Radiolysis of aqueous phenol solutions with nanoparticles. 1. Phenol degradation and TOC removal in solutions containing TiO2 induced by UV,gamma-ray and electron beams

Aqueous phenol solutions containing TiO(2) nanoparticles were irradiated with ultraviolet (UV), gamma-ray and electron beams. Organic compounds were fully removed by each type of radiation in the presence of the particles. The absorbed energy of the ionizing radiation (gamma-ray and electron beams) needed for removal was much lower than that of UV photocatalysis. Phenol was decomposed by the ionizing radiation in the absence of the nanoparticles and the addition of TiO(2) had no significant effect on phenol decomposition rate. Instead, total organic carbon (TOC) removal using the ionizing radiation was accelerated drastically by TiO(2). It is suggested that TiO(2) particles affect the intermediate compounds produced through the decomposition of phenol. The amount of removed TOC per absorbed energy were compared in the absence and the presence of TiO(2) nanoparticles. Radiolysis with the nanoparticles showed consistently high rate and high efficiency of TOC removal.     

Comparison of trace element accumulation in Baikal seals (Pusa sibirica), Caspian seals (Pusa caspica) and northern fur seals (Callorhinus ursinus)

Concentrations of 18 trace elements (V, Cr, Mn, Co, Cu, Zn, Se, Rb, Sr, Zr, Mo, Ag, Cd, Sb, Cs, Hg, Tl and Pb) were determined in liver, kidney, muscle and hair of Baikal seals, Caspian seals and northern fur seals. All the three species showed the highest concentrations of Hg, V, Mn, Se and Ag in liver, Cd, Co and Tl in kidney, and Cs in muscle among the soft tissues examined. The highest burdens of Zn, Rb and Cs were observed in muscle, Mo and Ag in liver, and Sb and Pb in hair in all the three species. Concentrations of non-essential elements, Rb, Cd, Cs and Hg, showed significant positive correlations among liver, kidney and muscle, whereas correlation coefficients for essential elements, Mn, Co, Cu, Zn and Se, between the three tissues were generally low for all the species, suggesting that homeostasis controls the concentrations of essential elements but not the non-essential elements in the tissues of these animals. Significant age-dependent increase was found in the concentrations of V, Se and Ag in liver and Hg in liver and kidney of all the three species. Hair concentrations showed significant positive correlations with Zn levels in liver and kidney and Hg in muscle for Caspian seals, Hg in liver and kidney for Baikal seals, and Pb in liver for northern fur seals. Furthermore, regression analysis using the data in the present study and in the literature showed significant positive correlations between Hg levels in hair, and liver, kidney and muscle for various species of pinnipeds. These results indicate the possibility of using hair samples for monitoring these trace elements in pinnipeds.     

The Impact of Sika Deer on Vegetation in Japan: Setting Management Priorities on a National Scale

Irreversible shifts in ecosystems caused by large herbivores are becoming widespread around the world. We analyzed data derived from the 2009–2010 Sika Deer Impact Survey, which assessed the geographical distribution of deer impacts on vegetation through a questionnaire, on a scale of 5-km grid-cells. Our aim was to identify areas facing irreversible ecosystem shifts caused by deer overpopulation and in need of management prioritization. Our results demonstrated that the areas with heavy impacts on vegetation were widely distributed across Japan from north to south and from the coastal to the alpine areas. Grid-cells with heavy impacts are especially expanding in the southwestern part of the Pacific side of Japan. The intensity of deer impacts was explained by four factors: (1) the number of 5-km grid-cells with sika deer in neighboring 5 km-grid-cells in 1978 and 2003, (2) the year sika deer were first recorded in a grid-cell, (3) the number of months in which maximum snow depth exceeded 50 cm, and (4) the proportion of urban areas in a particular grid-cell. Based on our model, areas with long-persistent deer populations, short snow periods, and fewer urban areas were predicted to be the most vulnerable to deer impact. Although many areas matching these criteria already have heavy deer impact, there are some areas that remain only slightly impacted. These areas may need to be designated as having high management priority because of the possibility of a rapid intensification of deer impact.     

