Characterization of Pu concentration and its isotopic composition in soils of Gansu in northwestern China

The total ^239+240Pu activities and ²⁴⁰Pu/²³⁹Pu atom ratios in surface soil samples (0–5 cm) in the Kumtag Desert in western Gansu Province, and in a soil core sample in Lanzhou were investigated using a sector-field ICP-MS. In the surface soil samples, ^239+240Pu activities in fine particles (<150 μm) were 1.3–2.1 times of those in coarse particles (150 μm–1 mm) which ranged from 0.005 to 0.157 mBq/g. Atom ratios of ²⁴⁰Pu/²³⁹Pu in the surface soils ranged from 0.168 to 0.192 with a mean of 0.182 ± 0.008. The mean ratio was similar to the typical global fallout value although the Kumtag Desert was believed to have received close-in fallout derived from Chinese nuclear weapons tests mainly conducted in the 1970s. Furthermore, the mean ²⁴⁰Pu/²³⁹Pu atom ratio observed in the soil core sample in Lanzhou was similar to the typical global fallout value. In the soil core sample, ^239+240Pu activities in the various layers ranged from 0.012 to 0.23 mBq/g, and the inventory of ^239+240Pu (32.4 Bq/m², 0–23 cm) was slightly lower than that expected from global fallout (42 Bq/m²) at the same latitude. Rapid downward migration of Pu isotopes was observed in Lanzhou soil core sample layers. The contribution of the 10-cm deep top layers of surface soils to total inventory was only 17%, while the contribution of deeper layers (10–23 cm) was as high as 83%. The ^239+240Pu activity levels and ²⁴⁰Pu/²³⁹Pu atom ratios in soils in Gansu Province, China are similar to those in atmospheric deposition samples collected in the spring in recent years in Japan.     

Horizontal distribution of steroid estrogens in surface sediments in Tokyo Bay

A monitoring survey was conducted to investigate the distribution of steroid estrogens and their conjugates in surface sediments of Tokyo Bay for the first time, which is known as one of the most heavily polluted marine embayments in the world. The surface sediment samples were collected at 20 locations covering the whole area of Tokyo Bay and analyzed for steroid estrogens and their conjugates using liquid chromatography-tandem mass spectrometry. The concentrations of 17beta-estradiol (beta-E2) and estrone (E1) ranged from ND (below the detection limit; <0.07) to 0.59 and from 0.05 to 3.60 ng g-1 dry, respectively. Those concentrations were higher in the northern part of the bay, which is directly receiving huge quantities of pollutants from adjacent rivers containing a large amount of municipal and industrial wastewater. 17alpha-Estradiol (alpha-E2) and estrone-3-sulfate (E1-3S) were detected in some of the samples, whereas neither of the other conjugates, estriol (E3) or 17alpha-ethynylestradiol (EE2), was found.     

Effects of parabens on apoptosis induced by serum-free medium

Alkyl esters of p-hydroxybenzoic acids (parabens), an endocrine disrupter, are used as preservatives in cosmetics and foods. In this study, to understand the relationship between parabens and differentiation in infants, the effects of parabens on apoptosis induced by serum deprivation in PC12 cells were investigated. In addition, apoptosis-related factors were assayed. As results, a tendency toward enhancement of apoptosis was observed in the cells cultured in the serum-free medium with methylparaben, and this tendency was suggested to be related to the contents of BAD, a pro-apoptotic protein. Butylparaben did not show any tendency to enhance apoptosis.     

