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 children's 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 children's 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 children's 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.

Characteristics of biosolids in dimethyl ether dewatering method.

In this study, a method for removing water from biosolids that uses dimethyl ether (DME) as an extractant was considered. This study evaluates the applicability of the DME dewatering method to biosolid cakes by using a DME flow-type experimental apparatus. It was found that a high dewatering ratio is clearly achieved by increasing the liquefied DME/biosolid ratio and lowering the liquefied DME linear velocity. As the liquefied DME/biosolid ratio was increased, the carbon content in dewatered biosolid showed a slight decrease and the TOC concentration in separated liquid increased significantly. Finally, the input energy Es to remove 1 kg of water from the biosolid cake, using both the DME dewatering method and the conventional drying method was estimated. The calculation shows that Es for the DME dewatering process is approximately a third of Es for the conventional thermal drying process.

Methodology for setting risk-based concentrations of contaminants in soil and groundwater and application to a model contaminated site.

In Japan, environmental standards for contaminants in groundwater and in leachate from soil are set with the assumption that they are used for drinking water over a human lifetime. Where there is neither a well nor groundwater used for drinking, the standard is thus too severe. Therefore, remediation based on these standards incurs excessive effort and cost. In contrast, the environmental-assessment procedure used in the United States and the Netherlands considers the site conditions (land use, existing wells, etc.); however, a risk assessment is required for each site. Therefore, this study proposes a new framework for judging contamination in Japan by considering the merits of the environmental standards used and a method for risk assessment. The framework involves setting risk-based concentrations that are attainable remediation goals for contaminants in soil and groundwater. The framework was then applied to a model contaminated site for risk management, and the results are discussed regarding the effectiveness and applicability of the new methodology.

The calcination process in a system for washing, calcinating, and converting treated municipal solid waste incinerator fly ash into raw material for the cement industry.

Calcination is the second step in a washing-calcination-conversion system in which treated municipal solid waste incinerator fly ash and bottom ash can be reused as raw material in the cement industry and can decompose or stabilize hazardous compounds, reduce residue amounts, and alter residue characteristics. In this research, only fly ash is discussed. Chloride reduction is important if treated fly ash is to be reused in cement; however, the relationship between washed fly ash properties and chloride reduction by calcination is not well understood. This study used washed residues of three types of fly ash-raw fly ash (RFA) from the boiler or economizer of an incineration system, fly ash collected in a bag filter injected with calcium hydroxide (Ca(OH)2) for acid removal (CaFA), and fly ash collected in a bag filter injected with sodium bicarbonate (NaHCO3) for acid removal (NaFA)-in calcination experiments with varying temperature (400-1100 degrees C) and atmosphere (100% nitrogen [N2] at 25 mL/min or 10% oxygen [O2] [90% N2] at fluxes of 25, 50, and 75 mL/min). From the perspective of chloride reduction, heating to 1000 degrees C with 1-hr heating time, 1-hr holding time, and an atmosphere of 10% O2/90% N2 was most suitable for calcination. Under these conditions, chloride levels were reduced by 91, 52, and 96% in washed residues of RFA, CaFA, and NaFA, respectively. Among the washed residues, the weight of the washed residue of NaFA decreased the most.

Deodorization and dewatering of biosolids by using dimethyl ether.

We proposed a method for the deodorising and dewatering of biosolids. In the proposed method, liquefied dimethyl ether (DME) was used as an extractant for odorous components and water. We developed a bench-scale experiment to almost completely deodorize and dewater biosolids by using liquefied DME at room temperature. The deodorized and dewatered biosolids have sufficient caloric density and can be used as a carbon neutral fuel.

Chlorination mechanism of carbon during dioxin formation using Cl-K near-edge X-ray-absorption fine structure.

Many environmental organic chemicals have chloride in their structure. Thus, researching the chlorination mechanism of carbon is of interest. Dioxins are typically concentrated in fly ash collected from the post-combustion zone during the operation of municipal solid waste incinerators. In this study, we report the application of Cl-K near-edge X-ray-absorption fine structure (NEXAFS) in determining the chlorination mechanism of carbon in fly ash. The separation of a chloride-carbon (C-Cl) bond was readily recognizable as a peak in the Cl-K NEXAFS spectrum. Chlorination effects could be estimated using Cl K-edge NEXAFS with no dependence on metal species. Analysis of Cl K-edge NEXAFS spectra showed the reduction of copper(II) chloride at 300°C and oxidation of iron(III) chloride at 400°C in connection with the chlorination of carbon.

