Evolutionary ecology of settlement size in planktotrophic neritimorph gastropods

Body size during larval development is one of the most important attributes of aquatic animals. The optimal size for changing form or habitat may vary according to ecological traits of species, while phylogenetic constraints also play a significant role. The major goal of this study is to reveal the patterns in the settlement size of planktotrophic larvae in an archaic gastropod superorder Neritimorpha. We take advantage of the fact that size at various ontogenetic stages of neritimorphs can be rigorously estimated by measuring features of the adult opercula. This unique feature of neritimorphs has allowed us to generate the largest data set so far on larval settlement sizes within a group of marine invertebrates that recruit into very different post-metamorphic habitats. Eighty-eight species that represent most extant genera from rocky shores, seagrass beds, mangroves, estuaries, streams, submarine caves, deep-sea vents or seeps showed negligible intraspecific variation and considerable interspecific differences in settlement size, particularly between genera or families. Settlement size is determined primarily by phylogenetic constraints, while parallel evolution toward smaller sizes was shown to occur exclusively in four independent clades (two living and two extinct) of amphidromous snails with a marine larval period followed by a limnic adult phase. The smaller settlement size may possibly reduce the risk of being wafted away from the estuaries of their natal streams through less time achieving metamorphic competence, while ability to make occasional long-distance trips is retained by the presence of a sufficiently long delay period. This delay period also seems to obscure the possible correlation between settlement size and geographic distribution range of neritimorph species, both fully marine and amphidromous.     

Source and material balance of total organic halogen pollution in the Ayase River system,Japan

The total organic halogen (TOX) pollution in the highly polluted Ayase River system was investigated. Using the concentration of coexisting linear undecylbenzenesulfonate and the difference in the flowing water volume between summer and winter, the fractions of domestic and agricultural wastewaters in the whole water column were calculated and the variety of the TOX sources in the river was estimated. The river carried about 100 kgCl of TOX materials in one day; about 50 kgCl of the materials was from residential area in the basin. The contribution of agricultural drainage from paddy field was not negligible in summer. Highly contribution of industrial wastewater was observed in a tributary Furuayase River basin while the amount of TOX loaded in the area was widely varied; 0–105 kgCl of the materials was discharged as industrial wastewater.     

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.     

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.     

Sustainability of silicon feedstock for a low-carbon society

We need to ensure the sustainable management of advanced materials, such as purified silicon, that contribute to a low-carbon society. Because a drastic increase in the demand for photovoltaic (PV) systems is tightening the supply of silicon for PV cells, the sustainability of silicon feedstock needs to be explored. For this purpose, a material flow analysis of silicon in Japan from 1996 to 2006 is presented in this paper. Our analysis finds that rapid growth in demand for polycrystalline silicon (pc-silicon) and single crystalline silicon (sc-silicon) has changed the structure of the purified silicon supply. The strong demand for purified silicon for solar cells is responsible for this change. While off-grade silicon obtained as a by-product of electronic-grade silicon (EG-Si) covered the demand for solar sells before 2000, pc-silicon is currently produced independently for solar cells via an energy-intensive process. Analysis of the resource effective-use index (REI), which indicates how effectively purified silicon is used, shows progress in the effective use of pc- and sc-silicon. REI analysis indicates that the effective use of pc-silicon is reaching a maximum, while the effective use of sc-silicon is advancing, with a corresponding increase in price. To ensure a sustainable supply of silicon feedstock, this paper proposes four solutions: (1) production of solar-grade pc-silicon by a less costly and less energy-consuming method; (2) reduction in the amount of crystalline silicon per watt in solar cells; (3) acceleration of the development and deployment of other solar cell types; and (4) reuse and recycling of solar cells in the future.     

Spectroscopic analysis of NIR-dye sensitization in bulk heterojunction polymer solar cells

The photovoltaic conversion efficiency for near-infrared (NIR) sunlight is improved successfully by dye sensitization of bulk heterojunction polymer solar cells, in which the active layer was prepared by a ternary blend of poly(3-hexylthiophene), a fullerene derivative (1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]-methanofullerene), and an NIR dye, silicon phthalocyanine bis(trihexylsilyl oxide). The mechanism of the NIR-dye sensitization is studied by femtosecond transient absorption spectroscopy.     

