PCDD/PCDF formation in the chlor-alkali process—laboratory study and comparison with patterns from contaminated sites

Studies on the formation of polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) during the electrolysis of sodium chloride solution (brine) using graphite or titanium electrodes were carried out at a laboratory scale. High concentrations of PCDFs but no PCDDs were formed in tests using graphite electrodes. With titanium electrodes, PCDFs were only formed when tar pitch was added and mainly originated from the dibenzofuran present in the tar. For the first time, a detailed assessment of the formation of mono- to octachlorinated PCDD/PCDF from tar pitch was investigated. The assessment included of the chlorination steps proved that PCDFs were formed by successive lateral chlorinated from dibenzofuran to MonoCDFs, DiCDFs, and TriCDFs to form the typical known “chlorine pattern” of TetraCDF to OctaCDF with a dominance of 1,2,7,8- and 2,3,7,8-TetraCDFs, 1,2,3,7,8-PentaCDF, and 1,2,3,4,7,8-HexaCDF as marker congeners. The final homologue distributions depended on reaction time and reaction temperature. In addition, electrolysis with non-chlorinated dibenzo-p-dioxins, dibenzofuran, and biphenyl was carried out. As a result, PCDDs, PCDFs, and PCB were formed at comparable yields. Congener patterns in soil samples from a PCDD/F-contaminated site where chlor-alkali electrolysis had been operated for decades in Japan had identical isomer distribution demonstrating the source and contamination potential and risk of these processes. Therefore, sites where in the past 120 years chlor-alkali electrolysis has been operated or where residues from chlor-alkali production or other chlorine using industries have been disposed should be assessed for their pollution level and exposure relevance. The assessment of total organohalogen content revealed that PCDF is only a small fraction of organohalogens in the contaminated soils. For an appropriate risk assessment, also other chlorinated aromatic compounds such as PCBs or PCNs need to be considered.     

Effect of lower chlorinated hydroxylated-polychlorobiphenyls on development of PC12 cells

Hydroxylated polychlorobiphenyls (OH-PCBs) are major metabolites of PCBs that are widely distributed in the environment. While the effects of penta- to hepta-chlorinated OH-PCBs on neuronal differentiation have been widely reported, those of lower chlorinated OH-PCBs have not been extensively studied. To investigate the effects of lower chlorinated OH-PCBs on neuronal development, we studied the effects of mono- to hexa-chlorinated OH-PCBs on PC12 cells. Morphological changes were examined using an automatic system IN Cell Analyzer. Seventeen of the 20 OH-PCBs investigated promoted neuronal elongation in an OH-PCB concentration-dependent manner, while three OH-PCB congeners suppressed neuronal elongation based on Dunnett’s analysis. In particular, the top five OH-PCBs (4OH-PCB2, 4′OH-PCB3, 4′OH-PCB25, 4′OH-PCB68, and 4′OH-PCB159), which have hydroxyl groups at the para-position and chlorine substitutions at the 2, 4, or 3′ positions, significantly promoted neuronal elongation. Moreover, these neuronal elongations were suppressed by U0126, and phosphorylation of extracellular signal-regulated kinase (ERK) 1/2 was observed in PC12 cells treated with 4OH-PCB2, 4′OH-PCB25, and 4′OH-PCB159. Taken together, our results indicate that the effect of OH-PCB on neuronal development is not dependent on the number of chlorine groups but on the chemical structure, and the mitogen-activated kinase kinase (MEK)-ERK1/2 signaling pathway is involved in this process.     

Gonadotropic effects of dopamine in isolated workers of the primitively eusocial wasp, Polistes chinensis

In social insects, biogenic amines are thought to play regulatory roles in the transition between reproductive states in females. To determine the effect of dopamine on the reproductive development of workers in primitively eusocial societies, isolated workers of the paper wasp Polistes chinensis were supplied with oral dopamine. Ovarian development was accelerated in dopamine-fed workers as compared to control workers of the same age fed only sucrose solution. Oral dopamine increased brain levels of dopamine and its metabolite (N-acetyldopamine). Brain levels of tyramine or octopamine were also increased by dopamine application in one of two colonies; levels of the tyramine metabolite N-acetyltyramine were unchanged. These results indicate that dopamine plays a gonadotropic role in isolated workers in the primitively eusocial wasp, similar to the gonadotropic role previously reported for juvenile hormone. This is the first study to report effects of dopamine on ovarian development in workers of the paper wasp.     

Preparation and performance of arsenate (V) adsorbents derived from concrete wastes

Solid adsorbent materials, prepared from waste cement powder and concrete sludge were assessed for removal of arsenic in the form of arsenic (As(V)) from water. All the materials exhibited arsenic removal capacity when added to distilled water containing 10–700 mg/L arsenic. The arsenic removal isotherms were expressed by the Langmuir type equations, and the highest removal capacity was observed for the adsorbent prepared from concrete sludge with heat treatment at 105 °C, the maximum removal capacity being 175 mg-As(V)/g. Based on changes in arsenic and calcium ion concentrations, and solution pH, the removal mechanism for arsenic was considered to involve the precipitation of calcium arsenate, Ca₃(AsO₄)₂. The enhanced removal of arsenic for the adsorbent prepared from concrete sludge with heat treatment was thought to reflect ion exchange by ettringite. The prepared adsorbents, derived from waste cement and concrete using simple procedures, may offer a cost effective approach for arsenic removal and clean-up of contaminated waters, especially in developing countries.     

