Initial ecological risk assessment of eight selected human pharmaceuticals in Japan.

Eight pharmaceuticals were selected on the basis of their domestic consumption in Japan, the excretion ratio of the parent compound and the frequency of detection in the aquatic environment or wastewater treatment plant effluent. Toxicity tests on these pharmaceuticals were conducted using Japanese medaka (Oryzias latipes), daphnia (Daphnia magna), and green algae (Psuedokirchneriella subcapitata). Predicted no effect concentration (PNEC) was calculated using lethal or effect concentration 50 (LC50 or EC50) values and no effect concentration (NOEC) obtained in the toxicity tests for these compounds. Predicted environmental concentration (PEC) was also calculated from annual consumption, the excretion rate of the parent compound, and removal rate in the preliminary batch activated sludge treatment performed in this study. Maximum concentrations found in the aquatic environment or sewage effluent in Japan or foreign countries were also used for another calculation of PEC. Initial risk assessment on the selected pharmaceuticals was performed using the PEC/PNEC ratio. The results of initial risk assessment on the eight selected pharmaceuticals suggest neither urgent nor severe concern for the ecological risk of these compounds, but further study needs to be conducted using chronic toxicity tests, including reproduction inhibition and endocrine disruption assessments.     

Inception of formation and early morphogenesis of the bacterial light organ of the sea urchin cardinalfish, <Emphasis Type="Italic">Siphamia versicolor</Emphasis>

The cardinalfish Siphamia versicolor (Perciformes: Apogonidae) forms a bioluminescent symbiosis with the marine luminous bacterium Photobacterium mandapamensis, harboring the bacteria in a ventral, disc-shaped light organ and using the bacterial light apparently for counterillumination and attracting prey. Little definitive information has been available on the developmental and microbiological events surrounding the initiation of symbiosis, a critical stage in the life history of the fish, in S. versicolor or any of the many other species of bacterially luminous fish. To identify the stage at which light organ formation begins, to determine the origin of cells forming the light organ, and to characterize its bacterial colonization status during development, early developmental stages of S. versicolor obtained and reared from wild-caught mouth-brooding males were examined with histological and microbiological methods. A light organ primordium was not evident in embryos, post-embryos, or pre-release larvae, whereas the light organ began to form within 1 day of release of full-term pre-flexion larvae from the mouths of male fish. Analysis of post-release larvae revealed that the light organ arises from a proliferation and differentiation of intestinal epithelial cells, and that it quickly develops structural complexity, including the formation of chambers and gaps contiguous with the intestinal epithelium. However, the nascent light organ remained uncolonized by the symbiotic bacteria through several days of post-release development, even in the presence of high numbers of the symbiotic bacteria. These results demonstrate that the inception of light organ formation in S. versicolor occurs independently of its symbiotic bacteria and that receptivity to bacterial colonization apparently requires substantial post-release development of the light organ. Larvae therefore most likely acquire their symbiotic bacteria from seawater, during or shortly after the transition from the pre-flexion to the flexion developmental stage.     

Reduction in toxicity and generation of slag in secondary lead process

This paper focuses on the improvement of a secondary lead recycling processing plant, giving special attention to the generation of lead slag. The study was conducted using two different industrial rotary furnaces that together produce three different slag types, which depend on charge composition and lead-containing raw material obtained from a lead-acid battery recycling process. First, characterization of three slag types from different batches was performed, and such characterization included chemical, mineralogical, and structural analyses. By analyzing these data and the operational conditions of the process, it was possible to identify certain deficiencies in the recycling process and implement modifications in order to improve it. A reduction of up to 25% in the quantity of slag generated could be achieved with certain charges. In addition to this process improvement, it was possible to reduce the toxicity of the slag produced when processing a charge containing the same proportion of paste and grid as the lead-acid battery. This improvement lessens the overall environmental impact of the process. By applying this methodology, it was possible to determine some principles of cleaner production in the lead recycling process. So, waste generation could be reduced via improvements in the process and slag characteristics were modified to decrease its toxicity (as determined by lead content in leaching tests).     

