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.     

Simplified heating time calculation using the Schmidt graphical method for PCB-contaminated capacitors undergoing the vacuum thermal recycling process

We discuss the use of the Schmidt graphical method to calculate the time required to heat a polychlorinated biphenyl (PCB)-contaminated capacitor in the vacuum thermal recycling process to the processing temperature of 400°C, and we evaluate the results of the heating time calculation by comparing the calculated values with the corresponding experimental values. The thermal conductivity and specific heat of the insulating paper and the carbonized paper in the capacitor were unknown, so we determined their values from experimental data obtained during the vacuum thermal recycling process. The capacitor element is a multilamination of aluminum foil and insulating paper, so we used an equation for a multilayer plane wall to calculate the value of the thermal conductivity. For the thermal conductivity and specific heat of the insulating paper impregnated with PCBs, we used values calculated from the mass ratios and thermal conductivities and specific heats of the individual materials. In addition, the physical properties vary according to the treatment because of the evaporation of PCBs and the carbonization of the insulating paper, so we modified the values of the thermal conductivity, specific heat, and density at the boiling point of the PCB and the carbonization point of the insulating paper before performing the calculations. Our calculated heating times were almost the same as, or were above, the experimental values, so we concluded that our method can be used as a simple calculation of the heating time.     

Non-degradable triazine substrates of atrazine and cyanuric acid hydrothermally and in supercritical water under the UV-illuminated photocatalytic cooperation

Strong oxidation by titanium dioxide photocatalysis can occur by photodegradation of organic contaminants in air and water. Some endocrine disruptors such as 2,4-dichlorophenoxy acetic acid (;;; ), 2,4-dichlorophenol (;;; ), nonylphenol (; ), bisphenol A (), diethyl phthalate (; ), etc. which can be neither biodegraded by bacteria nor degraded thermally can be degraded by TiO(2) photocatalytic treatment. However, incomplete photomineralization partly occurred, when TiO(2) photocatalytic degradation is employed for the treatment of certain endocrine disruptors. For example, no atrazine pesticide having triazine skeleton can be completely mineralized even by a photocatalytic procedure; the photodegradation of atrazine ultimately stops at the intermediate step of cyanuric acid, which cannot be photodegraded even after long illumination times ().In this study, the decomposition of atrazine and cyanuric acid was carried out with a device combining photocatalytic degradation in supercritical water (scH(2)O) or hydrothermal water (hyH(2)O). Atrazine and cyanuric acid can be degraded by the cooperation of either scH(2)O or hyH(2)O and UV illuminated TiO(2)-photocatalytic dispersed system under the fixed pressure of 23 MPa at 623 K or 683 K in a 120-ml Hastelloy batch reactor. The photocatalytic degradation method under high temperature and pressure has found appropriate for the photocatalytic oxidation of acetic acid and 2-chlorobiphenyl under continuous flow conditions at 160 degrees C and 20 atm (). In addition, the wet peroxide oxidation of PCBs by high temperature and pressure has been reported (). The main aims of this research are following. (i): the degradation of atrazine and cyanuric acid within the scH(2)O or hyH(2)O, (ii) the decomposition of atrazine and cyanuric acid catalyzed by TiO(2) particles under scH(2)O or hyH(2)O, and the synergistic effect for several reactions with TiO(2) and scH(2)O or hyH(2)O, and (iii) the mineralization yield of nitrogen and chlorine atoms concerning the chemical structures of atrazine or cyanuric acid (only nitrogen).     

mRNA expression of a cadmium-responsive gene is a sensitive biomarker of cadmium exposure in the soil collembolan Folsomia candida

The gene expression of environmental organisms is useful as a biomarker of environmental pollution. One of its advantages is high sensitivity. We identified the cDNA of a novel cadmium-responsive gene in the soil collembolan Folsomia candida. The deduced protein, designated “metallothionein-like motif containing protein” (MTC), was cysteine-rich and contained a metallothionein-like motif with similarity to metallothionein, but had a much longer sequence than metallothionein and contained repeated sequences of amino acids. Expression of MTC mRNA was sensitively induced by cadmium exposure at 0.3 mg/kg of dry food, a concentration at which toxic effects are not observed, but expression was not affected by γ-ray exposure (an inducer of oxidative stress). These findings suggest that MTC is involved in cadmium-binding processes rather than in oxidative-stress responses. In conclusion, we suggest that gene expression of MTC may be a candidate biomarker for detecting low levels of cadmium contamination in soil.     