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 Friedel's 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, Friedel's 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.

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.

Benzene risk estimation using radiation equivalent coefficients.

We estimated benzene risk using a novel framework of risk assessment that employed the measurement of radiation dose equivalents to benzene metabolites and a PBPK model. The highest risks for 1 microg/m(3) and 3.2 mg/m(3) life time exposure of benzene estimated with a linear regression were 5.4 x 10(-7) and 1.3 x 10(-3), respectively. Even though these estimates were based on in vitro chromosome aberration test data, they were about one-sixth to one-fourteenth that from other studies and represent a fairly good estimate by using radiation equivalent coefficient as an "internal standard."

Chloride Behavior in Washing Experiments of Two Kinds of Municipal Solid Waste Incinerator Fly Ash with Different Alkaline Reagents.

To efficiently reduce and reuse fly ash from incinerators, we suggest trying a new alkaline reagent to neutralize the acid compounds in discharged gas from incinerators and reuse fly ash as the raw material in the cement industry. Normally the washing process includes a pretreatment method to remove chlorides to comply with the strict standards for cement. We examined chloride behavior in washing experiments by X-ray absorption near edge structure (XANES) and X-ray diffraction (XRD) for two kinds of fly ash: (1) fly ash collected in a bag filter with the injection of calcium hydroxide (Ca(OH)2) for acid gas removal (CaFA), and (2) fly ash collected in a bag filter with the injection of sodium bicarbonate (NaHCO3) for acid gas removal (NaFA). We found that the insoluble chlorides in both CaFA and NaFA combined calcium chloride (CaCl2), with some sodium chloride (NaCl) also possibly combined. Under some conditions, the combined CaCl2 and NaCl were released. In particular, when the liquid/solid ratio was greater than 3 or the washing frequency was doubled, less chlorine, insoluble chlorine, and CaCl2 were left in the residues of NaFA than in the residues of CaFA. As a result, it is desirable to use NaHCO3 as the alkaline reagent instead of Ca(OH)2 in the air pollution control system of incinerators for recycling fly ash as a raw material in the cement industry.

Development of a physiologically based pharmacokinetic model for bisphenol A in pregnant mice.

Bisphenol A (BPA) is a weakly estrogenic monomer used to produce polymers for food contact and other applications, so there is potential for oral exposure of humans to trace amounts via ingestion. To date, no physiologically based pharmacokinetic (PBPK) model has been located for BPA in pregnant mice with or without fetuses. An estimate by a mathematical model is essential since information on humans is difficult to obtain experimentally. The PBPK model was constructed based on the pharmacokinetic data of our experiment following single oral administration of BPA to pregnant mice. The risk assessment of bisphenol A (BPA) on the development of human offspring is an important issue. There have been limited data on the exposure level of human fetuses to BPA (e.g. BPA concentration in cord blood) and no information is available on the pharmacokinetics of BPA in humans with or without fetuses. In the present study, we developed a physiologically based pharmacokinetic (PBPK) model describing the pharmacokinetics of BPA in a pregnant mouse with the prospect of future extrapolation to humans. The PBPK model was constructed based on the pharmacokinetic data of an experiment we executed on pregnant mice following single oral administration of BPA. The model could describe the rapid transfer of BPA through the placenta to the fetus and the slow disappearance from fetuses. The simulated time courses after three-time repeated oral administrations of BPA by the constructed model fitted well with the experimental data, and the simulation for the 10 times lower dose was also consistent with the experiment. This suggested that the PBPK model for BPA in pregnant mice was successfully verified and is highly promising for extrapolation to humans who are expected to be exposed more chronically to lower doses.

Development of a new E. coli strain to detect oxidative mutation and its application to the fungicide o-phenylphenol and its metabolites.

Oxidative mutation is mainly induced by reactive oxygen species (ROS), such as the superoxide anion radical (O(2)(-)) and hydrogen peroxide (H(2)O(2)). However, in Escherichia coli (E. coli), ROS are eliminated by enzymes such as superoxide dismutase and catalase, which are coded by sodAB and katEG genes. In this study, to detect mutagens that induce oxidative mutation, a mutant (WP2katEGsodAB) with katEG and sodAB deleted was constructed by gene manipulation of E. coli WP2. H(2)O(2) and menadione sodium bisulfite generated mutation in WP2katEGsodAB but not in WP2. o-Phenylphenol (OPP) and its metabolites (phenylhydroquinone (PHQ) and phenyl-1,4-benzoquinone (PBQ)), which had been shown to be negative in the Ames test but reported to be carcinogenic, induced mutation in WP2katEGsodAB but not in WP2. These results suggest that the new assay may be useful for the detection of oxidative mutagens.

