Anthropogenic Iron Invasion into the Ocean: Results from the East Sea (Japan Sea).

Iron (Fe) is an essential micronutrient for phytoplankton growth, and its availability limits primary production in half of the global ocean. Traditionally, atmospheric input of natural mineral dust has been considered as a main source of Fe in the surface ocean. However, here we show that about 45% of the water-soluble Fe in aerosols collected over the East Sea (Japan Sea) is anthropogenic, which originates mainly from heavy fuel oil combustion, based on the analyses of various chemical tracers (Al, K, V, Ni, Pb, and 210Pb). It is striking that a tiny quantity of oil, less than 1% of the aerosols in mass, can constitute the majority of water-soluble Fe in aerosols due to its high Fe solubility. Furthermore, we show that a quarter of dissolved Fe in the East Sea is anthropogenic using a 210Pb-based scavenging model. Since this sea is almost fully enclosed (200-3000 m) and located at the forefront of the Asian human footprint, our results provide an insight that the marine Fe cycle may be already perturbed by human activities.

Speciation and Sources of Brown Carbon in Precipitation at Seoul, Korea: Insights from Excitation-Emission Matrix Spectroscopy and Carbon Isotopic Analysis.

Brown carbon (BrC) plays a significant role in the Earth's radiative balance, yet its sources and chemical composition remain poorly understood. In this work, we investigated BrC in the atmospheric environment of Seoul by characterizing dissolved organic matter in precipitation using excitation-emission matrix (EEM) fluorescence spectroscopy coupled with parallel factor analysis (PARAFAC). The two independent fluorescent components identified by PARAFAC were attributed to humic-like substance (HULIS) and biologically derived material based on their significant correlations with measured HULIS isolated using solid-phase extraction and total hydrolyzable tyrosine. The year-long observation shows that HULIS contributes to 66 ± 13% of total fluorescence intensity of our samples on average. By using dual carbon (13C and 14C) isotopic analysis conducted on isolated HULIS, the HULIS fraction of BrC was found to be primarily derived from biomass burning and emission of terrestrial biogenic gases and particles (>70%), with minor contributions from fossil-fuel combustion. The knowledge derived from this study could contribute to the establishment of a characterizing system of BrC components identified by EEM spectroscopy. Our work demonstrates that, EEM fluorescence spectroscopy is a powerful tool in BrC study, on the basis of its chromophore resolving power, allowing investigation into individual components of BrC by other organic matter characterization techniques.

Biogeochemical conditions controlling the intensity of paralytic shellfish poisoning (PSP) outbreak caused by Alexandrium blooms: Results from 6-year field observations in Jinhae-Masan Bay, Korea.

Previous field observations from 2018 to 2019 revealed that paralytic shellfish poisoning (PSP) caused by the blooms of toxic dinoflagellate Alexandrium species occurred under low concentrations of dissolved inorganic nitrogen (DIN) and high concentrations of dissolved organic nitrogen (DON) and humic-like fluorescent dissolved organic matter (FDOMH) in Jinhae-Masan Bay, Korea. In this study, we obtained more data for DIN, DON, FDOMH, and Alexandrium cell density from 2020 to 2023 to further validate environmental conditions for the PSP outbreak. We also measured total hydrolyzed amino acids (THAA) to determine the bioavailability of DON fueling the PSP outbreak. Over the 6-year observations, there was a consistent pattern of low DIN concentrations and high DON and FDOMH concentrations during the PSP outbreak periods. The Alexandrium cell densities, together with the PSP toxin concentrations, increased rapidly under this environmental condition. The PSP outbreak occurs when a large amount of DIN originating from the stream waters near the upstream sites is transformed into DON by biological production before entering the PSP outbreak area. The produced DON is characterized by high bioavailability based on the various AA-derived indices (enantiomeric ratio, degradation index, non-protein AA mole%, and nitrogen-normalized AA yield). In addition, the intensities of PSP outbreaks are mainly dependent on the conversion stage of DIN to DON and enhanced FDOMH. We found that the strong PSP outbreak occurred consistently under a low level of DIN (<1.0 µM) and high levels of DON (>9.0 µM) and FDOMH (>1.5 R.U.). Thus, our results suggest that the monitoring data of environmental conditions can be used to predict the PSP outbreak in the coastal oceans.