Effect of phosphate addition on the sorption-desorption reaction of selenium in Japanese agricultural soils

Desorption levels of soil-sorbed selenium (Se) were studied by adding phosphate to 22 typical Japanese agricultural soils. Soil-soil solution distribution coefficients of Se (Kd-Se) were measured using a batch process as an index of Se sorption level, adding 75Se as a tracer. After the Kd measurement, extraction of soil-sorbed 75Se with a 0.1 M or 1 M Na2HPO4 solution followed to determine the amount of 75Se desorbed by the phosphate. When the 0.1 M Na2HPO4 solution was used, 18-70% of soil-sorbed Se was extracted (average: 47%). However, when the 1 M Na2HPO4 solution was used, 27-83% of soil-sorbed Se was extracted (average: 57%). The observed 75Se desorption percentage indicated the maximum Se removability by phosphate addition. The desorption percentage of Se with 1 M Na2HPO4 correlated with Kd-Se values, suggesting that the soil sample with higher Kd-Se contained more reactive components for phosphate-sorption than the soil sample with lower Kd-Se. To evaluate the effect of phosphate concentration on the Se sorption, the Kd-Se was measured for two typical soils under different levels of phosphate (0.1-10 mM PO4). The Kd values were decreased by phosphate addition for both soils. The Kd decrease was observed even for just 1 mM PO4. The phosphate addition with 1 mM PO4 is the same level as in P fertilizer applied to paddy fields in Japan. Therefore, it was suggested that Se desorption should occur in Japanese soils due to the phosphate input.     

Decomposition of dichloromethane and in situ alkali absorption of resulting halogenated products by a packed-bed non-thermal plasma reactor

For an effective decomposition and removal of organic halogenated compounds, a packed-bed non-thermal plasma reactor with in situ absorption of the resulting halogenated products by alkaline sorbent incorporated was proposed. In the plasma reactor, α-Al₂O₃ particles of 1 and 3 mm (mean particle diameter) were packed as solid dielectric medium to enhance the plasma power density in the reactor. Further, alkaline sorbent of Ca(OH)₂ was doped onto the surface of α-Al₂O₃ particles, in order to remove halogenated products by in situ absorption with Ca(OH)₂. A high-voltage and high-frequency pulsed power of −15 to 15 kV and 1 kHz was applied to the wire electrode of the plasma reactor by means of a DC power source. In the present study, as the sample of an organic halogenated compound that is most popularly used, we selected dichloromethane (CH₂Cl₂), and 500 ppm of the initial concentration of CH₂Cl₂ was fed into the reactor accompanied by air at a fixed flow rate of 500 × 10⁻⁶ m³ min⁻¹ at room temperature. As a result, it was recognized that the amount of CH₂Cl₂ decomposed by non-thermal plasma in an α-Al₂O₃ particle bed increased with an increase in plasma input power. The ratio of decomposition of CH₂Cl₂ was almost 100% at 13 kV of electric power and 1 kHz frequency, and CO₂, CH₃Cl, COCl₂, HCl, and Cl₂ were observed as the major reaction products. On the other hand, when CH₂Cl₂ was introduced into the plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ were packed, the ratio of decomposition of CH₂Cl₂ became higher, compared to the case that α-Al₂O₃ particles were not doped with Ca(OH)₂. Moreover, there were no halogenated by-product gases detected in the outlet gas from the reactor. As the solid reaction products, CaClOH and Ca(ClO)₂·4H₂O were detected on Ca(OH)₂ by X-ray diffraction. From these findings, it was recognized that CH₂Cl₂ was decomposed more effectively without producing unwanted harmful halogenated by-products in the proposed non-thermal plasma reactor where α-Al₂O₃ particles doped with Ca(OH)₂ sorbent were packed.     

