Re-initiation of bottom water formation in the East Sea (Japan Sea) in a warming world.

The East Sea (Japan Sea), a small marginal sea in the northwestern Pacific, is ventilated deeply down to the bottom and sensitive to changing surface conditions. Addressing the response of this marginal sea to the hydrological cycle and atmospheric forcing would be helpful for better understanding present and future environmental changes in oceans at the global and regional scales. Here, we present an analysis of observations revealing a slowdown of the long-term deepening in water boundaries associated with changes of water formation rate. Our results indicate that bottom (central) water formation has been enhanced (reduced) with more (less) oxygen supply to the bottom (central) layer since the 2000s. This paper presents a new projection that allows a three-layered deep structure, which retains bottom water, at least until 2040, contrasting previous results. This projection considers recent increase of slope convections mainly due to the salt supply via air-sea freshwater exchange and sea ice formation and decrease of open-ocean convections evidenced by reduced mixed layer depth in the northern East Sea, resulting in more bottom water and less central water formations. Such vigorous changes in water formation and ventilation provide certain implications on future climate changes.

Source identification and apportionment of halogenated compounds observed at a remote site in East Asia.

The sources of halogenated compounds in East Asia associated with stratospheric ozone depletion and climate change are relatively poorly understood. High-precision in situ measurements of 18 halogenated compounds and carbonyl sulfide (COS) made at Gosan, Jeju Island, Korea, from November 2007 to December 2011 were analyzed by a positive matrix factorization (PMF). Seven major industrial sources were identified from the enhanced concentrations of halogenated compounds observed at Gosan and corresponding concentration-based source contributions were also suggested: primary aluminum production explaining 37% of total concentration enhancements, solvent usage of which source apportionment is 25%, fugitive emissions from HCFC/HFC production with 11%, refrigerant replacements (9%), semiconductor/electronics industry (9%), foam blowing agents (6%), and fumigation (3%). Statistical trajectory analysis was applied to specify the potential emission regions for seven sources using back trajectories. Primary aluminum production, solvent usage and fugitive emission sources were mainly contributed by China. Semiconductor/electronics sources were dominantly located in Korea. Refrigerant replacement, fumigation and foam blowing agent sources were spread throughout East Asian countries. The specified potential source regions are consistent with country-based consumptions and emission patterns, verifying the PMF analysis results. The industry-based emission sources of halogenated compounds identified in this study help improve our understanding of the East Asian countries' industrial contributions to halogenated compound emissions.

Emissions of halogenated compounds in East Asia determined from measurements at Jeju Island, Korea.

High-frequency in situ measurements at Gosan (Jeju Island, Korea) during November 2007 to December 2008 have been combined with interspecies correlation analysis to estimate national emissions of halogenated compounds (HCs) in East Asia, including the chlorofluorocarbons (CFCs), halons, hydrochlorofluorocarbons (HCFCs), hydrofluorocarbons (HFCs), perfluorocarbons (PFCs), sulfur hexafluoride (SF(6)), and other chlorinated and brominated compounds. Our results suggest that overall China is the dominant emitter of HCs in East Asia, however significant emissions are also found in South Korea, Japan and Taiwan for HFC-134a, HFC-143a, C(2)F(6), SF(6), CH(3)CCl(3), and HFC-365mfc. The combined emissions of CFCs, halon-1211, HCFCs, HFCs, PFCs, and SF(6) from all four countries in 2008 are 25.3, 1.6, 135, 42.6, 3.6, and 2.0 kt/a, respectively. They account for approximately 15%, 26%, 29%, 16%, 32%, and 26.5% of global emissions, respectively. Our results show signs that Japan has successfully phased out CFCs and HCFCs in compliance with the Montreal Protocol (MP), Korea has started transitioning from HCFCs to HFCs, while China still significantly consumes HCFCs. Taiwan, while not directly regulated under the MP, is shown to have adapted the use of HFCs. Combined analysis of emission rates and the interspecies correlation matrix presented in this study proves to be a powerful tool for monitoring and diagnosing changes in consumption of HCs in East Asia.