Spectroscopic Analysis of NIR-Dye Sensitization in Bulk Heterojunction Polymer Solar Cells

The photovoltaic conversion efficiency for near-infrared (NIR) sunlight is improved successfully by dye sensitization of bulk heterojunction polymer solar cells, in which the active layer was prepared by a ternary blend of poly(3-hexylthiophene), a fullerene derivative (1-(3-methoxycarbonyl)propyl-1-phenyl-[6,6]-methanofullerene), and an NIR dye, silicon phthalocyanine bis(trihexylsilyl oxide). The mechanism of the NIR-dye sensitization is studied by femtosecond transient absorption spectroscopy.     

The sorption of heavy metal species by sediments in soakaways receiving urban road runoff

Infiltration facilities are designed for both the retention of non-point pollutants and the replenishment of groundwater in urban areas. In this study, sorption tests were conducted to evaluate the speciation of heavy metals and their behaviour in infiltration facilities receiving urban road runoff containing high DOC concentrations and stable heavy metal organic complexes. Road dust and three soakaway sediments were collected from heavy traffic areas and a residential area with an infiltration-type sewerage system in Tokyo, Japan. Sequential multiple batch tests were conducted by adding prepared road dust leachate (artificial road runoff) or deionised water to soakaway sediment to obtain soakaway sediment leachate (artificial percolating water from soakaway sediment), which mimicked the sorption by sediments in soakaways receiving urban road runoff. Heavy metal speciation was assessed by means of a combination of anion-exchange resin measurements and MINTEQA2 model calculations, and further validated by chelating resin measurements. In road dust leachates and soakaway sediment leachates, Cu predominantly existed as organic complexes and carbonates, whereas most Mn, Zn and Cd were found to exist in the form of free ions and carbonate complexes. Stable organic complexes of Cu in road dust leachates were strongly adsorbed by soakaway sediments despite the limited adsorption of DOC. On the other hand, desorption of free Mn, Zn and Cd ions from the sediment receiving road dust leachates was observed, indicating that heavy metals such as Mn, Zn and Cd may ultimately reach groundwater as free ions.     

Estrogen equivalent concentration of 13 branched para-nonylphenols in three technical mixtures by isomer-specific determination using their synthetic standards in SIM mode with GC-MS and two new diasteromeric isomers

Thirteen isomers of branched para-nonylphenols (para-NP) in three technical mixtures were isomer-specifically determined using their synthesized standards by SIM of structurally specific ions, m/z 135, 149 or 163 with GC–MS. Of the 13 isomers, four isomers, 4-(2,4-dimethylheptan-4-yl)phenol, 4-(4-methyloctan-4-yl)phenol, 4-(3-ethyl-2-methylhexan-2-yl)phenol (3E22NP) and 4-(2,3-dimethylheptan-2-yl)phenol synthesized for their determinations were first used as standard substances. The 13 isomers in the technical mixtures individually occurred at mass percent portion of more than 2%. The total mass percent portions in the mixtures from Tokyo Chemical Industry (TCI), Aldrich, and Fluka covered with 89 ± 2%, 75 ± 4% and 77 ± 2%, respectively. The abundance of 4-(3,6-dimethylheptan-3-yl)phenol in the three mixtures was the largest with 11.1 ± 2% to 9.9 ± 0.3%, while that of 4-(2-methyloctan-2-yl)phenol was the smallest with 2.9 ± 0.3% to 3.0 ± 0.2%. Additionally, structures of four new isomers of more than 1% portion present in a technical mixture were elucidated as two pairs of diastereomeric isomers: two types of 4-(3,4-dimethylheptan-4-yl)phenol (344NP) and those of 4-(3,4-dimethylheptan-3-yl)phenol (343NP). By estrogenic assay of 13 isomers with yeast estrogen screen system, the activity of 3E22NP was the highest, while that of 4-(3-methyloctan-3-yl)phenol was the least. Their relative activities to that of 3E22NP were individually calculated. Estrogenic equivalent concentrations of the three technical mixtures were predictively evaluated. The ratio of the EEC to the conventional concentration, total mass percent portions of the 13 isomers in technical mixtures were 0.208 for TCI, 0.206 for Aldrich and 0.205 for Fluka. The predicted estrogenic activity of measured concentration of para-NP in technical mixtures was approximately 5-fold greater than the measured estrogen agonist activity.     

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).