Determination of nonylphenol ethoxylates and octylphenol ethoxylates in environmental samples using 13C-labeled surrogate compounds

Alkylphenol polyethoxylates (APEOs) have been widely used as nonionic surfactants in a variety of industrial and commercial products. Typical compounds are nonylphenol polyethoxylates (NPEOs) and octylphenol polyethoxylates (OPEOs), which serve as precursors to nonylphenol (NP) and octylphenol (OP), respectively. NP and 4-t-OP are known to have endocrine disrupting effects on fish (medaka, Oryzias latipes), so it is important to know the concentrations of APEOs in the environment. Because the analytical characteristics of these compounds depend on the length of the ethoxy chain, it is necessary to use appropriate compounds as internal standards or surrogates. We synthesized two 13C-labeled surrogate compounds and used these compounds as internal standards to determine NPEOs and OPEOs by high-performance liquid chromatography (LC)-mass spectrometry. Method detection limits were 0.015 microg/L for NP (2)EO to 0.037 microg/L for NP(12)EO, and 0.011 microg/L for OP(3,6)EO to 0.024 microg/L for OP (4)EO. NPEO concentrations in water from a sewage treatment plant were less than 0.05-0.52 microg/L for final effluent and 1.2-15 microg/L for influent. OPEO concentrations were less than 0.05-0.15 microg/L for the final effluent and less than 0.05-1.1 microg/L for influent.     

210Pb deposition in the far East Asia: controlling factors of its spatial and temporal variations

In order to better understand the behavior of ²¹⁰Pb deposition in Far East Asia, comprehensive data of monthly ²¹⁰Pb deposition, which includes several time-series and spatial distribution data at 14 stations in Japan and 2 stations in Taiwan, were analyzed. Pb-210 deposition at most of the sites exhibited a typical seasonal change with higher values in winter and lower values in summer; especially, the greatest ²¹⁰Pb deposition in the world occurred in winter at sites beside the Japan Sea. The deposition behavior of ²¹⁰Pb in Far East Asia differed between winter and summer. The meteorological phenomenon peculiar to winter of the Japan Sea side, i.e., formation of the Japan Sea convergence zone, might cause the high ²¹⁰Pb concentration in rainwater, as may heavy snowfall. The ²¹⁰Pb concentration in rainwater showed long-term variability, although this differed between winter and summer. This long-term variability may be related to climatological factors such as El Niño.     

PCB decomposition and formation in thermal treatment plant equipment

In this study we investigated both the decomposition and unintentional formation of polychlorinated biphenyl congeners during combustion experiments of refuse-derived fuel (RDF) and automobile shredder residue (ASR) at several stages in thermal treatment plant equipment composed of a primary combustion chamber, a secondary combustion chamber, and other equipments for flue gas treatment. In both experiments, the unintentional formation of PCB occurred in the primary combustion chamber at the same time as the decomposition of PCB in input samples. By combusting RDF, non-ortho-PCB predominantly formed, whereas ortho-PCB and symmetric chlorinated biphenyls (e.g., #52/69, #87/108, and #151) tended to be decomposed. ASR formed the higher chlorinated biphenyls more than RDF. These by-products from ASR had no structural relation with ortho-chlorine. Lower chlorinated biphenyls appeared as predominant homologues at the final exit site, while all congeners from lower to higher chlorinated PCB were unintentionally formed as by-products in the primary combustion chamber. This result showed that the flue gas treatment equipments effectively removed higher chlorinated PCB. Input marker congeners of RDF were #11, #39, and #68, while those for ASR were #11, #101, #110/120, and #118. Otherwise, combustion marker congeners of RDF were #13/12, #35, #77, and #126, while those for ASR were #170, #194, #206, and #209. While the concentration of PCB increased significantly in the primary combustion chamber, the value of toxicity equivalency quantity for dioxin-like PCB decreased in the secondary combustion chamber and the flue gas treatment equipments.     