Horizontal distribution of steroid estrogens in surface sediments in Tokyo Bay

A monitoring survey was conducted to investigate the distribution of steroid estrogens and their conjugates in surface sediments of Tokyo Bay for the first time, which is known as one of the most heavily polluted marine embayments in the world. The surface sediment samples were collected at 20 locations covering the whole area of Tokyo Bay and analyzed for steroid estrogens and their conjugates using liquid chromatography-tandem mass spectrometry. The concentrations of 17beta-estradiol (beta-E2) and estrone (E1) ranged from ND (below the detection limit; <0.07) to 0.59 and from 0.05 to 3.60 ng g-1 dry, respectively. Those concentrations were higher in the northern part of the bay, which is directly receiving huge quantities of pollutants from adjacent rivers containing a large amount of municipal and industrial wastewater. 17alpha-Estradiol (alpha-E2) and estrone-3-sulfate (E1-3S) were detected in some of the samples, whereas neither of the other conjugates, estriol (E3) or 17alpha-ethynylestradiol (EE2), was found.     

Development of a Safe Solid-State Microorganism/Biodegradable Polymer Composite for Decomposition of Formaldehyde

A very safe and environmentally friendly solid-state material for bioremediation was prepared using a combination of Aspergillus oryzae and poly(ε-caprolactone) (PCL), a porous biodegradable polymer. The novel material was capable of decomposing 200 ppm formaldehyde solutions to 0 ppm within 7 days. Degradation ability was prolonged by addition of yeast extract-peptone-dextrose medium into the composite; 200 ppm formaldehyde was decomposed to 0 ppm over eight additional decomposition cycles and 100 days. A unique mechanism is proposed where, during PCL degradation, the solid-state composite provides nutrients to A. oryzae.     

Preparation of Natural Rubber/Condensed Tannin Semi-interpenetrating Polymer Network Composites by Hematin-Catalyzed Cross-Linking

In this study, the preparation of semi-interpenetrating polymer network (semi-IPN) composites composed of natural rubber and condensed tannin was performed by means of the enzyme-mimetic cross-linking of condensed tannin catalyzed by hematin. Prior to the preparation of the composites, the hematin-catalyzed cross-linking behavior of condensed tannin was evaluated by the TGA measurement. The TGA results indicated that condensed tannin was sufficiently cross-linked by the hematin-catalyzed reaction in the presence of appropriate amounts of 30% (w/v) H₂O₂ aq. to give the relatively thermostable materials. For the preparation of the composites, a solution of condensed tannin and hematin, and subsequently 30% (w/v) H₂O₂ aq. were added to natural rubber latex and the mixture was stirred at room temperature for 10 min to perform the cross-linking of condensed tannin, followed by drying of the reaction mixture at 50 °C for 5 h, which was subsequently put into a heat device and hot-pressed at 100 °C and 20 MPa for 20 min to give the semi-IPN composite. The tensile stress?Cstrain measurement of the composites was conducted to evaluate the mechanical properties, which were changeable depending on the weight ratios of natural rubber to condensed tannin and the amounts of 30% (w/v) H₂O₂ aq. Moreover, the miscibility of the cross-linked tannin with natural rubber in the composite was evaluated by the SEM measurement.     