Mercury volatilization by the most mercury-resistant bacteria from the seawater of Minamata Bay in various physiological conditions

The volatilization of mercuric chloride (HgCl₂) and methyl mercuric chloride (CH₃HgCl) by the 45 strains (35 Pseudoalteromonas sp., 2 Vibrio sp., 1 Aeromonas sp., and 7 unclassified) of the most mercury-resistant bacteria from Minamata Bay seawater was examined in various physiological conditions. The bacteria could grow and volatilize HgCl₂ in the liquid medium containing 1-10% NaCl. Two Pseudoalteromonas strains could grow and volatilize HgCl₂ at pH levels ranging from 5.0 to 10.0. The resting cells of 43 strains could volatilize HgCl₂ at concentrations ranging from 30 to 68% after 1-h incubation at 30vv°C. The resting cells of 41 strains could volatilize CH₃HgCl at concentrations ranging from 13 to 88% after 1-h incubation at 30vv°C. Ninety-two percent of mercury was removed from the phosphate buffer containing 0.1 7g/ml by a resting cell of Pseudoalteromonas strain H-4 after 30-min incubation at 30vv°C. We were able to screen the special bacteria, which could volatilize mercury compounds at a high rate in various physiological conditions, for the purpose of developing mercury removal methods using bacteria.     

Growth and reproductive biology of the small penaeid shrimp Trachysalambria curvirostris in Tokyo Bay

We investigated the growth and reproductive biology of the penaeid shrimp Trachysalambria curvirostris in Tokyo Bay, Japan, by monthly bottom-trawl surveys from May 2002 to December 2004. We also examined oogenesis in T. curvirostris by histological observation of the ovary. Females grew faster and attained a larger body size for age than males. The growth rate was high in summer and low in winter and was likely to be associated with seasonal changes in water temperature. The carapace length (CL) at which 50% of females contained vitellogenic oocytes was estimated to be 17.0 mm. The reproductive season extended from May to October. Young-of-the-year appeared in October and could be traced across the months on CL histograms to the following September or October, indicating a 1-year life cycle. This extended reproductive season, together with our observation of asynchronous development of oocytes in the ovary, suggests that multiple spawning by individual females may occur during the reproductive season. Postovulated oocytes were not found among the samples we collected during the daytime, suggesting that final oocyte maturation and spawning occur at night. Cortical crypts in the cytoplasm of the oocyte, considered to be a general feature of oogenesis in penaeid shrimps, were not found in T. curvirostris, even in oocytes undergoing germinal vesicle breakdown. This result implies that the cortical reaction after spawning of T. curvirostris may be different from that of other penaeid shrimps.     

The pollution and ecological risk of endosulfan in soil of Huai’an city, China

Endosulfan, a persistent organic pollutant newly listed under the Stockholm Convention, is currently widely produced and used as a pesticide in China. Concentrations of endosulfans (including α-, β-isomers, and their metabolite endosulfan sulfate) were determined in surface soil collected from Huai’an city, where the largest endosulfan producer is located. The concentrations of Σendosulfan (sum of α-endosulfan, β-endosulfan, and endosulfan sulfate) at all sites ranged from 0.28 to 44.81?ng/g dry weight (dw), following a lognormal distribution. The geometric mean was 1.09?ng/g dw, and the geometric standard deviation was 3.02. The β-endosulfan levels were consistently greater than those of α-isomer. The concentration ratios of α-endosulfan to β-endosulfan ranged from 0.03 to 0.70, which were much lower than the commercial endosulfan mixture. This is because that α-endosulfan is more volatile and degrades faster than β-endosulfan in soil. The contour map of Σendosulfan levels in soil indicates that the factory was the point pollution source with the highest endosulfan level in its surrounding area, especially the southern area. However, the non-point agricultural sources are more important. Based on Monte Carlo simulation, the Σendosulfan inventory in soil in Huai’an is estimated to be 0.8–3.0 tons. In order to understand the potential ecological risk of endosulfan, the Monte Carlo-based hazard quotient distribution was estimated and showed that Σendosulfan posed a potentially high risk to soil organisms. To our knowledge, this study is the first that reports soil pollution and risk of endosulfan around the manufacturer in China. This study will help China’s implementation of Stockholm Convention for the reduction and elimination of endosulfan in future.     