Long-term changes in the concentrations of nutrients in the marginal seas (Yellow Sea, East China Sea, and East/Japan Sea) neighboring the Korean Peninsula.

We examined the changes in the concentrations of dissolved inorganic nitrogen (DIN) and phosphorus (DIP) in the surface waters of the Yellow Sea (YS), the southern sea (SS) of Korea, and the East/Japan Sea (ES) from 1995 to 2021. These marginal seas neighboring the Korean Peninsula maintained nutrient concentrations approximately an order of magnitude higher than those in the Kuroshio waters, indicating extraordinarily large terrestrial source inputs. Generally, the DIN concentration in the YS increased gradually due to the accumulation of terrestrial inputs, while the nutrient concentrations in the ES declined gradually mainly due to enhanced water stratification. The SS showed the maximum DIN concentrations around 2005, associated with freshwater influence. In Korean coastal waters within ~10 km from the coastline, nutrient concentrations declined sharply during this period due to decreased terrestrial nutrient inputs. The rapid changes in the nutrient levels in these seas may significantly alter biological production.

Significant contribution of coastal fish-farm activities to the inventory of trace elements in coastal waters: Traced by ammonia and rare earth elements.

In this study, we investigated the influence of fish-farm activities on the inventory of trace elements (Mn, Fe, Co, Ni, and Cu) in the coastal waters off the fish-farm plants on Jeju Island, Korea. NH4+ and rare earth elements (REEs) were used as tracers to examine the production and removal processes. Relatively higher concentrations of trace elements were observed in the coastal waters and significantly correlated with NH4+. Our results suggest that the excess dissolved trace elements in the coastal waters could be mainly produced inside fish farms, together with the production of NH4+ and light-REEs (La to Nd). Although dissolved trace elements were found to be partially scavenged onto particles in the fish-farm rearing waters, indicated by the significant removal of particle-reactive Ce, these particles would be eventually discharged into the coastal ocean and release the dissolved trace elements back into the water columns.

Origins and characteristics of dissolved organic matter fueling harmful dinoflagellate blooms revealed by δ13C and D/L-Amino acid compositions.

We measured the concentrations of dissolved inorganic and organic nutrients, dissolved organic carbon (DOC), total hydrolyzable amino acids (THAA), fluorescent dissolved organic matter (FDOM), phytoplankton pigments, and δ13C-DOC during the summer of 2019 in the harmful dinoflagellate bloom regions of the southern coast of Korea. In the harmful dinoflagellate bloom region, the concentrations of inorganic nitrogen were depleted, inhibiting the growth of diatoms, while the concentrations of dissolved organic components (nutrients, DOC, FDOM, and amino acids) which fuel dinoflagellates were unusually high. Thus, we attempted to investigate the origins and characteristics of DOM which fuels the harmful dinoflagellate blooms. The δ13C-DOC values (- 22.2‰ to - 18.2‰) indicate that the elevated DOC concentrations result from in-situ biological production rather than terrestrial inputs. The enantiomeric (D/L) ratios of THAA indicate that dissolved organic nitrogen was more labile in the early stage of harmful dinoflagellate bloom and became more refractory in the final stage. Our results suggest that the marine production of bioavailable DOM plays an important role in initiating and sustaining harmful dinoflagellate blooms.

Mass balance of total mercury and monomethylmercury in coastal embayments of a volcanic island: significance of submarine groundwater discharge.

