Separation, synthesis and estrogenic activity of 4-nonylphenols: two sets of new diastereomeric isomers in a commercial mixture

Two sets of new diastereomeric 4-nonylphenol (NP) isomers [4-(3,4-dimethylheptan-4-yl)phenol (344NP, NP-J, L) and 4-(3,4-dimethylheptan-3-yl)phenol (343NP, NP-K, P)] were separated from a commercial NP mixture. The mixture of these diastereomers was synthesized at the same time by a single Friedel-Crafts reaction of 3,4-dimethyl-4-heptanol and phenol, and the mixture was separated into individual NPs by HPLC equipped with Hypercarb column. For the first time, in this study the stereostructure-estrogenic activity relationship of NP diastereomers was investigated. The NP isomers (NP-L and NP-P) having the beta-methyl group over the benzene ring were found to be 2-4 times more estrogenic than their diastereomers (NP-J and NP-K). In the case of the other set of diastereomer [4-(3,5-dimethylheptan-3-yl)phenol, (353NP, NP-E, G)] containing gamma-methyl group in the molecule, the gamma-methyl proton signal (delta 0.49) in the more estrogenic isomer (NP-G) also appeared in a higher field than the corresponding methyl signal (delta 0.76) of the less estrogenic isomer (NP-E).     

Global fallout Pu recorded in lacustrine sediments in Lake Hongfeng, SW China

Studies on the distribution and isotope compositions of fallout Pu are important for source characterization of possible future non-fallout Pu contamination in aquatic environments, and useful for dating of recent sediments to understand the pollution history of environmental contaminants. We present the historical record of atmospheric Pu fallout reconstructed from a sediment core from Lake Hongfeng, China. The Pu activity profile was in agreement with the 137Cs profile. Inventories were 50.7 Bq m(-2) for 239+240Pu and 1586 Bq m(-2) for 137Cs. The average 240Pu/239Pu atom ratio was 0.185+/-0.009, indicating that Pu originated from global stratospheric fallout rather than from direct tropospheric or close-in fallout from the Chinese nuclear testing conducted in the 1970s. Our data suggested that Lake Hongfeng would be an ideal setting for monitoring atmospheric fallout and environmental changes in this region.     

Human factors and tidal influences on water quality of an urban river in Can Tho, a major city of the Mekong Delta, Vietnam

In this study, we focused on water quality in an urban canal and the Mekong River in the city of Can Tho, a central municipality of the Mekong Delta region, southern Vietnam. Water temperature, pH, electrical conductivity, BOD₅, COD_Cr, Na⁺, Cl^?, NH₄ ⁺?N, SO₄ ^2??S, NO₃ ^??N, and NO₂ ^??N for both canal and river, and tide level of the urban canal, were monitored once per month from May 2010 to April 2012. The urban canal is subject to severe anthropogenic contamination, owing to poor sewage treatment. In general, water quality in the canal exhibited strong tidal variation, poorer at lower tides and better at higher tides. Some anomalies were observed, with degraded water quality under some high-tide conditions. These were associated with flow from the upstream residential area. Therefore, it was concluded that water quality in the urban canal changed with a balance between dilution effects and extent of contaminant supply, both driven by tidal fluctuations in the Mekong River.     

Accumulation and biological effects of metals in wild rats in mining areas of Zambia

The lead–zinc (Pb–Zn) mine in Kabwe City and the copper–cobalt (Cu–Co) mine in the Copperbelt Province are major mining areas in Zambia. To examine the effects of metal pollution on wildlife, wild black rats (Rattus rattus and Rattus tanezumi) were captured in Kabwe and Chingola (in the Copperbelt Province), and in Lusaka (a noncontaminated site). Wild black rats in Kabwe accumulated significantly higher concentrations of Pb and Cd in various organs than rats from Lusaka. In Chingola, significantly higher concentrations of Cu, Co, Pb, and Cd were accumulated in wild black rats than in rats from Lusaka. These results were in accordance with metal accumulation patterns in soil. From toxicological aspects, concentrations of Pb and Cd in rats were generally low. However, metallothionein-1 (MT-1) and metallothionein-2 (MT-2) mRNA expression levels in wild black rats from Kabwe were significantly higher than those in rats from Lusaka. A generalized linear model (GLM) showed that concentrations of Zn and Cu had positive effects on the MT-1 and MT-2 mRNA expression. These results suggest that wild black rats in Zambian mining sites were exposed to metals that accumulated in their organs, causing biological responses such as MT mRNA induction. GLM indicated that heme oxygenase-1 (HO-1) mRNA expression could be a marker for Cr exposure.     

Elemental composition of sediments in Lake Jinzai, Japan: Assessment of sources and pollution

Bottom sediments from Lake Jinzai in southwest Japan were analyzed to determine their chemical compositions and to assess the potential for ecological harm by comparison with sediment quality guidelines. The pollution status of lake sediments was evaluated by employing contamination factor (CF), pollution load index (PLI), and geoaccumulation index (I(geo)), focusing on a suite of elements in lakebed and core sediments. Elevated concentrations of As, Pb, Zn, Cu, TOC, N, and P were present in several layers of the upper core and other surface sediments. The elevated metal concentrations are likely related to the fine-grained nature of the sediments, reducing bottom conditions produced by abundant organic matter, and possibly minor non-point anthropogenic sources. Moreover, correlations between the concentrations of trace metals and organic carbon, nitrogen, phosphorus, and iron, suggest that these elements play a role in controlling abundances. Calculated CF, PLI, and I(geo) indicate that the sediments are strongly polluted with respect to As, moderately to strongly polluted with Zn, and moderately polluted with Pb and Cu. Metal concentrations exceed the New York State Department of Environmental Conservation (NYSDEC) lowest effect level and the Canadian Council of Ministers of the Environment (CCME) interim sediment quality guidelines that indicate moderate impact on aquatic organisms in the study area.     