Removal of Linear and Branched p-Alkylphenols from Aqueous Solution by Combined Use of melB Tyrosinase and Chitosan Beads

In this study, melB tyrosinase was applied for enzymatic removal of linear and branched p-alkylphenols from aqueous solutions. First, systematic studies were carried out to estimate the effects of the process parameters such as the temperature, pH value, and enzyme dose on quinone conversion of p-cresol as a model phenol compound. A variety of p-alkylphenols were removed from aqueous solutions through the tyrosinase-catalyzed quinone conversion and subsequent nonenzymatic adsorption of quinone derivatives on chitosan beads at pH 6.0 and 30 °C under the optimum conditions determined for p-cresol. The % removal values of 98–100 were obtained for p-n-alkylphenols. Branched p-alkylphenols with a weak estrogenic activity containing 4-tert-butylphenol and 4-tert-pentylphenol, which underwent no quinone conversion by commercially available mushroom tyrosinase in the absence of H₂O₂, were also effectively removed by further increasing either the melB tyrosinase concentration or the amount of added chitosan beads. The present technique is much effective in the fact that a series of reactions rapidly progress under mild conditions and the chitosan beads can be readily separated from the reaction medium after the enzymatic treatment.     

Detection of petroleum hydrocarbons at low ppb levels using quartz resonator sensors and instrumentation of a smart environmental monitoring system

Petroleum hydrocarbon vapors at low ppb levels can be detected using a thickness shear mode resonator (TSMR) coated with a chemical-sensing overlayer, prepared by radiofrequency sputtering of porous sintered-polyethylene (PS-PE). The sensing capabilities of PS-PE sensors were profoundly affected by the sputtering methods; they were enhanced by the photo-excitation effect, and were reduced by carbonization and water treatment. The photo-assisted PS-PE sensor was extremely sensitive and could detect linear hydrocarbon (> C12) vapors below the ppb level. The time constant of the sorption curve, however, was large, indicating a slow sensing speed. Toward creating instrumentation for a smart environmental monitoring system, the TSMR sensors were arrayed on a circuit board equipped with a serial interface and signal processing chips of the oscillation drive and frequency counter. Co-sorption with water vapor at a relative humidity of about 10% has almost no effect on the sensing ability of PS-PE sensors for 1,2,4-trimethylbenzene. Conversely, it enhances the sensitivity of the TSMR sensor coated with a D-phenylalanine film. Upward shifts in the baseline are evident with elapsed time. However, a rigorous ten-cycle iteration test for 100 ppm toluene vapor demonstrated good reproducibility of the sensor's signals.     

Mutagenicity of polyaromatic hydrocarbons by chemical models for cytochrome P450 in Ames assay

DNA damage is an important step in carcinogenesis. The Ames assay is a short-term screening of carcinogens that induce DNA damage. Most carcinogens require enzymatic activation through oxidation by cytochrome P450 (CYP450) in the presence of S9 mix. A combination of iron (Fe)(III) porphyrin and an oxidant is also able to oxidize compounds as an alternative metabolic pathway to CYP450. Previously it was reported that a chemical model containing a water-soluble 5,10,15,20-tetrakis(1-methylpyridinium4-yl)porphyrinatoiron(III) chloride (4-MPy) and tert-butyl hydroperoxide (t-BuOOH) activated aromatic amines and amides. In this study, a chemical model composed of an Fe porphyrin, water-insoluble 5,10,15,20-tetrakis(pentafluorophenyl)porphyrinatoiron(III) chloride (F₅P) or water-soluble 4-MPy was optimized with an oxidant – t-BuOOH, magnesium monoperoxyphthalate (MPPT), or iodosylbenzene (PhIO). Subsequently the mutagenicity of benzo[a]pyrene (B[a]P) and chrysene in Salmonella typhimurium TA strains was compared. B[a]P was activated by a combination of F₅P or 4-MPy plus MPPT or PhIO in S. typhimurium TA1538. The B[a]P-induced mutagenicity with F₅P plus oxidant was higher than 4-MPy plus oxidant. Mutagenicity of chrysene, a tetracyclic aromatic hydrocarbon, was not detected in the presence of F₅P/PhIO in S. typhimurium TA98, but was activated in the presence of F₅P/MPPT. The F₅P/MPPT activated other polyaromatic hydrocarbons (PAH) in the S. typhimurium TA98 assay including dibenz[a,c]anthracene, dibenz[a,h]anthracene, 3-methylcholanthrene, and benzo[a]anthracene. The results indicated that the F₅P/MPPT was the most efficient model for detecting PAH-induced mutagenicity in the Ames assay.