The spent adsorbents left after treating arsenic-contaminated water contain large amounts of arsenic. These spent adsorbents may come into contact with silicic acid leached from soil or cementitious solidification materials in the disposal environment. Thus, it is important to evaluate the effects of silicic acid on spent adsorbents containing arsenic. In this study, the effects of silicic acid on spent Mg-based adsorbents (magnesium oxide (MgO) and magnesium hydroxide (Mg(OH)(2))) containing arsenite were investigated. The arsenic leaching ratios of both spent adsorbents decreased slightly with an increase in the initial silicic acid concentration of the eluent. The arsenic leaching ratio decreased from 1.24% to 0.69% for MgO and from 5.97% to 4.71% for Mg(OH)(2) at an initial Si-normalized concentration of 100 mg/L. The primary mechanism behind the inhibition of arsenic leaching by silicic acid was determined to be the difficulty of arsenic desorption due to the coating effect following the adsorption of silicic acid species. The results indicate that the arsenic leaching related to the ion exchange reaction with silicic acid hardly occurred for the spent Mg-based adsorbents. Compared with various spent Mg-based and Ca-based adsorbents, the spent MgO adsorbent exhibited the highest environmental stability and best performance.

Gold (Au) mining area is known to be one of the major sources of toxic elements; however, the potential risks of toxic elements from abandoned Au mines to the surrounding river basin districts and human exposure pathways to toxic elements need to be clarified. In this study, the distribution and mobilities of nine toxic elements (As, Cd, Cu, Pb, Sb, Zn, Cr, Ni and V) in Kesennuma City, Tohoku Region in Japan, a typical Au-mining district with several river basins, were studied through a geochemical survey (including element total concentrations and water-/acid-leaching concentrations determinations, as well as GB calculations), and environmental assessment on these elements in soil, river sediment, and river water samples from the study area. The contamination evaluation by index of geo-accumulation (Igeo) and enrichment factor (EF) suggested that As, Cu, Ni and Sb enrichments were greatly observed in the vicinity of the abandoned Au mines; moreover, calculated GB upper values for Cu in the river sediment surpass that of Tohoku Region. It has been found in this study that each element has particular mobility, which eventually influences its exposure pathway to humans. For instance, As in soil and sediment poses adverse non-carcinogenic risks and unacceptable carcinogenic risks to especially children mainly through groundwater ingestion. To minimize the potential risks associated with exposure to toxic elements in Au-mining districts, effective risk management measures should be implemented around river system by Au-mining companies even after their long-time closures, based on the consideration of each element’s mobility.

The spent adsorbents that remain after being used to purify As-contaminated water constitute waste containing a large amount of As. These spent adsorbents, after being disposed, are likely to come into contact with silicic acid leached from the soil or cementitious solidification materials. Thus, it is crucial the evaluate the effects of silicic acid on spent adsorbents. In this study, the effects of silicic acid on spent Ca-based (CaO and Ca(OH)(2)) adsorbents with arsenite were investigated. The As leaching ratio for the spent adsorbents decreased with an increase in the initial concentration of silicic acid in the liquid. Under the tested conditions, the As leaching ratio decreased from 8-9% to less than 0.7% in the presence of silicic acid at an initial Si-normalized concentration of 100 mg/L. The primary mechanism behind the inhibition of As leaching by silicic acid was determined to be re-immobilization via the incorporation of arsenite during the formation of calcium silicates. In the presence of silicic acid, spent Ca-based adsorbents with arsenite had a lower As leaching ratio than those with arsenate. Therefore, spent Ca-based adsorbents with arsenite were found to have a higher environmental stability than those with arsenate.

<title>Abstract</title>This work developed a model for predicting the volatilization flux from the unsaturated soil contaminated by volatile chemical substances (VCSs) such as mercury and benzene. The model considers a series of phenomena under the unsaturated condition such as multi-phase flow consisting of a non-aqueous phase liquid, water, and gases together with the permeation of rainfall into the surface soil, the volatilization/condensation of VCSs, and the adsorption/desorption of VCSs. On this basis, this work clarified a mechanism for the generation of a volatilization flux at the ground surface. In addition, the effects of various transport phenomena in the surface soil on the magnitude and seasonal changes in this flux due to variations in weather factors such as rainfall level, temperature, and air pressure were quantitatively evaluated. This newly developed prediction model can be utilized to estimate dynamic variations in the flux under real-environmental conditions.

Chloroethenes are common soil and groundwater pollutants. Their dechlorination is impacted by environmental factors, such as the presence of metal ions. We here investigated the effect of ferrous iron on bacterial reductive dechlorination of chloroethenes and on methanogen community. