Shinsuke Morisawa

Behaviour and adsorptive removal of siloxanes in sewage sludge biogas.

We investigated the behaviour of siloxanes, which adversely affect biogas engines, as well as their concentration levels in sewage sludge biogas in Japan. We also performed experiments on the absorptive removal of siloxanes using various adsorbents and determined the main adsorbent characteristics required for the removal of siloxanes. The results of our study on the concentration and composition of siloxanes in biogas were similar to previous reports. Moreover, we found that the concentration of siloxanes changes in relation to the outside air temperature based on real-time measurements of siloxanes using a continuous analyser. We further speculated that the continuous analyser would accurately indicate the siloxane concentration in model biogas but overestimate the siloxane concentration in actual biogas because of positive interference by VOCs and other biogas components. In the siloxane adsorption experiment, the equilibrium uptake of both cyclic siloxanes, D4 and D5, was positively related to the BET-specific surface area of the adsorbents and the fraction of the external surface area taken up by relatively large diameter pores. We attributed the adsorption results to the fact that the siloxane molecules are generally larger than micropores; therefore, they are less susceptible to adsorption to micropores. Based on these results, we concluded that adsorbents with large BET-specific surface areas, especially those with a high external specific surface area and pores of relatively large diameters, are desired for the removal of siloxanes.

Chlorides behavior in raw fly ash washing experiments

Chloride in fly ash from municipal solid waste incinerators (MSWIs) is one of the obstructive substances in recycling fly ash as building materials. As a result, we have to understand the behavior of chlorides in recycling process, such as washing. In this study, we used X-ray absorption near edge structure (XANES) and X-ray diffraction (XRD) to study the chloride behavior in washed residue of raw fly ash (RFA). We found that a combination of XRD and XANES, which is to use XRD to identify the situation of some compounds first and then process XANES data, was an effective way to explain the chlorides behavior in washing process. Approximately 15% of the chlorine in RFA was in the form of NaCl, 10% was in the form of KCl, 51% was CaCl(2), and the remainder was in the form of Friedels salt. In washing experiments not only the mole percentage but also the amount of soluble chlorides including NaCl, KCl and CaCl(2) decreases quickly with the increase of liquid to solid (L/S) ratio or washing frequency. However, those of insoluble chlorides decrease slower. Moreover, Friedels salt and its related compound (11CaO.7Al(2)O(3).CaCl(2)) were reliable standards for the insoluble chlorides in RFA, which are strongly related to CaCl(2). Washing of RFA promoted the release of insoluble chlorides, most of which were in the form of CaCl(2).

Chlorinated aromatic compounds in a thermal process promoted by oxychlorination of ferric chloride.

The relationship between the formation of chlorinated aromatic (aromatic-Cl) compounds and ferric chloride in the solid phase during a thermal process motivated us to study the chemical characteristics of iron in a model solid sample, a mixture of FeCl(3) x 6H(2)O, activated carbon, and boron nitride, with increasing temperature. Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy revealed drastic changes in the chemical form of amorphous iron, consistent with other analytical methods, such as X-ray diffraction using synchrotron radiation (SR-XRD) and Fourier-transform infrared (FT-IR) spectroscopy. Atomic-scale evidence of the chlorination of aromatic carbon was detected by Cl-K X-ray absorption near edge structure (XANES) spectroscopy. These results showed the thermal formation mechanism of aromatic-Cl compounds in the solid phase with ferric chloride. We attribute the formation of aromatic-Cl compounds to the chlorination of carbon, based on the oxychlorination reaction of FeCl(3) at temperatures in excess of ca. 300 degrees C, when the carbon matrix is activated by carbon gasification, catalyzed by Fe(2)O(3), and surface oxygen complexes (SOC) generated by a catalytic cycle of FeCl(2) and FeOCl. Chemical changes of trace iron in a thermal process may offer the potential to generate aromatic-Cl compounds in the solid phase.

