by grab sampling. The concentration of THg was estimated to be about 1.0-1.2 ng/L, which is similar to the values measured by grab sampling. The additional diffusion thickness formed outside the DGT filter was 0.018 mm and 0.093 mm at 1 and 3 weeks, respectively, which is not larger than the diffusion gel thickness (0.5-1.0 mm). This was because DGT was installed in a region where the flow velocity is high, and the thickness of the diffusion boundary layer outside the filter is negligible.

Nontarget screening using passive air and water sampling with a level II fugacity model to identify unregulated environmental contaminants.

It is thought that there are many unregulated anthropogenic chemicals in the environment. For risk assessment of chemicals, it is essential to estimate the predicted environmental concentrations. As an effort of identifying residual organic contaminants in air and water in Korea, nontarget screening using two-dimensional gas chromatography time-of-flight mass spectrometry (GC×GC-TOFMS) was conducted at 10 sites using polyurethane foam passive air sampler and at 6 sites using polydimethyl siloxane (PDMS) passive water sampler in three different seasons in 2014. More than 600 chemical peaks were identified satisfying the identification criteria in air and water samples, respectively, providing a list for further investigation. Chemical substances with reported national emission rates in 2014 (n=149) were also screened for potential existence in the environment using a level II fugacity model. Most of chemical substances classified as not detectable were not identified with detection frequency greater than 20% by nontarget screening, indicating that a simple equilibrium model has a strong potential to be used to exclude chemicals that are not likely to remain in the environment after emissions from targeted monitoring.

Significance of metabolite extraction method for evaluating sulfamethazine toxicity in adult zebrafish using metabolomics.

Recently, environmental metabolomics has been introduced as a next generation environmental toxicity method which helps in evaluating toxicity of bioactive compounds to non-target organisms. In general, efficient metabolite extraction from target cells is one of the keys to success to better understand the effects of toxic substances to organisms. In this regard, the aim of this study is (1) to compare two sample extraction methods in terms of abundance and quality of metabolites and (2) investigate how this could lead to difference in data interpretation using pathway analysis. For this purpose, the antibiotic sulfamethazine and zebrafish (Danio rerio) were selected as model toxic substance and target organism, respectively. The zebrafish was exposed to four different sulfamethazine concentrations (0, 10, 30, and 50mg/L) for 72h. Metabolites were extracted using two different methods (Bligh and Dyer and solid-phase extraction). A total of 13,538 and 12,469 features were detected using quadrupole time-of-flight liquid chromatography mass spectrometry (QTOF LC-MS). Of these metabolites, 4278 (Bligh and Dyer) and 332 (solid phase extraction) were found to be significant after false discovery rate adjustment at a significance threshold of 0.01. Metlin and KEGG pathway analysis showed comprehensive information from fish samples extracted using Bligh and Dyer compared to solid phase extraction. This study shows that proper selection of sample extraction method is critically important for interpreting and analyzing the toxicity data of organisms when metabolomics is applied.

Characterizing isotopic compositions of TC-C, NO3--N, and NH4+-N in PM2.5 in South Korea: Impact of China's winter heating.

The origin of PM2.5 has long been the subject of debate and stable isotopic tools have been applied to decipher. In this study, weekly PM2.5 samples were simultaneously collected at an urban (Seoul) and rural (Baengnyeong Island) site in Korea from January 2014 through February 2016. The seasonal variation of isotopic species showed significant seasonal differences with sinusoidal variation. The isotopic results implied that isotope species from Baengnyeong were mostly originated from coal combustion during China's winter heating seasons, whereas in summer, the isotopic patterns observed that were more likely to be from marine. In Seoul, coal combustion related isotopic patterns increased during China's winter heating period while vehicle related isotopic patterns were dominated whole seasons by default. Therefore, aerosol formation was originated from long-range transported coal combustion-related NOx by vehicle-related NH3 in Seoul. δN-NH4+ in Seoul showed highly enriched 15N compositions in all seasons, indicating that NH3 from vehicle emission is the important source of NH4+ in PM2.5 in Seoul. In addition, Baengnyeong should be consistently considered as a key region for observing the changes of isotopic features depend on the contribution of individual emissions to the atmospheric as a result of the reduction of coal consumption in China.

Updated national emission of perfluoroalkyl substances (PFASs) from wastewater treatment plants in South Korea.

A nationwide emission estimate of perfluoroalkyl substances (PFASs) from wastewater treatment plants (WWTPs) is required to understand the source-receptor relationship of PFASs and to manage major types of WWTPs. In this study, the concentrations of 13 PFASs (8 perfluorocarboxylic acids, 3 perfluoroalkane sulfonates, and 2 intermediates) in wastewater and sludge from 81 WWTPs in South Korea were collected. The emission pathways of PFASs were redefined, and then the national emission of PFASs from WWTPs was rigorously updated. In addition to the direct calculations, Monte Carlo simulations were also used to calculate the likely range of PFAS emissions. The total (Σ13PFAS) emission (wastewater + sludge) calculated from the direct calculation with mean concentrations was 4.03 ton/y. The emissions of perfluorooctanoic acid (PFOA, 1.19 ton/y) and perfluorooctane sulfonate (PFOS, 1.01 ton/y) were dominant. The Monte Carlo simulations suggested that the realistic national emission of Σ13PFASs is between 2 ton/y and 20 ton/y. Combined WWTPs treating municipal wastewater from residential and commercial areas were identified as a major emission source, contributing 65% to the total PFAS emissions. The Han and Nakdong Rivers were the primary contaminated rivers, receiving 89% of the total PFAS discharge from WWTPs. The results and methodologies in this study can be useful to establish a management policy for PFASs.

