Identifying the external N and Hg inputs to the estuary ecosystem based on the triple isotopic information (δ15NNO3, Δ17ONO3 and δ18ONO3).

The supply and sources of N and Hg in the Geum estuary of the western coast of Korea were evaluated. Triple isotope proxies (δ15NNO3, Δ17ONO3 and δ18ONO3) of NO3- combined with conservative mixing between river and ocean waters were used to improve isotope finger-printing methods. The N pool in the Geum estuary was primarily influenced by the Yellow Sea water, followed by riverine discharge (821 × 106 mol yr-1) and atmospheric deposition (51 × 106 mol yr-1). The influence of the river was found to be greater for Hg than that of the atmosphere. The triple isotope proxies revealed that the riverine and atmospheric inputs of N have been affected by septic wastes and fossil fuel burning, respectively. From the inner estuary towards offshore region, the influence of the river diminishes, thus increasing the relative impact of the atmosphere. Moreover, the isotope proxies showed a significant influence of N assimilation in February and nitrification in May.

Mercury proxy for hydrothermal and submarine volcanic activities in the sediment cores of Central Indian Ridge.

Hydrothermal vent is the one of the main natural Hg sources to the deep ocean. Thus, we investigated which Hg speciation in the sediment core can be the past records for geothermal activities in mid-ocean ridges of the Central Indian Ocean. The result showed that the hydrothermal Hg in the core sediments was mainly associated with Fe-Mn oxides with the elevated concentrations of other hydrothermal-derived trace metals [Co + Zn + Cu]. In addition, the [Sm]/[Nd] and [Rb]/[Sr] ratios and ɛNdCHUR and 87Sr/86Sr isotopic values supported that the extremely high Hg concentrations were possibly originated from the hydrothermal vent. However, the Hg emitted from submarine volcano was mainly associated with sulfides-organic matters because the volcanos did not release Fe and Mn. Thus, our results showed that the sedimentary Hg is an independent toll for reconstruction of paleodynamics of hydrothermal and/or volcanic activities in deep sea basin of the Central Indian Ocean.

Input of terrestrial organic matter linked to deglaciation increased mercury transport to the Svalbard fjords.

Deglaciation has accelerated the transport of minerals as well as modern and ancient organic matter from land to fjord sediments in Spitsbergen, Svalbard, in the European Arctic Ocean. Consequently, such sediments may contain significant levels of total mercury (THg) bound to terrestrial organic matter. The present study compared THg contents in surface sediments from three fjord settings in Spitsbergen: Hornsund in the southern Spitsbergen, which has high annual volume of loss glacier and receives sediment from multiple tidewater glaciers, Dicksonfjorden in the central Spitsbergen, which receives sediment from glacifluvial rivers, and Wijdefjorden in the northern Spitsbergen, which receive sediments from a mixture of tidewater glaciers and glacifluvial rivers. Our results showed that the THg (52 ± 15 ng g-1) bound to organic matter (OM) was the highest in the Hornsund surface sediments, where the glacier loss (0.44 km3 yr-1) and organic carbon accumulation rates (9.3 ~ 49.4 g m-2 yr-1) were elevated compared to other fjords. Furthermore, the δ13C (-27 ~ -24‰) and δ34S values (-10 ~ 15‰) of OM indicated that most of OM were originated from terrestrial sources. Thus, the temperature-driven glacial melting could release more OM originating from the meltwater or terrestrial materials, which are available for THg binding in the European Arctic fjord ecosystems.

Increase in anthropogenic mercury in marginal sea sediments of the Northwest Pacific Ocean.

Over the past century, the addition of anthropogenic mercury (HgANTH) to vast areas of North Pacific marginal seas adjacent to the northeast Asian continent has tripled. Analysis of sediment cores showed that the rate of HgANTH addition (HgANTH flux) was greatest in the East China and Yellow Seas (9.1 µg m-2 yr-1) in the vicinity of China (the source continent), but was small in the Bering and western Arctic Ocean (Chukchi Sea) (0.9 µg m-2 yr-1; the regions furthest from China). Our results show that HgANTH has reached open ocean sedimentary environments over extended areas of the northwestern Pacific Ocean, via the formation of organic-mercury complexes and deposition. The implication of these findings is that the addition of HgANTH (via atmospheric deposition and riverine input) to the ocean environment is responsible for elevated Hg flux into sedimentary environments in the northwest Pacific Ocean.

Sedimentary mercury (Hg) in the marginal seas adjacent to Chinese high-Hg emissions: Source-to-sink, mass inventory, and accumulation history.

We comprehensively investigated sedimentary Hg in Yellow and East China Seas (YECSs), which constitute potentially important depocenters for large anthropogenic Hg emissions from mainland China. A large dataset of Al-TOC-Hg concentrations led to an in-depth understanding of sedimentary Hg in the entire YECSs, including distribution and its determinants, source-to-sink, background levels, inventory in flux and budget, and accumulation history. Especially, the net atmospheric Hg flux to the sediments was estimated to be 1.3 × 10-5 g/m2/yr, which corresponded reasonably well to that calculated using a box model. About 21.2 tons of atmospheric Hg (approximately 4% of the total anthropogenic atmospheric Hg emissions from China) were buried annually in the YECS basin. This result implies that most of atmospheric Hg from China is transferred to the surface of the Pacific (including the East/Japan Sea and South China Sea) by the westerlies and, consequently, can play a critical role in open-sea aquatic ecosystems.