Comparison of the mutations induced by p-benzoquinone, a benzene metabolite, in human and mouse cells

Benzene is one of the chemicals widely contaminating the environment. Benzene is suggested to be a human leukemogen. When benzene is absorbed in the human body, it is metabolized firstly in the liver and subsequently in the bone marrow where it provokes initiation of leukemia. In the present study, we analyzed mutations induced by p-benzoquinone (p-BQ), a benzene metabolite, in human cells using a shuttle vector plasmid pMY189, and compared frequencies, types and spectra of the mutations with those of the mutations previously revealed in mouse cells using a similar plasmid pNY200. We found that p-BQ induces mutations in human and mouse cells at similar frequencies but with different types of mutagenesis. The proportion of tandem base mutations was significantly lower in human cells than in mouse cells. Most base substitutions were induced in G:C base pairs in both human and mouse cells. However, the proportion of G:C-->C :G transversion is significantly higher in human cells. These findings indicate that the p-BQ-induced DNA damage in human and mouse cells is processed in a different manner, and that extrapolation of mice findings on experimental benzene carcinogenesis to human cancer risk assessment should be conducted carefully.

Optimum allocation of monitoring wells around a solid-waste landfill site using precursor indicators and fuzzy utility functions

Abstract An optimum monitoring well network (number of wells and their locations) is proposed which enables rapid, redundant and economical detection of contaminants in groundwater around a solid-waste landfill site. The procedure also guarantees detection of the contaminants given data on the probability of detection at different points in the saturated zone. The well selection is accomplished using a two-step procedure: 1. (1) A Monte Carlo simulation of contaminant transport in the unconsolidated shallow saturated zone is conducted. In this zone hydrogeological parameters are variable but their stochastic distributions are known. Three governing equations are solved numerically using the finite-difference method to obtain the travel time distribution of each contaminant: the two-dimensional steady-state groundwater flow equation; the two-dimensional transient convective-dispersion equation for sorptive contaminants; and the sorptive-desorptive isotherm equation. 2. (2) The procedure utilizes “fuzzy” theory, comprising of a set of newly developed mathematical techniques to deal with uncertainty in a wide range of man-machine interface issues, to assist in the design of a monitoring well network. The procedure requires a mathematical description of a four-attribute design problem using fuzzy utility functions and fuzzy weights. An optimum monitoring well network is then defined as the network having maximum total utility, which is evaluated as a fuzzy expectation of weighted arithmetic sums of the four utilities. One result of the simulation is the definition of relationships between the contaminant of interest and precursor materials. The precursor material can then serve as an “indicator” for faster detection of contaminant leaked from solid-waste landfill site. The procedures are applied to a hypothetical solid-waste landfill site under appropriate conditions to obtain the optimum monitoring well network for detection of precursor indicators. Sensitivity analysis of the optimum network was conducted by considering changes in components of the mathematical description of the design problem. Components which were changed include total utility evaluation, quality of uncertainty in weight factor and utility evaluation, weigth level determination, delay time requirement, well number limitation and perfect detection constraint.

Extraction of PCBs and water from river sediment using liquefied dimethyl ether as an extractant.

We investigated whether polychlorinated biphenyls (PCBs) and water could be simultaneously removed from river sediment by solvent extraction using liquefied dimethyl ether (DME) as the extractant. DME exists in a gaseous state at normal temperature and pressure and can dissolve organic substances and some amount of water; therefore, liquefied DME under moderate pressure (0.6-0.8 MPa) at room temperature can be effectively used to extract PCBs and water from contaminated sediment, and it can be recovered from the extract and reused easily. First, we evaluated the PCB and water extraction characteristics of DME from contaminated sediment. We found that 99% of PCBs and 97% of water were simultaneously extracted from the sediment using liquefied DME at an extraction time of 4320 s and a liquefied DME/sediment ratio of 60 mL g(-1). The extraction rate of PCBs and water was expressed in terms of a pseudo-first-order reaction rate. Second, we estimated the amount of DME that was recovered after extraction. We found that 91-92% of DME could be recovered. In other words, approximately 5-10% of DME was lost during extraction and recovery. It is necessary to optimize this process in order to recover DME efficiently. The extraction efficiency of the recovered DME is similar to that of the pure DME. From the results, we conclude that solvent extraction using liquefied DME is suitable for extracting PCBs and water from contaminated sediment.

