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.

Assessment of organochlorine pesticides in the atmosphere of South Korea: spatial distribution, seasonal variation, and sources.

Organochlorine pesticides (OCPs) are widely used in certain countries. We determined atmospheric concentrations, distribution patterns, and seasonal variations of OCPs at four sites in South Korea for 1 year. Samples of 22 OCPs were collected using a high-volume air sampler, and measured via the isotope dilution method with HRGC/HRMS. In South Korea, pentachlorobenzene (PeCB), hexachlorocyclohexane (HCB), and endosulfan (EnSF) were dominant, accounting for > 87% of total OCPs. Spatial distributions showed significant differences and the highest levels were observed in Seosan (295.2 pg·m-3), indicating the compounding potential of diverse sources as Seosan has concentrated large-scale industrial complexes and agricultural activity (Seoul: 243.6 pg·m-3 > Jeju: 193.5 pg·m-3 > Baengnyeong: 178.2 pg·m-3). The isomeric ratios of OCPs in the South Korean atmosphere indicated that the dominant sources of HCB and dichlorodiphenyltrichloroethane were primarily used in the past; meanwhile, chlordane (CHL) and EnSFs were derived from recent material inputs. Seasonally, OCP concentrations largely peaked in summer with minimum values in winter. This apparent temperature dependence suggests the re-volatilization of accumulated chemicals into the atmosphere. Additionally, an air mass back trajectory indicated the influence of pollutants released from a reservoir through long-range atmospheric transport in the summer. In particular, restricted OCPs are primarily released into the atmosphere by inadvertent sources, such as industrial activities and volatilization from contaminated areas. Thus, severe OCP pollution in Korea is due to the mobile nature of the particles. These data can be useful for the continuous monitoring of long-range transported air pollutants that are transferred between countries.

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.

Potential contributions of dissolved organic matter to monomethylmercury distributions in temperate reservoirs as revealed by fluorescence spectroscopy.

The monomethylmercury (MMHg) concentrations, water quality parameters (e.g., pH, suspended particles, total phosphorus, sulfate, and chlorophyll-a), and compositions of dissolved organic matter (DOM) were analyzed to understand how the quality of DOM is related to the MMHg distributions in the surface waters of 14 reservoirs. The excitation-emission matrix (EEM) fluorescence spectroscopy identified six fluorescence peaks, and a parallel factor analysis (PARAFAC) of EEM spectra identified three components of DOM: microbial humic-like (C1), terrestrial humic-like (C2), and protein-like DOM (C3). Using the observation data, the principal component analysis (PCA) were carried out to understand the relative importance of the fluorescence properties of DOM, representing DOM quality, on the MMHg distribution. The loading plot of PCA showed a strong positive correlation between the MMHg and protein regions of the EEM spectra and no correlation between MMHg and the terrestrial humic regions of the EEM, suggesting that autochthonous DOM production is a key factor in increasing MMHg concentration in reservoir water. The preliminary mass flux estimation, which was carried out to identify the major sources of MMHg in Okjeong reservoir, revealed that the major sources are sediment diffusion and water column methylation. Because the studied reservoirs are located remotely from a large-sized river and industrial region, most MMHg in reservoir water is likely diffused from the surface sediment or produced in the water column, and these sources tend to increase in reservoirs enriched with autochthonous DOM. It is suggested that EEM fluorescence can improve our ability to trace the major sources of MMHg in diverse reservoirs.

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.

Assessing correlations between monomethylmercury accumulation in fish and trophic states of artificial temperate reservoirs.

We investigated monomethylmercury (MMHg) concentrations in 448 samples of four common fish species (barbel steed, largemouth bass, leopard mandarin, and bluegill) and the trophic states of 14 artificial reservoirs in South Korea in order to understand how trophic states of reserviors affect MMHg concentrations in fish. The trophic state index (TSI) of each reservoir was determined using empirical equations based on the monthly chlorophyll-a, total phosphorus, and Secchi depth, collected over a three-year period. The length-normalized MMHg concentrations in fish showed a negative correlation with the TSI based on chlorophyll-a (r2=0.90) and total phosphorus (r2=0.75) that may be a result of particle dilution of MMHg in surface waters. This study revealed that MMHg accumulation in fish was better correlated with TSI than MMHg in water, therefore, we suggest that the measurement of TSI based on chlorophyll-a and total phosphorus is an effective way to predict MMHg bioaccumulation across diverse reservoirs.

Methylmercury Mass Budgets and Distribution Characteristics in the Western Pacific Ocean.