The effects of pH on fluoxetine in Japanese medaka (Oryzias latipes): acute toxicity in fish larvae and bioaccumulation in juvenile fish

Recent detection of fluoxetine in the aquatic environment and fish suggests a possibly high accumulation of fluoxetine; however, no report is available on the bioaccumulation of fluoxetine in aquatic organisms. Since bioaccumulation of fluoxetine was probably dependent on pH near the pK(a) value of 10.1, experiments were conducted approximately at pH 7, 8, and 9. Distribution coefficients between 1-octanol and water (D(ow)), and those between synthetic membrane vesicles (liposomes) and water (D(lip-wat)) were determined at pH 7, 8, and 9. The D(ow) and D(lip-wat) values increased significantly with increasing pH. Acute toxicity tests were performed using Japanese medaka (Oryzias latipes) prior to the bioaccumulation test, and 96-h LC(50) values were 5.5, 1.3, and 0.20mgl(-1) at pH 7, 8, and 9, respectively. In the bioaccumulation test, concentrations of fluoxetine and its major metabolite, norfluoxetine, in the fish body and liver were measured. The bioconcentration factors (BCF) of fluoxetine for Japanese medaka were 8.8, 3.0x10, and 2.6x10(2) in the body and 3.3x10(2), 5.8x10(2), and 3.1x10(3) in the liver at pH 7, 8, and 9, respectively. The BCF values were lower at pH 7 and higher at pH 9 mainly because of the increase in nonionized species with significantly higher hydrophobicity than the ionized species at pH values closer to pK(a). A similar trend was obtained for the concentration of norfluoxetine in the fish but the pseudo-BCF values (the ratio of the norfluoxetine concentration in the fish and the fluoxetine concentration in test water) were higher than the BCF value of fluoxetine at all pH conditions.     

Formation of estrogenic products from environmental phthalate esters under light exposure

Phthalate esters (PEs) have been suspected to be environmental endocrine disruptors and the detailed mechanism remains unclear. The activities of these chemicals can be enhanced through chemical modification under the environmental conditions. We demonstrate that PEs acquire unequivocal estrogenic activity by light exposure. Through UV exposure of an aqueous PE solution, one active photoproduct, identified as 4-hydroxyPE (PE-4OH) based on its characteristic UV and mass spectra, was detected in an estrogen receptor alpha-dependent transactivation assay. PE-4OH was effectively generated by UV 290 nm. The PE-4OH production accompanied H2O2 generation in a UV dose-dependent manner. Both PE and UV irradiation were indispensable in the generation of H2O2. Addition of H2O2 to the PE solution increased PE-4OH production under UV irradiation. The PE-4OH production was also observed in the PE reaction with the Fenton reagent generating hydroxyl radical without UV irradiation. The proposed mechanism for PE-4OH production based on these results is such that by PE-mediated photosensitization H2O2 is generated from O2 and H+ and decomposed to hydroxyl radical, thus oxidizing the PE benzene ring. The PEs-4OH are remarkably active estrogenic products of PEs and would be involved in ER-mediated endocrine disruption.     

Production of male neonates in four cladoceran species exposed to a juvenile hormone analog, fenoxycarb

Previous studies have found that exposure of a cyclic parthenogen, the water flea Daphnia magna (Cladocera, Crustacea), to juvenile hormones and their analogs results in the production of neonates of male sex at concentration-dependent rates. We conducted reproduction experiments in four different species (Moina macrocopa, M. micrura, Ceriodaphnia dubia and C. reticulata) of cladoceran to test for the first time whether the occurrence of this phenomenon after exposure of the parent to such hormones is a generalized phenomenon. In the presence of a juvenile hormone analog, fenoxycarb, all four species produced male neonates and showed reduced rates of reproduction. The estimated median effective concentration (EC50) for the production of male neonates varied with species, ranging from 0.60 x 10(3) to 9.3 x 10(3) ng/l. Although there was a wide range of sensitivity to fenoxycarb, the production of male neonates in all four species demonstrates that this phenomenon is a common response to juvenile hormone analogs and further suggests that these hormones are capable of initiating sexual reproduction in cladocerans, most of which exhibit cyclic parthenogenesis.     