To understand the contribution of submarine groundwater discharge (SGD) to the coastal mass budgets of Hg and monomethylmercury (MMHg), preliminary mass balance estimates were made for Hwasun and Bangdu Bays on Jeju Island, known to have large SGD due to the high permeability of the volcanic rocks. The mass balance results indicate that SGD is a main source of Hg in Hwasun Bay (23 ± 14 × 10(-2) mol yr(-1), 34%) and Bangdu Bay (23 ± 20 × 10(-2) mol yr(-1), 67%), although the contribution from atmospheric deposition was considerable (25% for Hwasun and 23% for Bangdu). MMHg was also discharged primarily from submarine groundwater at Hwasun (0.30 ± 0.17 × 10(-2) mol yr(-1), 55%) and Bangdu (0.65 ± 0.49 × 10(-2) mol yr(-1), 64%), which was higher than atmospheric deposition (6% for Hwasun and 2% for Bangdu) and sediment diffusion flux (5% for Hwasun and 3% for Bangdu). The overall mass balance results suggest that, although there are large spatial variations in SGD rates throughout the region, the coastal mass budgets of Hg and MMHg need to include SGD as well as atmospheric deposition and sediment diffusion as primary sources of Hg and MMHg.

Anthropogenic gadolinium in lakes and rivers near metrocities in Korea.

We measured dissolved rare earth elements (REEs) in the water samples from Shihwa Lake (SL), which was assumed to be highly polluted, and in the downstream portion of the Han River (HR), which runs through Seoul, Korea. Among the investigated REEs, only gadolinium (Gd) was found to be significantly enhanced after REE concentrations were shale-normalized (SN). The calculated Gd anomaly (Gd/Gd* = 3 × GdSN/(SmSN + 2 × TbSN)) was about 1.5 ± 0.1 (n = 16) in SL and 1.6 ± 0.3 in the HR (n = 26) water relative to other types of natural water such as groundwater, seawater, and river water in uncontaminated areas (Gd/Gd* ∼ 1.2, n > 400). These significant Gd anomalies seem to be due to the inputs of anthropogenic Gd (Gdanth), especially from the use of Gd-based contrast agents for magnetic resonance imaging (MRI) tests from a number of hospitals and medical institutes surrounding our study areas. The amount of Gdanth was estimated to be 190 ± 80 g and 680 ± 360 kg Gd in SL and the HR (watersheds in our study area), respectively. The Gdanth flux to the Yellow Sea from the HR is estimated to be 530 ± 330 g Gd d-1. These results suggest that quantitative evaluation of anthropogenic REEs in natural waters near big cities is needed, because considerable amounts of REEs are now used by modern high-tech industries.

Tracing river water versus wastewater sources of trace elements using rare earth elements in the Nakdong River estuarine waters.

The concentrations of dissolved rare earth elements (REEs) and trace elements (Al, V, Mn, Fe, Co, Ni, Cu, Zn, Mo, Cd, and Pb) were measured along the Nakdong River Estuary. In general, REE concentrations presented negative correlations with salinity, except for the sampling sites close to the wastewater treatment plant (WWTP), where the concentrations were approximately two orders of magnitude higher. In this study, we attempted to utilize REEs as tracers for river versus WWTP sources of trace elements. The main sources of trace elements can be attributed as follows: the seawater for Mo and Cd, the seawater and WWTP for V, the river and WWTP for Ni and Cu, and the WWTP for Al, Mn, Fe, Co, Zn, and Pb. Our results suggest that REEs can serve as powerful tracers for WWTP sources, particularly in coastal waters where various trace element sources are present.

Conditions of nutrients and dissolved organic matter for the outbreaks of Paralytic Shellfish Poisoning (PSP) in Jinhae Bay, Korea.

We measured the concentrations of nutrients, fluorescent dissolved organic matter (FDOM), and photosynthetic pigments in seawater during the springs of 2018 and 2019 in Jinhae Bay, Korea. The samplings were carried out during the severe and weak outbreaks of paralytic shellfish poisoning (PSP) in April 2018 and March 2019, respectively. The additional sampling campaigns were carried out before and after the PSP outbreak for the comparison. During the severe PSP outbreak, lower salinities, higher organic and total nutrients, and higher humic-like FDOM were observed. Although the environmental condition of April 2018 is favorable for the growth of dinoflagellates, the lowest peridinin (dinoflagellate index) and highest fucoxanthin (diatom index) concentrations were observed amongst all sampling periods. Thus, our results suggest that PSP could be more effectively produced by dinoflagellates in the course of the ecological shift by interspecific competition under the environmental condition favorable for dinoflagellates.