Readability of Characters on Mobile Phone Liquid Crystal Displays

Subject performance in reading characters on mobile phone liquid crystal displays was researched by using (a) English sentences with 3 or 4 different sizes of characters on 2 types of displays with different resolutions(n = 23; age = 31.0 ± 6.0 years), (b) Japanese characters in 3 different sizes and 2 types of font (n = 98; age = 44.5 ± 18.5 years), and (c) Japanese characters vertically enlarged 1—4 times (n = 120; age = 46.9 ± 18.6 years). Subjective evaluation, reading speed, number of reading errors, and viewing distance were recorded. Readability was higher with higher resolution displays, and with Gothic than with Mincho font in Japanese. Young subjects shortened the viewing distance as characters became smaller, whereas elderly subjects increased the viewing distance irrespective of the size of characters. Characters of 3–5 mm are appropriate for the young but inadequate for the elderly. Readability of Japanese characters improved when they were vertically enlarged to approximately twice the width.     

Utilization of water chestnut for reclamation of water environment and control of cyanobacterial blooms

Overgrowth of water chestnut (Trapa spp.) is a regional problem throughout Asia and North America because of waterway blockage and water fouling upon decomposition. In the present study, we investigated the potential of water chestnut to control cyanobacterial blooms, via a high content of phenolic compounds. In addition, we assessed the impact of biomass harvesting and crude extract application on nutrient balance. We showed that the floating parts of water chestnut contained high concentrations of total phenolics (89.2 mg g^?1 dry weight) and exhibited strong antioxidant activity (1.31 mmol g^?1 dry weight). Methanol-extracted phenolics inhibited growth of Microcystis aeruginosa; the half maximal effective concentration (EC₅₀) of the extracted phenolics was 5.8 mg L^?1, which was obtained from only 103 mg L^?1 of dry biomass (the floating and submerged parts). However, the crude extracts also added important quantities of nitrogen, phosphorus, and potassium (1.49, 1.05, and 16.3 mg g^?1, respectively; extracted dry biomass weight basis); therefore, in practice, nutrient removal before and/or after the extraction is essential. On the other hand, biomass harvesting enables recovery of nitrogen, phosphorus, and potassium from the water environment (23.1, 2.9, and 18.7 mg g^?1, respectively; dry biomass weight basis). Our findings indicate that water chestnut contains high concentrations of phenolics and exhibits strong antioxidant activity. Utilization of these resources, including nutrients, will contribute to reclamation of the water environment, and also to disposal of wet biomass.     

Spatial and temporal variation in nutrient parameters in stream water in a rural-urban catchment, Shikoku, Japan: effects of land cover and human impact

Seasonal and spatial variations in major ion chemistry and isotope composition in the rural-urban catchment of the Shigenobu River were monitored to determine the influences of agricultural and urban sewage systems on water quality. Temporal patterns of biochemical oxygen demand (BOD), total nitrogen (TN), total phosphorus (TP), and suspended sediment (SS) were examined at four sites in the rural-urban catchment. Urban land cover, incorporating the effects of increased population, domestic water use, and industrial wastewater, was positively associated with increases in water pollution and was included as an important explanatory variable for the variations in all water quality parameters. Significant trends were found in each parameter. BOD concentrations ranged widely, and were high in urban regions, due to the presence of a waste water treatment plant. TN and SS showed various trends, but did not vary widely, unlike TP. TP concentrations varied greatly, with high concentrations in cultivated areas, due to fertilizer use. Local water quality management or geology could further explain some of the variations in water quality. Non-point-source pollution exhibited strong positive spatial autocorrelation, indicating that incorporating spatial dimensions into water quality assessment enhances our understanding of spatial patterns of water quality. Data from the Ministry of Land Infrastructure and Transport (MLIT) and Environment Ministry (EM) were used to investigate trends in land management. Stepwise regression analysis was used to test the correlation between specific management practises and substance concentrations in surface water and sediment. MLIT and EM data for 1981-2003 showed an increase in TN, TP, and SS concentrations in surface water. High levels of fertilizer in dormant sprays and domestic water use were associated with high pesticide concentrations in water and sediment. This paper presents a novel method of studying the environmental impact of various agricultural management practises and recommends a management strategy that combines the use of reduced-risk pesticides with irrigation and non-irrigation periods in paddy fields.