Dietary and Inhalation Intake of Lead and Estimation of Blood Lead Levels in Adults and Children in Kanpur, India

This research was initiated to study lead levels in various food items in the city of Kanpur, India, to assess the dietary intake of lead and to estimate blood lead (PbB) levels, a biomarker of lead toxicity. For this purpose, sampling of food products, laboratory analysis, and computational exercises were undertaken. Specifically, six food groups (leafy vegetables, nonleafy vegetables, fruits, pulses, cereals, and milk), drinking water, and lead air concentration were considered for estimating lead intake. Results indicated highest lead content in leafy vegetables followed by pulses. Fruits showed low lead content and drinking water lead levels were always within tolerable limits. It was estimated that average daily lead intake through diet was about 114 microg/day for adults and 50 microg/day in children; tolerable limit is 250 microg/day for adults and 90 microg/day for children. The estimated lead intakes were translated into the resultant PbB concentrations for children and adults using a physiologically-based pharmacokinetic (PBPK) model. Monte Carlo simulation of PbB level variations for adults showed that probability of exceeding the tolerable limit of PbB (i.e.,10 microg/dL) was 0.062 for the pre-unleaded and 0.000328 for the post-unleaded gasoline period. The probability of exceeding tolerable limits in PbB level was reduced by a factor of 189 in the post-unleaded scenario. The study also suggested that in spite of the introduction of unleaded gasoline, children continue to be at a high risk (probability of exceeding 10 microg/dL = 0.39) because of a high intake of lead per unit body weight.

Effect of particle size on risk assessment of direct soil ingestion and metals adhered to children's hands at playgrounds.

The quantity of heavy metals in soil is measured after 2-mm sieving in Japan for risk assessment of direct soil ingestion. A study was conducted on the relationship between the size of soil particles and quantity of heavy metals in soil, and the particle-size distribution of soil adhered to childrens hands, and the risks of direct intake of soil considering the particle sizes ingested were evaluated. The results showed that smaller particles had a tendency to contain more heavy metals than bigger ones, that the particle size of approximately 90% of the soil particles from playgrounds adhered to childrens hands was less than 100 μm, and that 2-mm sieving in preparation for measuring heavy metal content caused underestimation of the risk of direct soil intake. The amount of heavy metals on childrens hands after playing outside was investigated. Various metals and soil were adhered to their hands, and the amount of soil adhered could be estimated from the concentration of metals. To develop accurate risk assessment, the particle-size distribution of ingested soil and more detailed scenarios of soil intake are necessary.

Molecular analysis of mutations induced by a benzene metabolite, p-benzoquinone, in mouse cells using a novel shuttle vector plasmid.

Human population has been continually exposed to benzene which is present in our environment as an essential component of petroleum. p-Benzoquinone (p-BQ) is one of the benzene metabolites and is thought to be an ultimate toxic or carcinogenic substance. For molecular analysis of carcinogen-induced mutations in mouse cells, we constructed a new shuttle vector plasmid pNY200 that has supF gene as a target of the mutations and replicates in mouse and in Escherichia coli cells. In p-BQ-treated pNY200 propagated in mouse cells, base substitutions were induced predominantly at G:C sites, and the major mutation was G:C-->A:T transition. Many tandem base substitutions were also induced at CC:GG sequences. By a postlabeling analysis and a polymerase stop assay, we confirmed that p-BQ adducts formed in DNA and mutation sites roughly correspond to the sites where the adducts were formed. Comparing data of pNY200 in mouse cells with those of the similar shuttle vector plasmid pMY189 in human cells should be important for extrapolation of data from mouse to human, because carcinogenicity of chemicals is tested in mice.

Distribution Coefficient kd of Radionuclide between Sample Soil and Water

Distribution coefficients between sample soil and water were determined for 17 soil samples and 9 radionuclides by batch and/or column method. Those experimental data were analyzed on some environmental factors, such as macro ionic component in liquid phase, percolation rate of water through soil column, saturation degree of the soil pore with water, cation exchange capacity of soil and so on, which might have large influence on a variation of kd. Some instructive results were obtained such as: (1) Relative magnitude of kd for 90Sr, 137Cs and 60Co does not depend on the sample soil. kdos is the largest among 3 nuclides and is followed by kdco. kdSr is the smallest. (2) kd for calcium rich soil might be estimated mainly based on Ca+Mg concentration in water phase, and kd for calcium poor soil based on pH in water phase. (3) Positive correlation is observed between kd of 90Sr and cation exchange capacity of soil. (4) kd for unsaturated soil with water are observed to be larger than kd determined for saturated soil with water. (5) 90Y, 110mAg and 59Fe among 9 nuclides used in this work might be stable in non-ionic form in water.