Removal of Refractory Dissolved Organic Carbon in the Amundsen Sea, Antarctica.

The removal mechanism of refractory deep-ocean dissolved organic carbon (deep-DOC) is poorly understood. The Amundsen Sea Polynya (ASP) serves as a natural test basin for assessing the fate of deep-DOC when it is supplied with a large amount of fresh-DOC and exposed to strong solar radiation during the polynya opening in austral summer. We measured the radiocarbon content of DOC in the water column on the western Amundsen shelf. The radiocarbon content of DOC in the surface water of the ASP reflected higher primary production than in the region covered by sea ice. The radiocarbon measurements of DOC, taken two years apart in the ASP, were different, suggesting rapid cycling of DOC. The increase in DOC concentration was less than expected from the observed increase in radiocarbon content from those at the greatest depths. Based on a radiocarbon mass balance, we show that deep-DOC is consumed along with fresh-DOC in the ASP. Our observations imply that water circulation through the surface layer, where fresh-DOC is produced, may play an important role in global DOC cycling.

Nutrient inputs from submarine groundwater discharge (SGD) in Masan Bay, an embayment surrounded by heavily industrialized cities, Korea.

In order to estimate the magnitude of submarine groundwater discharge (SGD) and the associated nutrient fluxes in Masan Bay on the southern coast of Korea, we measured the concentrations of 226Ra and nutrients in seawater, brackish groundwater, and stream water in May and August 2006. Gauging unidentified nutrient fluxes through SGD is very important in this bay since diatom red tides have been occurring from April to October every year since the 1980s. Based on a 226Ra mass balance model, the submarine inputs of coastal groundwater were estimated to be 4.8x10(6) and 5.7x10(6) m3 d(-1) (61 and 71 L m(-2) d(-1)) in May and August, respectively, which were approximately 840% and 540% of the surface water discharge into the bay. The fluxes of dissolved inorganic phosphorus (DIP) and silicate (DSi) through SGD were 2-3 fold higher than those via stream water, while the fluxes of dissolved inorganic nitrogen (DIN) were comparable to those from surface waters during both sampling periods. Nutrient fluxes through stream waters relative to those from SGD were more significant in the inner part of the bay, which appears to be due to the direct influence of heavily polluted stream waters. Our study shows that the large and continuous supply of inorganic nutrients through SGD may play an important role in eutrophication and the occurrence of red tides in this bay, which should be taken into consideration in the environmental management of the bay.

Large seasonal variations in fine aerosol precipitation rates revealed using cosmogenic 7Be as a tracer.

To determine the seasonal variations in the removal efficiency of fine aerosols (PM2.5) in the Northeast Asia, we analyzed 7Be data collected for the surface air and precipitation over 20 years in Korea. The 7Be activity concentrations in the surface air were relatively higher in spring owing to tropopause folding but lower in summer owing to efficient removal by precipitation. The monthly 7Be concentrations decreased as the precipitation amounts increased showing a negative correlation (r2 = 0.34) against the precipitation amount. These results indicate that the concentrations of 7Be and fine aerosols are mainly controlled by the same washout effect, although the sources are different. The mean depositional velocities of fine aerosols, based on the 7Be mass balance model, showed a large seasonal variation, with its maximum value (1.9 cm s-1) in July and minimum value (0.22 cm s-1) in March. The 7Be depositional velocity reflects the net deposition of fine aerosols excluding moisture effects. Thus, the concentrations of fine aerosols can occur as high as five-fold in the dry season, if the input terms of fine aerosols remain the same. Our results imply that precipitation plays a critical role in the seasonal changes in the concentrations of fine aerosols, providing much clean air in the summer monsoon season in the Northeast Asia.

Tracing nitrogen sources fueling coastal green tides off a volcanic island using radon and nitrogen isotopic tracers.

