Description: Perfluorinated alkyl substances (PFASs) have been found widely in the environment including remote marine locations. The mode of transport of PFASs to remote marine locations is a subject of considerable scientific interest. Assessment of distribution of PFASs in wet precipitation samples (i.e., rainfall and snow) collected over an area covering continental, coastal, and open ocean will enable an understanding of not only the global transport but also the regional transport of PFASs. Nevertheless, it is imperative to examine the representativeness and suitability of wet precipitation matrixes to allow for drawing conclusions on the transport PFASs. In this study, we collected wet precipitation samples including rainfall, surface snow, and snow core from several locations in Japan to elucidate the suitability of these matrixes for describing local and regional transport of PFASs. Rain water collected at various time intervals within a single rainfall event showed high fluxes of PFASs in the first 1-mm deposition. The scavenging rate of PFASs by wet deposition varied depending on the fluorocarbon chain length of PFAS. The depositional fluxes of PFASs measured for continental (Tsukuba, Japan) and open ocean (Pacific Ocean, 1000 km off Japanese coast) locations were similar, on the order of a few nanograms per square meter. The PFAS profiles in "freshly" deposited and "aged" (deposited:on the ground for a few days) snow samples taken from the same location varied considerably. The freshly deposited snow represents current atmospheric profiles of PFASs, whereas the aged snow sample reflects sequestration of local sources of PFASs from the atmosphere. Post-depositional modifications in PFAS profiles were evident, suggesting reactions of PFASs on snow/ice surface. Transformation of precursor chemicals such as fluorotelomer alcohols into perfluoroalkylcarboxylates is evident on snow surface. Snow cores have been used to evaluate time trends of PFAS contamination in remote environments. Snow collected at various depths from a core of up to 7.7 m deep, at Mt. Tateyama (2450 m), Japan, showed the highest concentrations of PFASs in the surface layer and the concentrations decreased with increasing depth for most PFASs, except for perfluorobutanesulfonate (PFBS). Downward movement of highly water soluble PFASs such as PFBS, following melting and freezing cycles of snow, was evident from the analysis of snow core

Description: The widespread distribution of perfluorinated chemicals (PFCs) in different environmental matrices has prompted concern about the sources, fate, and transport of these classes of chemicals. PFCs are present in the atmosphere, but only a few studies have investigated their occurrence in precipitation. In this study, concentrations of 20 PFCs, including C3-C5 short-chain PFCs, were quantified using HPLC-MS/MS in precipitation samples from Japan (n = 31), the United States In = 12), China (n = 5), India (n = 2), and France (n = 2). Among the PFCs measured, perfluoropropanoic acid (PFPrA) was detected in all of the precipitation samples. Average total PFC concentrations ranged from 1.40 to 18.1 ng/L for the seven cities studied. The greatest total PFC concentrations were detected in Tsukuba, Japan, whereas the lowest concentrations were detected in Patna, India. PFPrA, perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA) were found to be the dominant PFCs in Japanese and U.S. precipitation samples. No observable seasonal trend was found in precipitation samples from two locations in Japan. Annual fluxes of PFCs were estimated for Japan and the U.S. and the evidence for precipitation as an effective scavenger of PFCs in the atmosphere is reported.

Description: Determination of polychlorinated biphenyls (PCBs) and nonylphenols (NoPhs) in the Sea of Japan not only points out the extent of marine pollution but also helps to understand the deep sea structure of that semi-enclosed “small ocean”. Using an in-situ filtration/extraction technique, two vertical profiles (deep water and shallow coastal water) and two space-integrated surface profiles were taken. Concentrations of ∑CBs (sum of 30 individual congeners) in solution were between 0.1 and 1.2 pg dm-3 and in suspension were between 0.2 and 1.5 pg dm-3; those of ∑NoPhs in solution were 2−150 pg dm-3 and below detection limits in suspension. The concentrations of ∑CBs and nonylphenols in solution as well as the compositions of the CB mixtures in solution in the vertical profile indicates a vertical structure similar to the situation in the open ocean as suggested by Kim (Biogeochemical processes in the North Pacific; Tsunogai, S., Ed.; Japan Marine Science Foundation:  Tokyo 1996; pp 41−51). The concentrations of CBs in solution were determined primarily by characteristics of the water bodies involved, solution−suspension interactions playing only a minor role. Principal component analyses of the data revealed a relation between deep and bottom waters and surface waters of the nearby region.