Widespread Anthropogenic Nitrogen in Northwestern Pacific Ocean Sediment.

Sediment samples from the East China and Yellow seas collected adjacent to continental China were found to have lower δ15N values (expressed as δ15N = [15N:14Nsample/15N:14Nair - 1] × 1000‰; the sediment 15N:14N ratio relative to the air nitrogen 15N:14N ratio). In contrast, the Arctic sediments from the Chukchi Sea, the sampling region furthest from China, showed higher δ15N values (2-3‰ higher than those representing the East China and the Yellow sea sediments). Across the sites sampled, the levels of sediment δ15N increased with increasing distance from China, which is broadly consistent with the decreasing influence of anthropogenic nitrogen (NANTH) resulting from fossil fuel combustion and fertilizer use. We concluded that, of several processes, the input of NANTH appears to be emerging as a new driver of change in the sediment δ15N value in marginal seas adjacent to China. The present results indicate that the effect of NANTH has extended beyond the ocean water column into the deep sedimentary environment, presumably via biological assimilation of NANTH followed by deposition. Further, the findings indicate that NANTH is taking over from the conventional paradigm of nitrate flux from nitrate-rich deep water as the primary driver of biological export production in this region of the Pacific Ocean.

Abundant iron and sulfur oxidizers in the stratified sediment of a eutrophic freshwater reservoir with annual cyanobacterial blooms.

The microbial community in eutrophic freshwater sediment was investigated from a 67-cm-deep sediment core collected from the Daechung Reservoir in South Korea, where cyanobacterial blooms have occurred annually for the past 30 years. The majority of core sediments were characterized by dark-grayish, fine-grained mud with abundant gas-escaped and thinly laminated layers. Intervals of summer and winter seasons were represented by periodic peaks of geochemical profiles of parameters such as grain size and relative carbon mass ratios to various nutrients such as nitrogen, sulfur, and phosphorus. In bacteria, Proteobacteria (66.6%) was the most prevalent phylum, followed by Chloroflexi (8.9%), Bacteroidetes (5.1%), and Spirochaetes (2.6%). Archaea were also abundant, representing approximately half of the total prokaryotes in the sediments. Notably, three Bacteria (Sulfuricurvum, Sideroxydans, and Gallionella) and one Archaea (Thermoplasmata) accounted for 43.4% and 38.4% of the total bacteria and archaea, respectively, implying that iron and sulfur oxidizing microorganisms dominate in this eutrophic freshwater sediment. These results indicate that 1) eutrophic freshwater lakes in monsoon climates undergo a stratified sedimentary process with seasonal and annual variations in geochemical and microbial profiles, and 2) the microbial oxidative metabolism of iron and sulfur is notably active in sediments from a eutrophic lake.

Effects of temperature and nutrients on changes in genetic diversity of bacterioplankton communities in a semi-closed bay, South Korea.

Bacterioplankton communities in a semi-closed bay (Jangmok Bay, South Korea) were analysed using a 16S rDNA multiplex 454 pyrosequencing approach. Diversity and operational taxonomic units of bacterioplankton communities in the Jangmok Bay are highest in cold water seasons and lowest in warm water ones. During cold seasons, α-proteobacteria respond rapidly to pulses of the concentration of inorganic nutrients, while γ-proteobacteria during warm water seasons are the most active type of bacterioplankton resent in the prevailing conditions, which include high dissolved organic carbon, chemical oxygen demand and primary production. Cyanobacteria, a minor group constituting 4.58% of the total bacterioplankton, are more abundant at low temperature. Flavobacteria are more abundant in nutrient-rich conditions and the abundance of this group also demonstrated a delayed decline following summer phytoplankton blooms. The pronounced seasonal oscillations in phosphorus concentration and temperature exert strong selection pressure on bacterioplankton communities.

Can the algicidal material Ca-aminoclay be harmful when applied to a natural ecosystem? An assessment using microcosms.

We assessed the ability of an artificial clay (Ca-aminoclay) to suppress harmful algal bloom species (HABs) such as Cochlodinium polykrikoides and Chattonella marina and investigated the ecological responses in the closed and open microcosm systems. The Ca-aminoclay induced rapidly and selectively cell lysis in the HABs. However, applying Ca-aminoclay could cause adverse impacts in terms of biological and environmental changes. The bacterioplankton abundance increased and then, the abundances of heterotrophic nanoflagellates and ciliates increased rapidly. Extremely poor environmental conditions such as increase in nutrients and development of anoxic conditions were sustained continuously in a closed system, while the environmental conditions in open systems deteriorated before recovering to the initial conditions. We evaluated the potential for the occurrence of a bloom of another phytoplankton after HABs had been controlled using the Ca-aminoclay. The Ca-aminoclay controlled blooms of Chattonella marina in mixed cell cultures containing a Tetraselmis chui. However, T. chui increased over time and then bloomed. Therefore, caution should be taken when considering the direct application of Ca-aminoclay in natural environments even though it offers the rapid removal of HABs.