Detoxification of hexachlorobenzene by dechlorination with potassium-sodium alloy

Dechlorination of hexachlorobenzene (HCB) was achieved by a liquid potassium–sodium (K–Na)-alloy. HCB in a cyclohexane/benzene solution (22 mmol/l, 4.67 g/l as chlorine) was dechlorinated by almost 100% after a 30-min reaction, indicating high reactivity of K–Na alloy and high proton donating power of cyclohexane. Decreasing orders of chlorobenzenes identified after a 15-min reaction, by amount were 1,2,3,4- > 1,2,3,5- > 1,2,4,5- for tetrachlorobenzenes, 1,2,4- > 1,2,3- > 1,3,5- for trichlorobenzenes, and 1,4- > 1,3- > 1,2- for dichlorobenzenes. It was hypothesized that once one chlorine atom in HCB was replaced with a proton, the adjacent chlorine atom to the proton tended to be replaced with another hydrogen atom. A total of 63 PCBs formed via the Wurtz–Fittig reaction were identified as by-products in the sample after a 15-min reaction. Among PCBs found, 2,3^′,4^′,5-tetrachlorobiphenyl, which was a product from 1,2,4-trichlorobenzene formed via the Wurtz–Fittig reaction, was detected in relatively high concentration (48.9 nmol/ml). The sample obtained from a reaction mixture after 30 min contained only 14 PCBs in trace amounts, indicating that the PCBs formed were also further dechlorinated by K–Na alloy. Non-chlorinated compounds––such as methylbenzene, dimethylbenzene, dimer of tetrahydrofuran, and dicyclohexyl (dimer of cyclohexane)––were also identified in the samples. A method using K–Na alloy developed in the present study dechlorinated satisfactorily HCB at room temperature.     

Effect of metabolism on bioconcentration of geometric isomers of d-phenothrin in fish

Yearling carp (Cyprinus carpio) were exposed to d-phenothrin (a 1:4 mixture of d-cis and d-trans isomers) in the absence and the presence of piperonyl butoxide under the flow-through test condition and the bioconcentration factors (BCF's) of the geometric isomers were separately evaluated. It was demonstrated that BCF values for the d-cis isomer were significantly higher by 1.1 to 2.2-fold than those for the d-trans isomer and the subsequent exposure in the presence of piperonyl butoxide resulted in elevated BCF values for the d-cis isomer, but no remarkable change in BCF's was observed for the d-trans isomer. The elevation observed here was presumably attributable to a reduced elimination caused by inhibited oxidative reactions characteristic to the d-cis isomer. The contribution of biotransformation to the elimination rate constant (K₃/K₂ was estimated to be 2.3–11. Thus, the result was well explained by a distinct oxidative metabolism of the d-cis isomer and a significance of metabolism in bioconcentration phenomenon was exemplified.     

Decomposition and removal of ionic liquid in aqueous solution by hydrothermal and photocatalytic treatment

We demonstrated a complete decomposition method for ionic liquids (ILs; organic cation part: butyl-methyl or ethyl-methyl imidazolium, and inorganic anion part: PF₆ ⁻, BF₄ ⁻ or Br⁻) in aqueous media by combining a hydrothermal mineralization method with a photocatalytic decomposition (PD) method. As a result, the hydrothermal treatment with Ca(OH)₂ mineralizer could effectively remove the inorganic anion part, such as PF₆ ⁻ or BF₄ ⁻ and the PD could decompose the organic cation part effectively. Therefore, the detoxification of ILs in aqueous media was accomplished by the present method.     

Polychlorinated dibenzo-p-dioxins and dibenzofurans in invertebrate animals from a rural beach in Japan

PCDDs and PCDFs were analyzed by high resolution GC MS in several invertebrate animals collected from a rural beach in Japan. PCDDs and PCDFs were detected in all samples. Total concentration of PCDDs and PCDFs ranged 8.8–120 pg g⁻¹ wet and 3.5–38 pg g⁻¹ wet, respectively. TEQs of invertebrate animals examined ranged from 0.048 pg g⁻¹ wet in sea slug to 0.91 pg g⁻¹ wet in mussel. Isomer profiles in all samples were similar to each other despite of variety of species. Their major sources are estimated to be herbicides such as CNP and PCP, and combustion by using a statistical analysis of isomer profiles.