Municipal solid waste composition and food loss reduction in Kyoto City

For 35 years, Kyoto City has conducted detailed household waste composition surveys under the guidance of Kyoto University by dividing household waste into approximately 400 categories. In addition, the city has conducted detailed composition surveys of commercial waste generated by businesses. These surveys show that food loss accounts for approximately 40% of total waste, of which leftovers and untouched food account for about 40% in both households and business facilities. Consequently, the annual generation of household and commercial food loss is estimated at about 30,000 tons. Various efforts have been made to reduce waste, including food loss, but further reduction in environmental burden is needed. Thus, Kyoto City revised the ordinance for waste reduction, and in March 2015, formulated a new municipal waste management plan. The plan not only includes the 2Rs (reduce, reuse), but also, for the first time in Japan, sets quantitative targets for reducing food loss. Kyoto City must ensure that the necessary waste reduction measures are clearly explained to the residents and business operators. To ensure that this plan is successful, it is important to clarify concrete actions that residents and business operators should implement, along with their effects.     

Destruction of polychlorinated naphthalenes by a high-temperature melting treatment (GeoMelt process)

A series of treatment experiments were carried out to evaluate the applicability of a high-temperature melting treatment (GeoMelt process) to the destruction of polychlorinated naphthalene (PCN) formulation. We started with 10-kg-scale experiments in which a small melting furnace was used and then scaled up to a 1-t-scale experiment in which a melting furnace that resembled an actual treatment system was used. These runs were evaluated whether destruction efficiency (DE) of total PCNs was more than 99.999 % and whether concentrations of PCNs and polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDDs/DFs) in vitrified materials, emission gas, and scrubber water were below the target levels. Because DE values and the target levels of PCNs and PCDDs/DFs in these runs were satisfactory, then we carried out a demonstrative experiment using the actual treatment system and confirmed destruction of PCNs. Based on good results of the demonstrative experiment, stock of PCN formulation was successfully treated continuously.     

Consistent assessments of pathways toward sustainable development and climate stabilization

Many of the numerous difficult issues facing the world today involve relationships entailing trade‐offs and synergies. This study quantitatively assesses some alternative scenarios using integrated assessment models, and provides several indicators relating to sustainable development and climate change, such as indicators of income (per capita GDP), poverty, water stress, food access, sustainable energy use, energy security, and ocean acidification, with high consistencies among the indicators within a scenario. According to the analyses, economic growth helps improve many of the indicators for sustainable development. On the other hand, climate change will induce some severe impacts such as ocean acidification under a non‐climate intervention scenario (baseline scenario). Deep emission reductions, such as to 2°C above the pre‐industrial level, could cause some sustainable development indicators to worsen. There are complex trade‐offs between climate change mitigation levels and several sustainable development indicators. A delicately balanced approach to economic growth will be necessary for sustainable development and responses to climate change.     

Gene expression profiles in the testis associated with testis-ova in adult Japanese medaka (Oryziaslatipes) exposed to 17α-ethinylestradiol

The occurrence of oocytes in the testis (testis-ova) of several fish species is often associated with exposure of estrogenic chemicals. However, induction mechanisms of the testis-ova remain to be elucidated. To develop marker genes for detecting testis-ova in the testis, adult male medaka were exposed to nominal concentration of 100 ng L⁻¹ of 17α-ethinylestradiol (EE2) for 3-5 weeks, and 800 ng estradiol benzoate (EB) for 3 weeks (experiment I), and a measured concentration of 20 ng L⁻¹ EE2 for 1-6 weeks (experiment II). Histological analysis was performed for the testis, and microarray analyses were performed for the testis, liver and brain. Microarray analysis in the estrogen-exposed medaka liver showed vitellogenin and choriogenin as estrogen responsive genes. Testis-ova were induced in the testis after 4 weeks of exposure to 100 ng L⁻¹ EE2, 3 weeks of exposure to 800 ng EB, and 6 weeks of exposure to 20 ng L⁻¹ EE2. Microarray analysis of estrogen-exposed testes revealed up-regulation of genes related to zona pellucida (ZP) and the oocytes marker gene, 42Sp50. Using quantitative RT-PCR we confirmed that Zpc5 gene can be used as a marker for the detection of testis-ova in male medaka.     

Anthropogenic and naturally occurring polybrominated phenolic compounds in the blood of cetaceans stranded along Japanese coastal waters

We determined the residue levels and patterns of hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and related compounds, such as PBDEs, methoxylated PBDEs (MeO-PBDEs), and bromophenols (BPhs) in the blood of eleven cetacean species stranded along the Japanese coasts. The dominant OH- and MeO-PBDE isomers found in all cetaceans were 6OH-BDE47 and 6MeO-BDE47. Additionally, 2,4,6-triBPh was dominant isomer in all cetaceans. In contrast, specific differences in the distribution of para- and meta- OH-PBDE isomers and some BPhs (potential PBDEs metabolites) were found among the cetaceans.Residue levels of ΣMeO-PBDEs and 6OH-BDE47 + 2′OH-BDE68, and 2,4,6-triBPh and 6OH-BDE47 + 2′OH-BDE68 showed a significant positive correlation. These results may suggest that the large percentages of OH-PBDEs, MeO-PBDEs and 2,4,6-triBPh might share common source (i.e. biosynthesis by marine organisms), or metabolic pathway in cetacean species. Significant correlations were found between the concentrations of BDE99 and 2,4,5-triBPh. This result suggested that 2,4,5-triBPh in cetaceans could be a metabolite of BDE99.