Source- and region-specific distribution of polycyclic aromatic hydrocarbons in sediments from Jinhae Bay, Korea.

This study surveyed polycyclic aromatic hydrocarbons (PAHs) at 80 sites in sediment from Jinhae Bay, which consists of Masan Bay (MSB), Haengam Bay (HAB), Bay Proper (JBP), Wonmoon Bay (WMB), and Gohyun Bay (GHB). Levels of the EPA 16 priority PAHs, 5 groups of alkylated PAH homologues and 2 biogenic PAHs were determined. Total PAHs (sum of all target PAHs) ranged from 37.0 ng/g to 3,110 ng/g with a mean of 339 ng/g. WMB had the highest concentration (473 ± 665 ng/g: average ± standard deviation) followed by GHB (214 ± 141 ng/g), MSB (175 ± 358 ng/g), JBP (133 ± 86.0 ng/g) and HAB (118 ± 129 ng/g). A tiered-source identification approach using the pyrogenic index, PAH isomer ratios and alkylated PAH double ratios found that both pyrogenic and petrogenic PAHs were dominant, and identified three different source- and region-specific groups. Input pathway tracers, such as butyltins, nonylphenols and dibenzothiophenes, were used to track the main input pathways. A shipyard and urban runoff were identified as the major input pathways of PAHs into GHB, and urban runoff was identified as a major pathway into MSB and WMB. Used crankcase oil, diesel exhaust, tyre debris and asphalt were considered to be the dominant PAH sources in urban runoff. Several PAH compounds exceeded the interim marine sediment quality guidelines for the protection of aquatic environments, among which dibenz[a,h]anthracene exceeded the guidelines in 16% of surveyed sites. Current PAH levels in MSB indicated an improving situation following the implementation of a total pollutant load management system (TPLMS); this is in accordance with other studies. WMB was recognised as an area of concern within this bay, suggesting the update of the TPLMS in this region.

Historical record of metal accumulation and lead source in the southeastern coastal region of Korea.

Concentrations of heavy metals and Pb isotopes were measured in the 1-M HCl leaching fraction of core sediments spanning the last 400 years. This sedimentary record of pollution history in metal concentrations shows a good correlation with the increases in industrialization, urbanization, and energy consumption since 1901s. Notably, the Pb concentration and the (207)Pb/(206)Pb and (208)Pb/(206)Pb ratios were constant before the 1910s (16.7 µg/g, 0.844, and 2.098, respectively), whereas they increased steadily up to 21.9 µg/g, 0.848, and 2.101 after the 1910s. The correlations between Pb isotope ratios ((206)Pb, (207)Pb, and (208)Pb) showed different linear regression trends for core sediments before and after the 1910s, indicating differences in Pb sources. Our interpretation suggests that the source of anthropogenic Pb in Korean coastal region and the Yellow Sea shelf was presumed to be Chinese coals or ores, which have also played a major role as sources of atmospheric particulate Pb.

Toxicological impact assessment of heavy metal contamination on macrobenthic communities in southern coastal sediments of Korea.

In the heavily industrialized Masan Bay of southern coast, Korea, the potential harmful effects of heavy metals (Cd, Co, Cu, Ni, Pb, Sn, Zn, and Hg) were evaluated in terms of the pollution load index (PLI) and ecological risk assessment index (ERI) methods, and the results obtained were considered alongside the health of the macrobenthic fauna communities. The results revealed that the bay sediments, especially in the inner bay and the outfall area of a sewage treatment plant, are exposed to moderate to serious levels of metal pollution. Hg and Cd contributed the most to the potential toxicity response indices in sediments recently deposited in the bay. The potential ecological risk assessment of heavy metals in the bay was highlighted by the use of the benthic biological pollution index (BPI), suggesting that the ERI is a useful toxicity response index, which can quantify the overall ecological risk level to a target environment.

Sedimentary records of metal contamination and eutrophication in Jinhae-Masan Bay, Korea.

Historical environmental pollution in a semi-enclosed coastal bay was investigated using high-resolution sedimentary records for C(org), N(tot), CaCO(3,) δ(13)C, and δ(15)N signatures, and trace metals. A temporal increase in organic matter might have been attributable to enhanced primary marine productivity, presumably caused by increased anthropogenic nutrient inputs in the semi-enclosed, eutrophic system. Metal accumulation occurred in three stages: a preindustrial stage before the 1930s with natural concentrations of metals, an industrialization stage (1940s-1970s) with the highest concentrations, and a postindustrial stage (post 1970s) with stable or decreasing concentrations. However, Hg exhibited a different accumulation history, with concentrations increasing in the early 1900s and accelerating after the 1920s, probably in response to coal burning.