Occurrence of perfluorooctanoate and perfluorooctanesulfonate in the Korean water system: implication to water intake exposure.

Perfluorinated compounds (PFCs) measured in surface running waters indicated the existence of different emission sources in eight main city basins. The tap water reflected the contamination pattern and levels in their corresponding source water basins. The daily intakes through tap water consumption ranged from <0.01 to 0.73 ng kg(-1) d(-1) for perfluorooctanoate (PFOA) and <0.01 to 0.08 ng kg(-1) d(-1) for perfluorooctanesulfonate (PFOS). Tap water intake-derived exposure accounted for 8.6%-101% (for PFOA) and while <10% (for PFOS) of total daily exposure, which was estimated from Korean serum concentrations using a pharmacokinetic model. Our findings indicate that tap water intake could be an important contributor to PFOA exposure in Korean populations; accordingly, additional efforts are necessary to improve the removal efficiency of perfluorinated compounds (PFCs) in the water purification process. However, more fundamentally the aim would be to reduce the discharge of PFCs from potential sources within the basin.

Distribution of perfluorochemicals between sera and milk from the same mothers and implications for prenatal and postnatal exposures.

The levels of six perfluorocarboxylates (PFCAs), four perfloroalkylsulfonates (PFASs), and one sulfonamide were measured in paired samples of maternal serum, umbilical cord serum, and breast milk. The maternal and cord sera were strongly correlated with each other for all measured compounds (r>0.5 and p<0.01). Nevertheless, there was a significant difference in compound composition profile between the two sera matrices, with a more depletion of the longer chain compounds in cord serum. The transfer efficiency values from maternal to cord serum (TFCS/MS) decreased by 70% with each increasing unit of -CF2 chain within a PFCA group, and for perfluorooctanesulfonate (PFOS), by a half compared to perfluorooctanoate (PFOA). In contrast to the strong correlation in concentrations between the two sera matrices, the pattern of compounds in breast milk differed considerably with those in sera. Accordingly, compound- and matrix-specific transfer must be considered when assessing prenatal and postnatal exposure.

Vertical variability of seawater DMS in the South Pacific Ocean and its implication for atmospheric and surface seawater DMS.

Shipboard measurements of atmospheric dimethylsulfide (DMS) and sea surface water DMS were performed aboard the R/V Onnuri across the South Pacific from Santiago, Chile to Fiji in February 2000. Hydrographic profiles of DMS, dissolved dimethylsulfoniopropionate (DMSP(d)), and particulate DMSP(p) in the upper 200m were obtained at 16 stations along the track. Atmospheric and sea surface water DMS concentrations ranged from 3 to 442pptv and from 0.1 to 19.9nM, respectively; the mean values of 61pptv and 2.1nM, respectively, were comparable to those from previous studies in the South Pacific. The South Pacific Gyre was distinguished by longitudinal-vertical distributions of DMS, DMSP(d), and DMSP(p), which was thought to be associated with the characteristic modification of biological activities that occurs mainly due to significant change in water temperature. The averaged DMS maximum appeared at 40m depth, whereas DMSP(p) and DMSP(d) maxima coincided with that of dissolved oxygen content at 60-80m. The sea-to-air fluxes of DMS were estimated to be 0.4-11.3micromold(-1)m(-2) (mean=2.8micromold(-1)m(-2)). A fairly good correlation between atmospheric DMS and sea-to-air DMS flux indicated that atmospheric DMS concentration was more sensitive to change in physical parameters than its photochemical removal process or surface seawater DMS concentrations.

Distribution of organochlorine pesticides in intertidal and subtidal sediments in coastal wetland with high tidal ranges.