A physiologically based pharmacokinetic model for endosulfan in the male Sprague-Dawley rats.

Endosulfan, an organochlorine (OC) insecticide belonging to the cyclodiene group, is one of the most commonly used pesticides to control pests in vegetables, cotton, and fruits. To date, no physiologically based pharmacokinetic (PBPK) model has been located for endosulfan in animal species and humans. The estimation by a mathematical model is essential since information on humans can scarcely be obtained experimentally. The PBPK model was constructed based on the pharmacokinetic data of our experiment following single oral administration of (14)C-Endosulfan to male Sprague-Dawley rats. The model was parameterized by using reference physiological parameter values and partition coefficients that were determined in the experiment and optimized by manual adjustment until the best visual fit of the simulations with the experimental data were observed. The model was verified by simulating the disposition of (14)C-Endosulfan in vivo after single and multiple oral dosages and comparing simulated results with experimental results. The model was further verified by using experimental data retrieved from the literature. The present model could reasonably predict target tissue dosimetries in rats. Simulation with three-time repeated administration of (14)C-Endosulfan and experimental data retrieved from the literature by the constructed model fitted fairly well with the experimental results; thus suggesting that the newly developed PBPK model was developed. Sensitivity analyses were used to determine those input parameters with the greatest influence on endosulfan tissue concentrations.

Development of an in vitro blood-brain barrier model to study the effects of endosulfan on the permeability of tight junctions and a comparative study of the cytotoxic effects of endosulfan on rat and human glial and neuronal cell cultures.

Endosulfan, an organochlorine (OC) insecticide that belongs to the cyclodiene group, is one of the most commonly used pesticides to control pests in vegetables, cotton, and fruits. Porcine brain microvascular endothelial cells were used to develop a model to study the effects of endosulfan on the permeability of tight junctions in the blood-brain barrier (BBB). BBB permeability, measured as transendothelial electrical resistance, decreased in a dose- and time-dependent manner when treated with alpha-endosulfan, beta-endosulfan, or endosulfan sulfate. Cytotoxicity testing revealed that the three endosulfans did not cause cell death at concentrations of 10 microM and below. The ratio of the average permeability of the filter-grown endothelial cell monolayer to 14C-endosulfan (Pe) going from the outer to the inner compartments with that going from the inner to the outer compartments was approximately 1:1.2-2.1 after exposure to concentrations of 0.01-10 microM. alpha-Endosulfan, beta-endosulfan, and endosulfan sulfate had cytotoxic effects on rat glial (C6) and neuronal (PC12) cell cultures as well as on human glial (CCF-STTG1) and neuronal (NT2) cell cultures. The effects of alpha-endosulfan were highly selective, with a wide range of LC50 values found in the different cultures, ranging from 11.2 microM for CCF-STTG1 cells to 48.0 microM for PC12 cells. In contrast, selective neurotoxicity was not so manifest in glial and neuronal cell cultures after exposure to endosulfan sulfate, as LC50 values were in the range of 10.4-21.6 microM. CCF-STTG1 cells were more sensitive to alpha-endosulfan and endosulfan sulfate, whereas NT2 cells were more sensitive to beta-endosulfan.

Toxicokinetics of 14C-endosulfan in male Sprague-Dawley rats following oral administration of single or repeated doses.

Endosulfan (ES), an organochlorine (OC) insecticide that belongs to the cyclodiene group, is one of the most commonly used pesticides to control pests in vegetables, cotton, and fruits. The toxicokinetics of 14C-endosulfan following oral administration of a single dose of 5 mg/kg body weight was investigated in male Sprague-Dawley rats. Three rats were sacrificed 30 min, 1 h, 2 h, 4 h, and 8 h after dosing. 14C-endosulfan radioactivity was detected in all tissues at each time point. In a separate experiment urine and feces were collected for 96 h. The total radioactivity recovered in the excreta for 4 days was 106.8% +/- 26.2%, with fecal elimination the major route of elimination route (94.4% +/- 21.4%). The cumulative excretion in the urine for 4 days was 12.4% +/- 4.8%. Radioactivity 8 h after administration was highest in gastrointestinal (GI) tract tissue (20.28 +/- 16.35 mg ES eq./L) and lowest in muscle (0.18 +/- 0.06 mg ES eq./L). The toxicokinetic parameters obtained from 14C-endosulfan-derived radioactivity in blood were distribution half-life (T1/2 x) = 31 min and terminal elimination half-life (T1/2 y) = 193 h. Blood concentration reached its maximum (Cmax) of 0.36 +/- 0.08 mg ES eq./L 2 h after the oral dose. Endosulfan was rapidly absorbed into the GI tract in rats, with an absorption rate constant (ka) of 3.07 h(-1).

