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.     

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.     

Improvement of an efficient separation method for chemicals in diesel exhaust particles: analysis for nitrophenols

GOAL, SCOPE, AND BACKGROUND: Diesel exhaust is believed to consist of thousands of organic constituents and is a major cause of urban pollution. We recently reported that a systematic separation procedure involving successive solvent extractions, followed by repeated column chromatography, resulted in the isolation of vasodilatory active nitrophenols. These findings indicated that the estimation of the amount of nitrophenols in the environment is important to evaluate their effect on human health. The isolation procedure, however, involved successive solvent extractions followed by tedious, repeated chromatography, resulting in poor fractionation and in a significant loss of accuracy and reliability. Therefore, it was crucial to develop an alternative, efficient, and reliable analytical method. Here, we describe a facile and efficient acid-base extraction procedure for the analysis of nitrophenols. MATERIALS AND METHODS: Diesel exhaust particles (DEP) were collected from the exhaust of a 4JB1-type engine (ISUZU Automobile Co., Tokyo, Japan). Gas chromatography-mass spectrometry (GC-MS) analysis was performed with a GCMS-QP2010 instrument (Shimadzu, Kyoto, Japan). RESULTS: A solution of DEP in 1-butanol was extracted with aqueous NaOH to afford a nitrophenol-rich oily extract. The resulting oil was methylated with trimethylsilyldiazomethane and subsequently subjected to GC-MS analysis, revealing that 4-nitrophenol, 3-methyl-4-nitrophenol, 2-methyl-4-nitrophenol, and 4-nitro-3-phenylphenol were present in significantly higher concentrations than those reported previously. DISCUSSION: Simple acid-base extraction followed by the direct analysis of the resulting extract by GC-MS gave only broad peaks of nitrophenols with a poor detection limit, while the GC-MS analysis of the sample pretreated with (trimethylsilyl)diazomethane gave satisfactorily clear chromatograms with sharp peaks and with a significantly lowered detection limit (0.5 ng/ml, approximately 100 times). CONCLUSION: The present method involving an acid-base extraction, in situ derivatization, and GC-MS analysis has shown to be a simple, efficient, and reliable method for the isolation and identification of the chemical substances in DEP.     

Human intake of PCDDs, PCDFs, and dioxin like PCBs in Japan, 2001 and 2002

PCDDs, PCDFs, and dioxin like PCBs (dioxin) surveillance results derived from regular environmental monitoring as well as other dioxin surveys by national and local governmental bodies in Japan were collected and analyzed. Several thousand data for air and soil in fiscal year 2001 (from 01/04/2001 to 31/03/2002) and 2002, water (from the sea, rivers and lakes), sediment (from the sea, rivers and lakes), ground water, aquatic organisms, purified water from water purification plants, raw water from water purification plants, human breast milk, and human blood in fiscal 2001, and total diet study (TDS) and various kinds of foodstuff in fiscal 1998-2002 were collected. Average human uptake of dioxin in Japan in fiscal 2001 was estimated at 1.68 pg-TEQ/kg-bw/day, while uptake in fiscal 2002 was estimated at 1.52 pg-TEQ/kg-bw/day. Diet accounted for more than 90% of the total intake. Contributions of inhalation and soil ingestion were relatively small. Age-group-specific contribution of various foodstuff to total dietary intake was also estimated. The estimates of intake through fish and shellfish accounted for approximately 45-70% of total dietary intake in each age group. Monte Carlo simulation was conducted, using the data of the air and soil concentrations in fiscal 2001 and the total diet study data in fiscal 1998-2001, in order to obtain information on the variability of dioxin intake; The estimated average, median, 5th percentile and 95th percentile of the intake distribution were 1.78, 1.69, 0.95 and 2.91 pg-TEQ/kg-bw/day, respectively. This study found that the average total intake estimates in Japan in both fiscal 2001 and 2002 were estimated to be below tolerable daily intake level (TDI) defined by the Ministry of Health, Labour and Welfare, Japan (i.e. 4 pg-TEQ/kg-bw/day). The 95th percentile of the dioxin intake distributions estimated with Monte Carlo simulation using the data of the air and soil concentrations in fiscal 2001 and TDS data in fiscal 1998-2001 was also below the Japanese TDI.     

Plutonium isotopes concentration in seawater and bottom sediment off the Pacific coast of Aomori sea area during 1991-2005

A radioactivity survey was launched in 1991 to determine the background levels of ^239+240Pu in the marine environment off a commercial spent nuclear fuel reprocessing plant before full operation of the facility. Particular attention was focused on the ²⁴⁰Pu/²³⁹Pu atom ratio in seawater and bottom sediment to identify the origins of Pu isotopes. The concentration of ^239+240Pu was almost uniform in surface water, decreasing slowly over time. Conversely, the ^239+240Pu concentration varied markedly in the bottom water and was dependent upon the sampling point, with higher concentrations of ^239+240Pu observed in the bottom water sample at sampling points having greater depth. The ²⁴⁰Pu/²³⁹Pu atom ratio in the seawater and sediment samples was higher than that of global fallout Pu, and comparable with the data in the other sea area around Japan which has likely been affected by close-in fallout Pu originating from the Pacific Proving Grounds. The ²⁴⁰Pu/²³⁹Pu atom ratio in bottom sediment samples decreased with sea depth. The land-originated Pu is not considered as the reason of the increasing ^239+240Pu concentration and also decreasing the ²⁴⁰Pu/²³⁹Pu atom ratio with sea depth, and further study is required to clarify it.     