Methylmercury (MeHg) accumulation in marine organisms poses serious ecosystem and human health risk, yet the sources of MeHg in the surface and subsurface ocean remain uncertain. Here, we report the first MeHg mass budgets for the Western Pacific Ocean estimated based on cruise observations. We found the major net source of MeHg in surface water to be vertical diffusion from the subsurface layer (1.8-12 nmol m-2 yr-1). A higher upward diffusion in the North Pacific (12 nmol m-2 yr-1) than in the Equatorial Pacific (1.8-5.7 nmol m-2 yr-1) caused elevated surface MeHg concentrations observed in the North Pacific. We furthermore found that the slope of the linear regression line for MeHg versus apparent oxygen utilization in the Equatorial Pacific was about 2-fold higher than that in the North Pacific. We suggest this could be explained by redistribution of surface water in the tropical convergence-divergence zone, supporting active organic carbon decomposition in the Equatorial Pacific Ocean. On the basis of this study, we predict oceanic regions with high organic carbon remineralization to have enhanced MeHg concentrations in both surface and subsurface waters.

Application of diffusive gradients in thin films and core centrifugation methods to determine inorganic mercury and monomethylmercury profiles in sediment porewater.

A diffusive gradient in thin films (DGT) is an in situ sampling technique for the quantitative analysis of contaminant concentrations that is based on the diffusion and adsorption of contaminants on to resin gels. In the present study, a DGT technique was applied to measure total mercury (Hg) and monomethylmercury (MMHg) concentrations in lake and coastal sediment porewaters and compare them with those from ex situ sediment centrifugation. To calculate the total Hg and MMHg concentrations in porewater using the DGT method, the diffusion coefficients of Hg species in a diffusive gel medium was first determined, and then total Hg and MMHg depth profiles were measured using the experimentally determined diffusion coefficients. Using the diffusion coefficients for artificial lake and estuarine waters containing inorganic salts, rather than those for lake and estuarine waters containing Suwannee River humic acid (∼5 mg C L(-1) ), the DGT method demonstrated similar Hg and MMHg profiles to those using the centrifugation method. Based on the need for fine vertical resolution and high metal concentrations to be collected, DGT is suggested to be a reliable method for determining Hg(II) and MMHg depth profiles in sediment porewater.

Physicochemical factors affecting the spatial variance of monomethylmercury in artificial reservoirs.

The aim of this study was to identify how hydrologic factors (e.g., rainfall, maximum depth, reservoir and catchment area, and water residence time) and water chemistry factors (e.g., conductivity, pH, suspended particulate matter, chlorophyll-a, dissolved organic carbon, and sulfate) interact to affect the spatial variance in monomethylmercury (MMHg) concentration in nine artificial reservoirs. We hypothesized that the MMHg concentration of reservoir water would be higher in eutrophic than in oligotrophic reservoirs because increased dissolved organic matter and sulfate in eutrophic reservoirs can promote in situ production of MMHg. Multiple tools, including Pearson correlation, a self-organizing map, and principal component analysis, were applied in the statistical modeling of Hg species. The results showed that rainfall amount and hydraulic residence time best explained the variance of dissolved Hg and dissolved MMHg in reservoir water. High precipitation events and residence time may mobilize Hg and MMHg in the catchment and reservoir sediment, respectively. On the contrary, algal biomass was a key predictor of the variance of the percentage fraction of unfiltered MMHg over unfiltered Hg (%MMHg). The creation of suboxic conditions and the supply of sulfate subsequent to the algal decomposition seemed to support enhanced %MMHg in the bloom reservoirs. Thus, the nutrient supply should be carefully managed to limit increases in the %MMHg/Hg of temperate reservoirs.

Bioconcentration of methylmercury in microzooplankton in a temperate river.

To understand the bioconcentration of methylmercury (MeHg) at the base of the riverine food chain, we determined levels of dissolved organic carbon, microseston, Hg, and MeHg in surface water in relation to the microzooplankton MeHg from Yeongsan River. The spatial distribution of unfiltered Hg (0.29-3.1 ng/L) and dissolved Hg (0.15-0.74 ng/L) closely followed the microseston distribution. The spatial distribution of unfiltered MeHg (0.0078-0.077 ng/L) and dissolved MeHg (0.0069-0.018 ng/L) increased with increasing distance from the river mouth and appeared to arise from the shallow wetlands surrounding the upper riverbanks and then to be transported downstream. The logarithm of the MeHg bioconcentration factor for microzooplankton ranged from 5.3 to 6.0 (5.7 ± 0.18), and for microseston ranged from 4.0 to 5.4 (4.9 ± 0.35). Linear correlation statistics comparing microzooplankton MeHg and river water characteristics revealed that microzooplankton MeHg concentration was most significantly correlated with unfiltered MeHg (r = 0.83) and particulate MeHg (r = 0.80) levels. This result suggests that MeHg in unfiltered river water, which is relatively easy to determine, can be used as a surrogate for MeHg in microzooplankton that may influence MeHg levels in higher-trophic-level organisms.