Determination of chemical form of antimony in contaminated soil around a smelter using X-ray absorption fine structure.

Only limited information is available about the behavior of antimony (Sb) in contaminated soils. However, understanding the behavior of Sb in contaminated soils is important, because the toxicity or solubility of this element depends on its chemical state. In this study, we investigated the levels of Sb and the chemical forms of Sb in the soil around a smelter using X-ray absorption fine structure (XAFS) spectra. The highest Sb concentration in the contaminated soil was 2900 mg/kg dry soil. According to Sb-K edge X-ray absorption near edge (XANE) spectra, the Sb in the soil was in the form of Sb(V) compounds. The similarity of extended XAFS (EXAFS) spectra suggests that Sb speciation was independent of the sampling site, which indicates that Sb or Sb2O3 emitted from the smelter was converted into Sb(V) compounds in the soil.

Comparison of mutagenic potentials and mutation spectra of benzene metabolites using supF shuttle vectors in human cells.

Benzene is a human leukemogen and the metabolites are thought to be deeply involved in benzene leukemogenesis. In a previous study we reported the molecular analysis of p-benzoquinone (p-BQ) mutagenesis by using a supF shuttle vector plasmid and here we report the mutagenesis of the other metabolites, hydroquinone (HQ) and trans, trans-muconaldehyde (MUC). HQ is a precursor of p-BQ and MUC is produced by a ring-opening metabolic pathway. We found that the HQ redox cycle produced an oxidative lesion in plasmid DNA and significant differences among the mutagenic potentials of MUC, HQ and p-BQ. HQ has stronger mutagenicity than the others. It is about 20 and 600 times stronger than p-BQ and MUC, respectively. Furthermore, we found notable differences in each mutational feature. The MUC mutational type was characterized by a high frequency of tandem base substitutions that could be due to crosslinks produced by its aldehyde moieties, while HQ was characterized by frequent deletion. This HQ feature is the same as in vivo benezene mutagenesis of Big Blue mice reported by Provost et al. in 1996 and is also quite similar to a hydrogen peroxide mutational feature. Therefore, we presume that HQ and reactive oxygen species may play an important role in benzene carcinogenesis.

The dynamic performances of DDTs in the environment and Japanese exposure to them: a historical perspective after the ban.

The fugacity model for evaluating DDTs dynamic performances in the environment was combined with the dietary exposure evaluation model, including the contribution of imported food, to develop the macroscopic mathematical model relating DDTs in the environment with the health risks of the reference Japanese. The model validity was examined by comparing the simulated DDTs concentrations in environmental media, various kinds of food, and dietary intake with those observed. Numerical simulations were done for the past half and future of one century to evaluate the effect of the DDTs usage prohibition in 1970 in Japan. The major results obtained under the limits considered are as follows. The DDTs concentrations in environmental media, various kinds of foods, and the dietary intake showed the steady exponential decrease after the DDTs usage prohibition in 1970. The DDE/DDTs ratio is larger in the higher position in an ecological system, and increased steadily with time. The critical exposure of DDTs occurred through animal product intake until 1960; after 1990 marine product intake caused the most exposure. The estimated DDTs intake was evaluated to be less than the PTDI and RfD. The annual excess cancer induction risk due to the annual dietary intake of DDTs was the largest at the level of (0.5 - 2.0) x 10(-6) (1/yr) in the early 1970s. The effect of the DDT usage prohibition on dietary exposure reduction was expected to appear after about 20 years. The life-span excess cancer induction risk was conservatively estimated to be larger than 10(-5) (1/lifespan) for the reference Japanese who were born before 1970. The DDTs usage prohibition in 1970 was effective to reduce the life-span cancer risk under the 10(-5) level.