Determination of fluoroquinolone antibiotics in wastewater effluents by liquid chromatography-mass spectrometry and fluorescence detection

The occurrence of quinolone antibiotics (QAs) was investigated in wastewater effluents and surface river/lake waters in the US and Canada by using solid-phase extraction with mixed phase cation exchange disk cartridge and liquid chromatography-mass spectrometry (LC-MS) and liquid chromatography fluorescence detection (LC-FLD). Ofloxacin (OFL) was detected in secondary and final effluents of a wastewater treatment plant (WWTP) in East Lansing, Michigan, at concentrations of 204 and 100 ng/l, respectively. The mass flow calculation, estimated by multiplying the OFL concentration in the final effluent by the average influent volume of the WWTP, showed that the discharge of OFL to the river was 4.8 g/day. The OFL concentrations in wastewater effluents measured in this study are comparable to or less than those observed in several European countries. QAs were not detected in river and lake waters analyzed in this study, which may due to dilution effects and to the higher detection limits, relative to those reported previously. OFL concentrations were approximately 1-2 orders of magnitude lower than the EC50 concentrations for environmental bacterium. However, greater concentrations of other QAs in sewage sludge from WWTPs may result in cumulative effects. Considering that the sewage sludge is applied to the land as fertilizers, soil-dwelling organisms could experience greater exposures to such antibiotics. Monitoring studies of QAs in sewage from WWTPs and in sediment/soil near aquaculture facilities and livestock farms will be necessary for the evaluation of the environmental distribution and risk of these compounds.     

Evaluation of mitogen-induced responses in marine mammal and human lymphocytes by in-vitro exposure of butyltins and non-ortho coplanar PCBs

The effects of exposure to butyltin compounds (BTs: tributyltin; TBT, dibutyltin; DBT and monobutyltin; MBT) and non-ortho coplanar PCBs (IUPAC 77, 126 and 169) on marine mammals and human lymphocyte were evaluated. Peripheral blood mononuclear cells (PBMCs) isolated from Dall's porpoises (Phocoenoides dalli), bottlenose dolphins (Tursiops truncatus), a California sealion (Zalophus californianus), a larga seal (Phocoa largha) and humans (Homo sapiens) were exposed at varying concentrations of BTs and coplanar PCBs. Concanavalin A (Con A)-stimulated mitogenesis found significantly suppressed (P<0.01) when the cells were exposed at 300 nM (89 ng/ml) of TBT and 330 nM of DBT (77 ng/ml), while MBT showed little cytotoxicity at treatment levels of up to 3,600 nM (620 ng/ml). BTs concentrations in the liver of Dall's porpoises from Japanese coastal waters ranged between 81-450 ng/g for TBT and 200-1,100 ng/g (wet wt.) for DBTs, which is greater than the cytotoxic levels registered in this study. In contrast, non-ortho coplanar PCBs did not suppress cell proliferation at concentrations of up to 30 nM (10 ng/ml). The residue levels of coplanar PCBs in the blubber of Dall's porpoises were 0.12-1.3 ng/g, which were one order of lower than those levels that do cell proliferation. When cells were exposed to a mixture of TBT/DBTand coplanar PCBs, the proliferation was significantly reduced to 33 nM DBT plus 34 nM CB-77 and 33 nM DBT plus 28 nM CB-169 mixtures, respectively. The investigations relating the contaminant-induced immunosuppression in marine mammals have been focused on persistent organochlorines such as PCBs. pesticides and dioxin compounds. However, this study suggested the possibility of BTs could also pose a serious threat to the immune functions in free-ranging marine mammals and humans.     

Levels of PCDDs, PCDFs and Co-PCBs in human milk in Saitama, Japan, and epidemiological research

From 1998 to 2000, the dioxin levels were measured in the milk of 299 mothers who lived in Saitama prefecture, Japan. Factors that influenced the dioxin levels were investigated based on a questionnaire given to the milk donors at that time. It was found that the dioxin levels in the milk of the mothers who smoked were lower than those of non-smokers, and the dioxin levels were generally low in the mothers who were heavy smokers. The average dioxin levels in the milk of mothers who had been breast-fed were higher than those given formula, and there was a significant difference in the dioxin congeners. It was also found that the dioxin levels in milk of the women who regularly consumed fish and shellfish were generally higher. There was a strong correlation between summation operator TEQ and PCB126. The data suggested that PCB126 could be a useful indicator for the simplified analysis of dioxin in human milk.     

Investigation of air pollution concentration in Kathmandu valley during winter season

The monthly concentrations of NO2, NOx, SO2 and O3 measured by a passive sampler from February 2003 to January 2004 showed that the air pollution during the winter season in Kathmandu valley was higher than the summer season. The O3 level was found the highest during April, May and June due to strong radiation. The hourly concentrations of NO2, NOx, O3 and suspended particulate matter（SPM） were also measured by automatic instruments on December 2003. Temperature at the height of 60 m and 400 m at Raniban Mountain in the northwest of Kathmandu valley was measured on February 2001 in the winter season and the average potential temperature gradient was estimated from observed temperature. Wind speed was also measured at the department of hydrology, airport section, from 18 February to 6 March 2001. It was found that the stable layer and the calm condition in the atmosphere strongly affected the appearance of the maximum concentrations of NO2 and SPM in the morning, and that the unstable layer and the windy condition in the atmosphere was considerably relevant to the decrease of air pollution concentrations at daytime. The emission amounts of NOx, HCs and total suspended particle（TSP） from transport sector in 2003 were estimated from the increasing rate of vehicles on the basis of the emission amounts in 1993 to be 3751 t/a, 30570 t/a and 1317 t/a, respectively. The diurnal concentrations in 2003 calculated by the two-layers box model reproduced the characteristics of air pollution in Kathmandu valley such as the maximum value of O3 and its time, the maximum value of NO in the morning, and the decrease of NO and NO2 at daytime. The comparison with the concentrations in 1993 calculated suggested that the main cause of air pollution was the emission from transport sector.     