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.     

Speciation of the radioactive nuclides in incinerator fly ash of municipal solid waste using sequential extractions

Journal of Material Cycles and Waste Management - The radioactive nuclides in the incinerator fly ashes from municipal solid waste sampled in June 2006 were analyzed with γ-ray spectrometry....     

Lectin-induced enhancement of superoxide anion production by red tide phytoplankton

Chattonella marina, a raphidophycean flagellate, is a highly toxic red tide phytoplankton which causes severe damage to fish farming. Recent studies demonstrated that Chattonella spp. continuously release superoxide anions (O₂ ⁻) while they are living. Heterosigma akashiwo, another raphidophycean flagellate, also produces O₂ ⁻. In the present study, we found that lectins such as concanavalin A (Con A), wheat germ agglutinin (WGA), and castor bean hemagglutinin (CBH) stimulated  C. marina and H. akashiwo to generate enhanced amounts of O₂ ⁻ in a concentration-dependent manner. The lectin-specific sugars potently inhibited the lectin-induced increase of O₂ ⁻ production, suggesting that the effects of lectins are mediated mainly through the interaction of these lectins with carbohydrate moiety present on the flagellate cell surface. In contrast to the potent ability of native Con A (tetravalent), succinylated Con A (divalent) showed only a slight stimulative effect on these flagellates. O₂ ⁻ production was totally inhibited by treatment with proteinase K for 30 min, without affecting the viabilities of flagellates. These results suggest that cell-surface redox enzymes may be involved in O₂ ⁻ production, and such enzymes are responsible for the lectin-stimulation. Received: 21 August 1997 / Accepted: 8 January 1998     

Hydrology, suspended sediment dynamics and nutrient loading in Lake Takkobu, a degrading lake ecosystem in Kushiro Mire, northern Japan

Suspended sediment and nutrient loadings from agricultural watersheds have lead to habitat degradation in Lake Takkobu. To examine their relationships with land-use activities, we monitored sediment, nutrient and water discharges into the lake for a 1-year sampling period. The Takkobu River contributed the largest portion of the annual water discharge into the lake, compared with the other tributaries. During dry conditions, lake water flowed into the Kushiro River, and conversely during flooding, Kushiro River water flowed into the lake. Inflows from the Kushiro River had a high proportion of inorganic matter, with high concentrations of total nitrogen and total phosphorus, attributed to agricultural land-use development and stream channelization practiced since the 1960s in the Kushiro Mire. Nutrient loadings from these two rivers were significantly higher during flooding than in dry conditions. However, there was no clear correlation between river discharge and nutrient concentrations. Since land-use activities in the Kushiro River and Takkobu River watersheds were concentrated near rivers, nutrients easily entered the drainage system under low flow conditions. In contrast, water discharged from small, forest-dominated watersheds contained a low proportion of inorganic matter, and low nutrient concentrations. The suspended sediment delivered to the lake during the sample period was estimated as approximately 607 tons, while the total nitrogen and total phosphorus inflows were about 10,466 and 1,433 kg, respectively. Suspended sediment input into the lake was 65%, and total nitrogen and total phosphorus were 40% and 48%, respectively, being delivered by the Kushiro River.     

Abundance versus presence/absence data for modelling fish habitat preference with a genetic Takagi–Sugeno fuzzy system

This study compared the accuracy of fuzzy habitat preference models (FHPMs) and habitat preference curves (HPCs) obtained from the FHPMs in order to assess the effect of two types of data [log-transformed fish population density (LOG) and presence-absence (P/A) data] on the habitat preference evaluation of Japanese medaka (Oryzias latipes). Three independent data sets were prepared for each type of data. The results differed according to the data sets and the types of data used. The HPCs showed a similar trend, whilst the degrees of preference were different. The model accuracy also differed according to the data sets used. Although almost no statistical difference was observed, on average, the P/A-based models showed a better performance according to the threshold-independent performance measures, whilst the LOG-based models showed better performance in predicting absence of the fish. These results can be explained partly from the different shapes of HPCs. This case study of Japanese medaka demonstrated the effect of different types of data on habitat preference evaluation. Further studies should build on the present finding and evaluate the effects of data characteristics such as the size of data sets and the prevalence for better understanding and reliable assessment of the habitat for target species.