Mercury distribution characteristics in primary manganese smelting plants.

The mercury (Hg) distribution characteristics were investigated in three primary manganese smelting plants in Korea for the assessment of anthropogenic Hg released. Input and output materials were sampled from each process, and Hg concentrations in the samples were analyzed. Among the input materials, the most mercury was found in the manganese ore (83.1-99.7%) and mercury was mainly released through fly ash or off gas, depending on the condition of off gas cleaning system. As off gas temperature decreases, proportion and concentration of emitted gaseous elemental mercury (Hg0) in off gas decreases. Based on mass balance study from these three plants and national manganese production data, the total amount of mercury released from those Korean plants was estimated to 644 kg/yr. About half of it was emitted into the air while the rest was released to waste as fly ash. With the results of this investigation, national inventory for Hg emission and release could be updated for the response to Minamata Convention on Mercury.

Sub-lethal pharmaceutical hazard tracking in adult zebrafish using untargeted LC-MS environmental metabolomics.

Antibiotics in the aquatic environment are dispersed through anthropogenic activities at low concentrations. Despite their sub lethal concentration, these biologically active compounds may still have adverse effects to non-target species. This study examined the response of adult zebrafish to 0.1mg/L concentration of clarithromycin, florfenicol, sulfamethazine, and their mixture using environmental metabolomics. Embryo and larvae of the fish were also used to assess fish embryo acute toxicity and behavior tests respectively. The fish embryo toxicity test did not show any inhibition of growth and development of the embryos after 96h of exposure to the antibiotics. Changes in swimming activity were seen in 5-dpf larvae which is believed to be correlated with the length of exposure to the compounds. Meanwhile, environmental metabolomics revealed diverse metabolites and pathways that were affected after 72h of exposure of the adult fish to sub-lethal concentration of the compounds. We found that even at low concentration of the antibiotics, behavioral and metabolic effects were still observed despite the lack of visible morphological changes. Further studies involving other aquatic organisms and bioactive compounds are encouraged to strengthen the findings presented in this novel research.

A national discharge load of perfluoroalkyl acids derived from industrial wastewater treatment plants in Korea.

Levels of 11 perfluoroalkyl acids (PFAAs), including perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), were measured in wastewater (influent and effluent) and sludge samples collected from 25 industrial wastewater treatment plants (I-WWTPs) in five industrial sectors (chemicals, electronics, metals, paper, and textiles) in South Korea. The highest ∑11PFAAs concentrations were detected in the influent and effluent from the paper (median: 411ng/L) and textile (median: 106ng/L) industries, and PFOA and PFOS were the predominant PFAAs (49-66%) in wastewater. Exceptionally high levels of PFAAs were detected in the sludge associated with the electronics (median: 91.0ng/g) and chemical (median: 81.5ng/g) industries with PFOS being the predominant PFAA. The discharge loads of 11 PFAAs from I-WWTP were calculated that total discharge loads for the five industries were 0.146ton/yr. The textile industry had the highest discharge load with 0.055ton/yr (PFOA: 0.039ton/yr, PFOS: 0.010ton/yr). Municipal wastewater contributed more to the overall discharge of PFAAs (0.489ton/yr) due to the very small industrial wastewater discharge compared to municipal wastewater discharge, but the contribution of PFAAs from I-WWTPs cannot be ignored.

Enrichment of PCDDs/PCDFs in peripheral utilities of the municipal solid waste incineration facility.

This study was performed to suggest the improvements through measuring the amounts of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs), re-synthesized in peripheral utilities (PUs) of a commercial-scale municipal solid waste incineration facility (MSWIF) where a few research results existed. The PUs examined in this study consisted of air pre-heaters (APHs) and gas/gas re-heater (GGRH) and kerosene-fired duct burner for selective catalytic reduction (SCR) process. PCDDs/PCDFs in flue gas were simultaneously measured at the inlet and outlet of PUs. Flue gas was cooled down from 380 °C to 249 °C by exchanging the heat with fresh air in APHs, and then heated up to 383 °C by GGRH and duct burner from 164 °C at the outlet of bag filter. The results showed that PCDDs/PCDFs were 3-4 times higher within this temperature range of PUs. In comparison of PCDDs/PCDFs concentrations at the inlet with those at the outlet of PUs, particulate-phase PCDDs/PCDFs were about 9.5-10 times enriched while gaseous-phase ones were decreased by about 33-41%. The PCDDs/PCDFs re-synthesized in the PUs, where PCDDs were relatively higher than PCDFs, showed somewhat different patterns compared to those formed at incinerators and emitted at stack. Through the investigations for PUs, we conclude that the PUs used in MSWIFs was a potential source for de novo synthesis of PCDDs/PCDFs.