The present study aimed to understand the distribution characteristics of organochlorine pesticides (OCPs) in wetlands experiencing high tides and the manner in which these characteristics are affected by various factors, in particular, two distinct physical and topographical features (i.e., sub- and intertidal zones). For all OCPs except HCHs, the distribution levels were higher in the intertidal zone than in the subtidal zone. The spatial heterogeneity in the isomer compositional pattern, distribution levels, and correlation among individual OCPs were pronounced in the intertidal zone. Spatial homogeneity was observed within the subtidal zone, indicating that the effect of flushing and mixing was strong enough to diminish the potential local concentration peaks and unique composition pattern. It was evident that input paths and their strength impact the horizontal and transversal distribution of OCPs. The OCP group-specific discrepancy in spatial distribution suggested that (1) chlordane and chlorobenzenes were from a single dominant innermost terrestrial input path, (2) DDTs were from multiple terrestrial input paths, and (3) HCH was likely to be from the outer sea. The observations in this study imply that (1) benthic organisms could experience greater exposure in the intertidal basin than in the subtidal zone and (2) management measures of OCPs should be set after considering the tidal effect and the OCP-specific input paths.

Characteristic behavior of peroxyacetyl nitrate (PAN) in Seoul megacity, Korea.

We measured the concentrations of peroxyacetyl nitrate (PAN) and other photochemically reactive species, including O3, NO2, and non-methane hydrocarbons (NMHCs), in the Seoul Metropolitan area (SMA) during May through June in 2004 and 2005. PAN was determined using a fast chromatograph with luminol-based chemiluminescence detection. Mixing ratios of PAN ranged from below the detection limit (0.1ppbv) to 10.4ppbv with an average of 0.8ppbv. O3 concentrations ranged from 0 to 141ppbv. The average PAN/O3 ratio of 0.07 was higher than that observed in cities of Europe and North America (0.02) where control strategies have been enforced to reduce hydrocarbon emissions through extensively reformulated gasoline programs. Strong positive correlations between daily PAN and O3 maxima during the day demonstrate that similar photochemical factors controlled the production of these two chemicals. However, relationships between PAN and its precursors, NO2 and NMHCs, suggest that PAN production was more sensitive to NO2 than NMHCs levels whereas O3 production was limited by the overall availability of NMHCs. It is likely that the compositions of NMHCs in SMA were favorable for PAN production because of the low fractions of oxygenated compounds in automobile fuels. PAN maxima were observed around noon, which was 2-3h earlier than the much broader O3 maxima that occurred in the midafternoon. After reaching the maximum, PAN concentrations rapidly dropped within a few hours, which could be largely due to thermal destruction and to limited production under the typically low NO2 levels that occurred in the early afternoon. The heterogeneous destruction of particulate matter could be an additional sink for PAN in SMA.

Atmospheric peroxides over the North Pacific during IOC 2002 shipboard experiment.

Atmospheric hydrogen peroxide and methyl hydroperoxide were determined onboard the Melville over the North Pacific from Osaka to Honolulu during May-June 2002. The concentrations of H(2)O(2) and CH(3)OOH increased from 0.64+/-0.57 ppbv and 0.27+/-0.59 ppbv in subpolar region (30-50 degrees N) to 1.96+/-0.95 ppbv and 1.56+/-1.3 ppbv in subtropical region (24-30 degrees N). The increase in concentrations towards the Equator was more pronounced for CH(3)OOH than H(2)O(2). In contrast, the levels of O(3) and CO were decreased at lower latitudes as air mass was more aged, denoted by the ratios of C(2)H(2)/CO and C(3)H(8)/C(2)H(6). CH(3)OOH concentrations showed a clear diurnal variation with a maximum around noon and minimum before sunrise. Frequently, the concentrations of peroxides remained over 1 ppbv in the dark and even gradually increased after sunset. In addition, the ratios of C(2)H(4)/C(2)H(6) and C(3)H(6)/C(3)H(8) were increased in aged subtropical air, which implies that these alkenes were emitted from the ocean surface. As a result, the reaction of these biogenic alkenes with O(3) was suggested to be a potential source for peroxides in aged marine air at lower latitudes.