Studies on materials containing polysaccharides as soil amendments 1: effects on animal waste water purification in a potting experiment

A potting experiment was carried out to determine the effects of soil amendments containing polysaccharides and earthworms on a land application system for the purification of animal waste water. The following soil amendments were used: purified Konjak powder (KP, powder containing glucomannan made from the root system of devil's tongue, Amorphophalus rivieri Dur.), crystallized cellulose (CC), and a mixture of the two (MX). These soil amendments were added to the pots, and then Chrysanthemum corondria were planted in the earthworm pots (A pots), the nonearthworm pots (B pots), and the control pots (C pots); the first two plots received primary-treated animal waste water, and the other one received tap water. The following items were then measured: pH, electrical conductivity, chemical oxygen demand (COD_Mn), total nitrogen (TN), total phosphorus, the volume of drained water from each pots, the height and dry matter weight of plants, and the water permeability into the soil. The MX-A pots, i.e., the pots containing both soil amendments and earthworms, gave good results, especially for water permeability, plant growth, the purification of COD_Mn, and TN. These results suggest that the presence of soil amendments and earthworms may enhance the improvement of water quality in land application systems using vegetation. Received: December 9, 1998 / Accepted: February 8, 2000     

Effect of tributyltin on veliger larvae of the Manila clam, Ruditapes philippinarum

We investigated the effects of waterborne and maternal exposure to tributyltin (TBT) on veliger larvae of the Manila clam, Ruditapes philippinarum. In a waterborne exposure test, veliger larvae (D-larvae stage: 24h after fertilization) were exposed to TBT at measured concentrations of <0.01 (control), 0.055, 0.130, 0.340, and 0.600microg/l for 13d. The percentage of normal veliger larvae (the ratio of normal veliger larvae to all larvae) decreased significantly in all TBT treatment groups compared with that in the control group. In a maternal exposure test, 100 clams were exposed to TBT at measured concentrations of <0.01 (control), 0.061, and 0.310microg/l at 20-22 degrees C for 3 weeks, and the percentage of normal veliger larvae assessed for 13d. No maternal effects on veliger larvae from TBT were observed in TBT treatment groups as compared with the control group. These results demonstrate that waterborne TBT affects Manila clam veliger larvae, and indicates that TBT may have reduced Manila clam populations by preventing the development and survival of veliger larvae.     

Methane recovery from acidic tofu wastewater using an anaerobic fixed-bed reactor with bamboo as the biofilm carrier

Journal of Material Cycles and Waste Management - Wastewater generated during acid coagulation in tofu processing has high organic concentrations and low pH. Several small industries in Indonesia...     

Genetic differences in the production of male neonates in Daphnia magna exposed to juvenile hormone analogs

We studied the susceptibility of three genetically different strains of the cyclical parthenogen Daphnia magna (Cladocera, Crustacea) in producing male neonates following exposure to juvenile hormone analogs. In experiment 1, NIES, Clone A, and Belgium A strains were exposed to the insect growth regulators (IGRs) fenoxycarb or epofenonane in a 21-day reproduction experiment. Fenoxycarb exposure decreased the total number of neonates and increased production of male neonates in a concentration-dependent manner in the NIES strain. The decrease in the total number of neonates was so great in Clone A following fenoxycarb exposure that male neonates were not observed, even at the highest concentration, where the total number of neonates was only 2% of the control. In the Belgium A strain, male neonates were observed at a rate of about 20% following exposure to the highest fenoxycarb concentration, but the total number observed was small. Epofenonane did not decrease reproduction in the NIES and Belgium A strains as dramatically as did fenoxycarb, but the neonatal sex ratio changed in a concentration-dependent manner. Although the ratio of males was as low as about 10%, induction of male neonates was also observed in Clone A following epofenonane exposure. In experiment 2, gravid females were exposed to high concentrations (5 or 10 microg/l) of fenoxycarb or pyriproxyfen for 12h. These treatments induced the production of male neonates in all strains, with a small decrease in the total number of neonates. Although induction of male neonates by juvenile hormones and their analogs was universal among genetically different strains, care is needed in interpreting the results of the 21-day reproduction tests, because decreased numbers of neonates at higher concentrations could obscure the presence of male neonates.