Seasonal variation of 228Ra/226Ra ratio in seaweed: implications for water circulation patterns in coastal areas of the Noto Peninsula, Japan

To examine water circulation patterns of coastal water, 72 seaweed (Sargasso) samples and 27 coastal water samples were collected from coastal areas of the Noto Peninsula, Japan, during the period from December 1998 to June 2002. The (228)Ra and (226)Ra activities of those samples were measured by low-background gamma-ray spectrometry. There was a wide range of activities of (228)Ra (0.5-2Bq/kg-fresh) and (226)Ra (0.5-1.2Bq/kg-fresh) in the Sargasso samples. The (228)Ra/(226)Ra activity ratio of Sargasso samples exhibited seasonal variation with minimum values in June ((228)Ra/(226)Ra= approximately 1) and maximum values in December (1.5-2.5), which was mainly governed by changes in (228)Ra activity. It is also notable that the seasonal variation of the (228)Ra/(226)Ra ratio of Sargasso is in approximate agreement with that of the ambient coastal water. Sargasso samples appear to have retained the (228)Ra/(226)Ra ratio of the ambient coastal waters, and the temporal variations in that ratio provide insight into seasonal changes in water circulation in the Noto Peninsula coastal area.     

Seasonal variation of Ra/Ra ratio in seaweed: implications for water circulation patterns in coastal areas of the Noto Peninsula, Japan

To examine water circulation patterns of coastal water, 72 seaweed (Sargasso) samples and 27 coastal water samples were collected from coastal areas of the Noto Peninsula, Japan, during the period from December 1998 to June 2002. The (228)Ra and (226)Ra activities of those samples were measured by low-background gamma-ray spectrometry. There was a wide range of activities of (228)Ra (0.5-2Bq/kg-fresh) and (226)Ra (0.5-1.2Bq/kg-fresh) in the Sargasso samples. The (228)Ra/(226)Ra activity ratio of Sargasso samples exhibited seasonal variation with minimum values in June ((228)Ra/(226)Ra= approximately 1) and maximum values in December (1.5-2.5), which was mainly governed by changes in (228)Ra activity. It is also notable that the seasonal variation of the (228)Ra/(226)Ra ratio of Sargasso is in approximate agreement with that of the ambient coastal water. Sargasso samples appear to have retained the (228)Ra/(226)Ra ratio of the ambient coastal waters, and the temporal variations in that ratio provide insight into seasonal changes in water circulation in the Noto Peninsula coastal area.     

Studies on automated survey system of environmental chemicals by gas chromatography-mass spectrometry-computer III. Construction of an automated survey system and its application

An automated survey system on the chemicals in environments by a gas chromatography-mass spectrometry-computer system has been constructed of Three Dimensional Mass Chromatography, Modified Probability Based Matching method, and Self Training Interpretive and Retrieval method. And it was applied to analyze environmental materials, with interesting results.     

Surface water mixing estimated from 228Ra and 226Ra in the northwestern North Pacific

We investigated the horizontal distributions of (228)Ra and (226)Ra in surface waters of the northwestern North Pacific Ocean and Okhotsk Sea. Ratios of (228)Ra/(226)Ra were relatively large in the Tsugaru Current (0.6-0.8) and Okhotsk Sea (0.4-0.5), and small in the Western Subarctic Gyre (<0.2) and the Oyashio (0.25-0.3). (228)Ra/(226)Ra ratios in western Subarctic Water (SAW) rose slightly upon mixing with Okhotsk Water (OKW), before becoming the Oyashio Water (OYW). Also, ratios in the OYW increased during mixing with Tsugaru Current Water (TCW). Estimating from (228)Ra/(226)Ra ratios and (226)Ra activities with a simple two-end members-mixing model, we assumed that approximately 23% of the OYW originated from the OKW and the coastal region off northern Honshu (Japan) was strongly influenced by the TCW. From a diagram of (228)Ra activities against salinity, we could roughly divide surface seawater in the study area into the five water masses, which were SAW, OYW, OKW, TCW, and Subtropical Water (STW).