Extraction and cleanup methods of dioxins in house dust from two cities in Japan using accelerated solvent extraction and a disposable multi-layer silica-gel cartridge

A simple and rapid method for the extraction and cleanup of dioxins from house dust was developed using an accelerated solvent extraction (ASE) method and a multi-layer silica-gel cartridge. It was found that the WHO-TEQ levels of dioxins extracted from the house dust obtained by both a conventional soxhlet extraction and the ASE were almost equal, when the data obtained by both methods were compared. As for the cleanup method, a multi-layer silica-gel cartridge yielded higher dioxin recoveries than the alkaline digestion method. The average values of the dioxins in house dust from Kumagaya city and Sendai city in Japan (Sendai city is bigger than Kumagaya city with respect to the population and industry), were 15.6 pg TEQ/g (8.6-26.0 pg TEQ/g, n=5, Kumagaya city) and 16.0 pg TEQ/g (5.9-30.5 pg TEQ/g, n=5, Sendai city), respectively.     

Influence of combined aging on the mechanical and physical properties of reclaimed asphalt pavement mixtures blended with rejuvenator agents

Recently, reclaimed asphalt pavement (RAP) with high RAP contents with rejuvenator agents have been implemented in Japan. However, a unified view of the durability of RAP mixtures with rejuvenators has not been established. Therefore, this paper aims to assess the durability of RAP mixtures blended with different types of rejuvenators through combined aging, compared with that of hot mixed asphalt (HMA) mixture. Mechanical and physical properties of RAP mixtures with rejuvenators subjected to a combination of moisture, heat, and oxidation were investigated. Saturation aging tensile stiffness conditioning was used to simulate the combined aging. Four types of RAP mixtures were prepared by employing two types of oil-based rejuvenators with two RAP contents. HMA mixtures were also prepared. The test results demonstrated that the RAP mixtures did not exhibit a reduction in the retained stiffness, whereas the HMA mixtures exhibited a significant drop in stiffness with conditioning. In addition, the RAP mixtures exhibited a longer residual service life than the HMA mixtures after conditioning. Detailed analyses revealed differences in the stiffness and fatigue behaviors of the RAP mixtures with different types of rejuvenators. Finally, certain aspects of the deterioration mechanisms of RAP mixtures with rejuvenators were discussed.

     

Start-up performances of dry anaerobic mesophilic and thermophilic digestions of organic solid wastes

Two dry anaerobic digestions of organic solid wastes were conducted for 6 weeks in a lab-scale batch experiment for investigating the start-up performances under mesophilic and thermophilic conditions. The enzymatic activities, i.e., β-glucosidase, N-α-benzoyl-Largininamide （BAA）-hydrolysing protease, urease and phosphatase activities were analysed. The BAA-hydrolysing protease activity during the first 2-3 weeks was low with low pH, but was enhanced later with the pH increase. β-Glucosidase activity showed the lowest values in weeks 1-2, and recovered with the increase of BAA-hydrolysing protease activity. Acetic acid dominated most of the total VFAs in thermophilic digestion, while propionate and butyrate dominated in mesophilic digestion. Thermophilic digestion was confirmed more feasible for achieving better performance against misbalance, especially during the start-up period in a dry anaerobic digestion process.     

Characterization of semi-volatile organic compounds emitted during heating of nitrogen-containing plastics at low temperature

Because of recent volume increases, appropriate management of plastic recycling, which generates various organic compounds, is required to ensure the chemical safety of the processes. The processing temperature and resin type are the important factors determining both the efficiency of the processes and the emission of chemicals. Therefore, we studied the thermal degradation of various plastics at various temperatures from 70 to 300 °C under oxygen-present conditions to identify the semi-volatile organic compounds (SVOCs) emitted and to understand their thermal behaviors. The plastics examined were nitrogen-containing resins, such as polyamide 6, polyurethane, melamine formaldehyde, urea formaldehyde and acrylonitrile-butadiene-styrene. Major commodity plastics were also investigated for comparison. In total, more than 500 SVOCs were detected as emissions from plastics. While various nitrogen-containing SVOCs were detected from nitrogen-containing resins, the major commodity plastics released only these, which possibly were included as additives. These results indicate that the nitrogen atoms in the SVOCs emitted originated from the resins and additives, and not from ambient air at low temperature. As a result of the detection of raw materials, degradation chemicals and by-products of the polymers in the emissions, we found that the variation in chemical species is dependent on the resins. Additives were also emitted from all the resins, meaning that these chemicals were also released to the environment at the temperature examined. In most cases, the numbers and concentrations of SVOCs increased with increasing heating temperature. The variation of thermal behaviors of SVOCs was related to the origins and chemical species of SVOCs.