Description: Highlights: • A remarkable increase in PFASs levels was found in the Japan Sea from 2005 to 2010. • The inventory of PFASs in whole water mass was firstly assessed in semi-closed sea. • The annual ΣPFASs inflow from the East China Sea to the Japan Sea was around 70.8 t. • The PFASs vertical profile in the Mediterranean Sea implied a few pollution sources. • PFOA predominated in the Japan Sea, the Mediterranean Sea, and the East China Sea. Abstract: Perfluoroalkyl substances (PFASs) have become an important class of global environmental contaminants, yet their vertical profile in the marine water column is still less understood, especially for the semi-closed seas. In this study, the contamination level and spatial distribution of 8 PFASs were investigated in both surface and vertical water samples from two semi-closed seas, the Japan Sea and the Mediterranean Sea. Similar levels and compositions of PFASs were found between these two seas. The vertical profile of PFASs in the Mediterranean Sea was variable while that was relatively steady in the Japan Sea, probably due to their different pollution sources. The accumulation rate of PFASs from the East China Sea to the Japan Sea was calculated, for which perfluorooctanesulfonic acid and perfluorooctanoic acid were found to have high accumulation potency in both surface and deep water; most of the investigated PFASs were accumulated in the deep water due to the long residence time while they were more likely to escape to the Pacific Ocean in the surface water. This work aimed (i) to study the distribution of PFASs in both surface and vertical water samples in two semi-closed seas, namely the Japan Sea and for the first time the Mediterranean Sea, (ii) to assess the temporal trend in the Japan Sea, and (iii) to firstly investigate the potential transport of PFASs from the East China Sea and Taiwan Strait in order to estimate the inventory of PFASs in whole water mass in the Japan Sea.

Description: Deep waters of the Sea of Japan and surface waters of the Pacific Coast of Honshu and the northeast Sea of Japan were analysed for polychlorinated biphenyls (PCBs) pollution. the ΣPCB concentrations in solution in the Sea of Japan (50–3000 m) were between 140 and 1230 fg dm−3. the space-integrated surface water concentration near the Pacific coast of northern Honshu was 140 fg dm−3and for the surface water of the Sea of Japan was 230 fg dm−3. Based on these analyses four water masses were deduced in the Sea of Japan during the summer months. It is shown for the first time in the Sea of Japan that polychlorinated biphenyls are excellent chemical indicators of not only the anthropogenic pollution, but also water masses.

Description: Perfluorinated acids and their salts have emerged as an important class of global environmental contaminants. Biological monitoring surveys conducted using tissues of marine organisms reported the occurrence of perfluorooctanesulfonate (PFOS) and related perfluorinated compounds in biota from various seas and oceans, including the Arctic and the Antarctic Oceans. Occurrence of perfluorinated compounds in remote marine locations is of concern and indicates the need for studies to trace sources and pathways of these compounds to the oceans. Determination of sub-parts-per-trillion (ng/L) or parts-per-quadrillion (pg/L) concentrations of aqueous media has been impeded by relatively high background levels arising from procedural or instrumental blanks. Our research group has developed a reliable and highly sensitive analytical method by which to monitor perfluorinated compounds in oceanic waters. The method developed is capable of detecting PFOS, perfluorohexanesulfonate (PFHS), perfluorobutanesulfonate (PFBS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), and perfluorooctanesulfonamide (PFOSA) at a few pg/L in oceanic waters. The method was applied to seawater samples collected during several international research cruises undertaken during 2002–2004 in the central to eastern Pacific Ocean (19 locations), South China Sea and Sulu Seas (five), north and mid Atlantic Ocean (12), and the Labrador Sea (20). An additional 50 samples of coastal seawater from several Asian countries (Japan, China, Korea) were analyzed. PFOA was found at levels ranging from several thousands of pg/L in water samples collected from coastal areas in Japan to a few tens of pg/L in the central Pacific Ocean. PFOA was the major contaminant detected in oceanic waters, followed by PFOS. Further studies are being conducted to elucidate the distribution and fate of perfluorinated acids in oceans.