The main sources of nutrients fueling coastal green tides off a volcanic island surrounded by an oligotrophic ocean are obscure, although they result in many societal and ecosystem problems. In this study, we attempted to trace the source inputs of nutrients in coastal waters off a volcanic island, Jeju, Korea, where the formation of green tides is perennial, using a radioisotope (222Rn) and stable isotopes (δ15N and δ18O) as tracers. Sampling of groundwater, seawater, fish-farm water, and Ulva spp. was performed during April and July 2015. The contribution of submarine fresh groundwater discharge (SFGD) to the dissolved inorganic nitrogen input was >70%, with additional inputs from aqua-cultural activities and bottom sediments. The δ15N-NO3 and δ18O-NO3 values in the coastal seawater and groundwater indicate that the main source of NO3- is fertilizer, rather than other potential sources, such as aquacultural wastewater, sewage/manure contamination, or precipitation, in this region. The δ15N value (+7.3-+7.7‰) in Ulva spp. also indicates the same source. Thus, our results suggest that the rapid infiltration of land N-fertilizer and subsequent leakage into the coastal ocean through submarine groundwater discharge (SGD) results in green tide massive occurrence in coastal waters off a high-permeability volcanic island.

Tracing the sources of nutrients fueling dinoflagellate red tides occurring along the coast of Korea using radium isotopes.

It is a well held concept that the magnitude of red-tide occurrence is dependent on the amount of nutrient supply if the conditions are same for temperature, salinity, light, interspecific competition, etc. However, nutrient sources fueling dinoflagellate red-tides are difficult to identify since red tides usually occur under very low inorganic-nutrient conditions. In this study, we used short-lived Ra isotopes (223Ra and 224Ra) to trace the nutrient sources fueling initiation and spread of Cochlodinium polykrikoides blooms along the coast of Korea during the summers of 2014, 2016, and 2017. Horizontal and vertical distributions of nutrient concentrations correlated well with 224Ra activities in nutrient-source waters. The offshore red-tide areas showed high 224Ra activities and low-inorganic and high-organic nutrient concentrations, which are favorable for blooming C. polykrikoides in competition with diatoms. Based on Ra isotopes, the nutrients fueling red-tide initiation (southern coast of Korea) are found to be transported horizontally from inner-shore waters. However, the nutrients in the spread region (eastern coast of Korea), approximately 200 km from the initiation region, are supplied continuously from the subsurface layer by vertical mixing or upwelling. Our study highlights that short-lived Ra isotopes are excellent tracers of nutrients fueling harmful algal blooms in coastal waters.

Distribution patterns of chalcogens (S, Se, Te, and 210Po) in various tissues of a squid, Todarodes pacificus.

In order to elucidate the relationship between the chemically similar chalcogen elements S, Se, Te, and 210Po in marine invertebrates, we conducted a comparative study of the distribution patterns of these elements in a squid, Todarodes pacificus. Elemental concentrations of the four chalcogens were determined in (mantle) muscle, gill, stomach, and hepatopancreas tissues. No relationship between chalcogen concentrations and morphological parameters (mantle length, body weight, and sex) was evident. Gills showed slightly elevated levels of Se and 210Po, which may indicate absorption and uptake of these elements over the gill surface. All four chalcogens have their highest concentrations in the hepatopancreas and the lowest concentrations in the muscle tissue. However, concentration differences between tissues, revealed by (1) bioaccumulation values based on reference seawater values and (2) internal relative enrichment factors (IREF) based on enrichment of hepatopancreas compared to muscle tissue, were least pronounced for S, most distinct for 210Po, and moderate for Se and Te. Furthermore, no significant correlation for Se, Te, and 210Po with S within tissue concentrations, and only a slightly negative correlation between S and 210Po in the squid muscle and hepatopancreas tissues were found, which indicates either an antagonistic effect between, or a disconnection of the two elements through metabolic processing. Overall, the distribution patterns of Se and Te resemble those of essential trace elements, such as Zn and Cu, whereas 210Po is partitioned in a manner similar to toxic heavy metals, such as Cd and Ag.

An efficient and simple method for measuring (226)Ra using the scintillation cell in a delayed coincidence counting system (RaDeCC).