Life cycle assessment of biodiesel fuel production from waste cooking oil in Okayama City

A life cycle assessment (LCA) is performed to make clear of the actual environment impacts from conversation of waste cooking oil (WCO) to biodiesel fuel (BDF) in Okayama. A scenario analysis is carried out based on different participation rate of residents who separate WCO from general waste, corresponding to different BDF utilisation rate in transportation system. Sub scenarios complying with different gas emission standards regarding vehicles are designed as well. Afterwards, life cycle impact assessment is conducted to focus on global warming, acidification, and urban air pollution. Overall improvement of almost all kinds of life cycle inventories is significant when diesel is replaced with BDF, demonstrating that a shift from WCO-to-incineration to WCO-to-BDF is more beneficial. Under carbon neutral, compared to base scenario (S0), about 746.05 ton CO₂ emission will be reduced annually in the scenario with 100 % BDF utilisation in vehicles (S4). Meanwhile, total external cost in three environmental impacts (EI) sharply reduces by 51.90 %, showing much economic sustainability in S4. Moreover, the manufacturing cost for producing one litter WCO-to-BDF is 97.32 Yen. Sensitivity analysis shows that the gas emission standard regarding vehicles had much bigger effect on EI than BDF manufacturing process in this research.     

Origin of major ions in monthly rainfall events at the Bamenda Highlands, North West Cameroon

Rainwater characteristics can reveal emissions from various anthropogenic and natural sources into the atmosphere. The physico-chemical characteristics of 44 monthly rainfall events （collected between January and December 2012） from 4 weather stations （Bamenda, Ndop plain, Ndawara and Kumbo） in the Bamenda Highlands （BH） were investigated. The purpose was to determine the sources of chemical species, their seasonal inputs and suitability of the rainwater for drinking. The mean pH of 5 indicated the slightly acidic nature of the rainwater. Average total dissolved solids （TDS） were low （6.7 mg/L）, characteristic of unpolluted atmospheric moisture/air. Major ion concentrations （mg/L） were low and in the order K＋ 〉 Ca2＋ 〉 Mg2~ 〉 Na＋ for cations and NO3 〉〉 HCO3 〉 SO] 〉 CI- 〉 PO3- 〉 F- for anions. The average rainwater in the area was mixed Ca-Mg-SO4-CI water type. The CI-/Na＋ ratio （1.04） was comparable to that of seawater （1.16）, an indication that N a＋ and CI originated mainly from marine （Atlantic Ocean） aerosols. High enrichments of Ca2＋, Mg2＋ and SO2- to Na＋ ratios relative to seawater ratios （constituting 44% of the total ions） demonstrated their terrigenous origin, mainly from Saharan and Sahelian arid dusts. The K＋/Na＋ ratio （2.24）, which was similar to tropical vegetation ash （2.38）, and NO3 was essentially from biomass burning. Light （〈 100 mm） pre-monsoon and post-monsoon convective rains were enriched in major ions than the heavy （〉 100 mm） monsoon rains, indicating a high contribution of major ions during the low convective showers. Despite the acidic nature, the TDS and major ion concentrations classified the rainwater as potable based on the WHO guidelines.     

Preparation of Galactomannan-Based Materials Compatibilized with Ionic Liquids

This paper reports the preparation of galactomannan/ionic liquid composite materials from the corresponding ion gels. Three kinds of galactomannans, that is, fenugreek gum (FG), guar gum (GG), and locust bean gum (LBG) and an ionic liquid of 1-butyl-3-methylimidazolium chloride (BMIMCl) were used. When the galactomannan/BMIMCl gels were immersed in ethanol, followed by dryness under reduced pressure, the galactomannan/BMIMCl composite materials were obtained. The crystalline structures of galactomannans in the materials were evaluated by the powder X-ray diffraction measurement. The mechanical property of the FG/BMIMCl composite material under compressive mode was superior compared with the GG and LBG/BMIMCl composite materials. Then, FG films compatibilized with polymeric ionic liquids (PILs) were also prepared by in situ radical polymerization of polymerizable ionic liquids, 1-(3-acryloyloxypropyl)-3-vinylimidazolium bromide and 1-methyl-3-vinylbenzylimidazolium chloride by AIBN in mixtures of FG with BMIMCl. The mechanical properties of the resulting films were affected by the FG/PIL ratios as well as the unit ratios in PILs.     

Do corals select zooxanthellae by alternative discharge?

Loss of zooxanthellae (dinoflagellate Symbiodinium) from corals will sometimes lead to mass mortality of corals. To detect and quantify Symbiodinium released from corals, we developed a zooxanthellae “trap” and a quantitative PCR (qPCR) system with Symbiodinium clades A–F-specific primer sets. The trap was attached to a branch or the surface of several wild stony corals, and the water samples within the traps, including released Symbiodinium, were subjected to qPCR. All tested corals released clade C Symbiodinium at estimates of ~5,900 cells h⁻¹ cm⁻² of coral surface. Although all tested Pocillopora eydouxi harboured both clades C and D, some of these colonies released only clade C or released a lesser amount of clade D than that in the tissues. Our Symbiodinium quantification system revealed that wild hermatypic corals constantly release Symbiodinium to the environment. Our result suggests that some corals may discharge certain clades of Symbiodinium alternatively.