Toxicity and metabolism of copper pyrithione and its degradation product, 2,2'-dipyridyldisulfide in a marine polychaete

We conducted acute toxicity tests and sediment toxicity tests for copper pyrithione (CuPT) and a metal pyrithione degradation product, 2,2′-dipyridyldisulfide [(PS)₂], using a marine polychaete Perinereis nuntia. The acute toxicity tests yielded 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 0.06 mg L⁻¹ and 7.9 mg L⁻¹, respectively. Sediment toxicity tests resulted in 14-d LC₅₀ concentrations for CuPT and (PS)₂ of 1.1 mg kg⁻¹ dry wt. and 14 mg kg⁻¹ dry wt., respectively. In addition to mortality, sediment avoidance behavior and decreases in animal growth rate were observed; growth rate was the most susceptible endpoint in the sediment toxicity tests of both toxicants. Thus, we propose lowest observed effect concentrations of 0.3 mg kg⁻¹ dry wt. and 0.2 mg kg⁻¹ dry wt. for CuPT and (PS)₂, respectively, and no observed effect concentrations of 0.1 mg kg⁻¹ dry wt. for both CuPT and (PS)₂. The difference in the toxicity values between CuPT and (PS)₂ observed in the acute toxicity test was greater than the difference in these values in the sediment toxicity test, and we attribute this to (PS)₂ being more hydrophilic than CuPT. In addition to the toxicity tests, we analyzed conjugation activity of several polychaete enzymes to the toxicants and marked activity of palmitoyl coenzyme-A:biocides acyltransferase and UDP-glucuronosyl transferase was observed.     

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.     

Photodechlorination of octachlorodibenzothiophene and octachlorodibenzofuran: comparison of experimental degradation pathways with degradation pathways predicted by DFT

Polychlorodibenzothiophenes (PCDTs) are sulfur analogues of polychlorodibenzofurans (PCDFs) and have been detected in environmental samples. We used density functional theory calculations (Gaussian 98W) to predict the photodechlorination pathways of octachlorodibenzothiophene (OCDT) and octachlorodibenzofuran (OCDF) in hexane, and we compared the predicted pathways with those observed during UV irradiation experiments. OCDT and OCDF were observed to degrade through first-order dechlorination processes, and the rate constant for OCDT was less than one-third that for OCDF. The main experimental photodechlorination pathways of OCDT and OCDF led to hexachlorinated and tetrachlorinated congeners, respectively; that is, the photodechlorination pathway of OCDT differed from that of OCDF. On the assumption that the dechlorination mechanisms involved radical reactions, we used DFT calculations to estimate bond-dissociation energies and single-point energies of OCDT and OCDF and their dechlorinated congeners, and we used the resulting information, along with hypotheses regarding the rate-controlling step of the degradations, to predict theoretical degradation pathways. We propose that reaction of dechlorinated radicals with a hydrogen donor was the rate-controlling step for OCDT and that C-Cl bond dissociation by UV light was the rate-controlling step for OCDF.     

Polychlorinated dibenzo-p-dioxins,polychlorinated dibenzofurans and non-ortho,mono-ortho chlorine substituted biphenyls in Japanese human liver and adipose tissue

We measured PCDDs/DFs levels in Japanese human livers and adipose tissues in 1999, and TEQ were calculated with WHO TEF. The mean total levels of PCDDs/DFs in livers and adipose tissues were 57 pg TEQ/g on a lipid basis and 49 pg TEQ/g on a lipid basis, respectively. 1,2,3,6,7,8-HxCDD, 1,2,3,4,6,7,8-HpCDD, OCDD, 2,3,4,7,8-PeCDF, 1,2,3,4,7,8-HxCDF, 1,2,3,6,7,8-HxCDF, 2,3,4,6,7,8-HxCDF, 1,2,3,7,8,9-HxCDF and 1,2,3,4,6,7,8-HpCDF concentrations in livers considerably differed from those in 1989 (p < 0.05). The mean non-ortho-chlorine substituted biphenyls levels showed 20 pg TEQ/g on a lipid basis and 17 pg TEQ/g on a lipid basis in livers and adipose tissues, respectively. In livers, the mean of 3,3',4,4'-TCB concentrations was 131 pg/g on a lipid basis, and 7.7-fold higher than that in 1989. The mean total mono-ortho-chlorine substituted biphenyls level was 13.0 pg TEQ/g on a lipid basis in livers and 21.6 pg TEQ/g on a lipid basis in adipose tissues. 3,3',4,4',5-PeCB and 3,3',4,4',5,5'-HxCB levels decreased in adipose tissues, and 3,3',4,4',5-PeCB level only decreased in livers. PCDDs, PCDFs, and mono- and non-ortho-chlorine substituted biphenyls levels may have decreased in livers and adipose tissues because of a governmental policy on dioxins discharge for the decade. Then, we estimated the correlations of PCDDs, PCDFs and the related compound levels between livers and adipose tissues. The correlative PCDDs congeners may have had a similar behavior to that between liver and adipose tissue. On the contrary, most PCDFs isomers may have different behavior between liver and adipose tissue, while 2',3,4,4',5-PeCB (IUPAC No. 123) may also have a different behavior between liver and adipose tissue.     

Differences in the Spatial Variability Among CO2, CH4, and N2O Gas Fluxes from an Urban Forest Soil in Japan

The spatial variability of carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O) fluxes from forest soil with high nitrogen (N) deposition was investigated at a rolling hill region in Japan. Gas fluxes were measured on July 25th and December 5th, 2008 at 100 points within a 100 × 100 m grid. Slope direction and position influenced soil characteristics and site-specific emissions were found. The CO₂ flux showed no topological difference in July, but was significantly lower in December for north-slope with coniferous trees. Spatial dependency of CH₄ fluxes was stronger than that of CO₂ or N₂O and showed a significantly higher uptake in hill top, and emissions in the valley indicating strong influence of water status. N₂O fluxes showed no spatial dependency and exhibited high hot spots at different topology in July and December. The high N deposition led to high N₂O fluxes and emphasized the spatial variability.     

Technical Procedures for CDM Project Design

The success of CDM depends on active participation of public and private entities. In particular, participation of wide range of private companies is an important factor for the success. In order to promote the participation of private companies in the CDM project activities as project participants, the authors clarify the steps and technical issues involved in the CDM project design procedures in a step-by-step approach. The steps consist of outlining the project plans, identifying project impacts, defining a project boundary, estimating GHG emissions reduction/enhancement of removals, documenting the results of estimation, and designing of monitoring plans. The authors also propose guidance for project participants, especially for those not familiar with the CDM, which provides plain explanation of major technical issues. In order to further develop a complete guideline, it is necessary to integrate the outputs of the ongoing international initiatives concerning technical issues of CDM into the stepwise approach proposed in this paper. This revised version was published online in August 2006 with corrections to the Cover Date.