A delayed coincidence counter (RaDeCC), developed to determine ultra-low levels of (223)Ra (half life = 11.1 days) and (224)Ra (half life = 3.6 days) in seawater, was adapted to measure (226)Ra (half life = 1622 years). After pre-concentration of Ra from seawater onto MnO(2)-coated fiber we show in this study that the (226)Ra activity can be determined using the RaDeCC's ability to record alpha decay of its daughters as total counts. For sufficient ingrowth of (222)Rn, the Mn-fiber is hermetically sealed in a column for a few days. Then, the ingrown (222)Rn is circulated through the RaDeCC air-loop system followed by shutting down of the pump and closure of the scintillation cell for equilibration. Counting may be completed within a few hours for seawater samples. Sample measurements with this method agreed well with data obtained using gamma-ray spectrometry. This proves that a set of Ra isotopes ((223)Ra, (224)Ra, and (226)Ra), commonly used for geophysical studies such as mixing rates of different water masses and submarine groundwater discharge, can be efficiently and rapidly measured using the RaDeCC.

Dispersion and removal characteristics of tritium originated from nuclear power plants in the atmosphere.

The activities of tritium in water-vapor (n = 649) and precipitation (n = 2404) samples were measured from 1998 to 2015 around the Wolsong nuclear power plant (NPP) site where four pressurized heavy water reactors and two pressurized water reactors operated. The activity concentrations of tritium in the water-vapor and precipitation samples were in the ranges of 2.2-2200 Bq/L and 0.3-1090 Bq/L, respectively. The concentrations of tritium in the water-vapor in spring were approximately 7 times higher than those in fall and winter, mainly owing to the wind directions at the power plant location. The annual geometric mean activities of tritium in the water-vapor and precipitation samples varied within 56% and 83% from the average, respectively, depending primarily on the annual discharge amount of tritium to the atmosphere. The activities of tritium in the water-vapor and precipitation samples rapidly decreased away from the power plant. Approximately 0.5-30% of tritium discharged from the NPP site was removed by precipitation to the ground within an area with a radius of 30 km from the NPP site, which linearly depended on the precipitation amount. Our results suggest that the wind direction and precipitation, in addition to the amount of discharge, are important factors that control the tritium concentrations in air near the NPP site.

Significant production of humic fluorescent dissolved organic matter in the continental shelf waters of the northwestern Pacific Ocean.

Fluorescent dissolved organic matter (FDOM) is important for marine organisms and the global carbon cycle contributing to the optical properties of surface seawater and organic carbon budgets. Rivers are known to be the main source of FDOM in coastal oceans and marginal seas. In this study, however, we show that the contribution of FDOM produced from organic sediments of the northwestern Pacific continental shelf is similar to that from the Changjiang River. FDOM showed relatively higher concentrations at stations off the Changjiang River mouth and in the central Yellow Sea. Based on temperature-salinity diagrams, the major source of surface FDOM in summer surface waters was found to be from the Changjiang River while that observed in the winter water column was produced mainly in the continental shelf. A good correlation between 228Ra and the humic-like FDOM (FDOMH) during the winter suggests that the FDOMH is produced mainly from marine sediments and enriched in water over the water residence times. A simple mass balance calculation shows that the excess FDOMH fluxes produced from marine sediments account for 30-40% of the riverine source. This result suggests that the continental shelf is an important hidden source of FDOM in the upper ocean.

Significant and conservative long-range transport of dissolved organic nutrients in the Changjiang diluted water.

The Changjiang River is one of the main nutrient sources in the northwestern Pacific marginal seas. However, most of the previous studies have neglected the long-range transport (>200 km) of riverine nutrients since they are rapidly consumed. In this study, we examined the long-range transport (200-800 km) of nutrients in the surface layer during the summer of 2017. The plots of nutrients against salinity display that dissolved organic nitrogen (DON) was conservative over ~800 km, while more than 99% of the dissolved inorganic nitrogen (DIN) was removed within 200 km. As a result, in the study region, DON concentrations (avg. 7.0 ± 1.3 µM), which are minor in the river water, were much higher than DIN concentrations (avg. 0.28 ± 0.26 µM). Both nutrients, N and P, showed a similar pattern. Our results suggest that dissolved organic nutrients play a critical role on the long-range transport of riverine nutrients in surface waters and subsequent ecosystem changes.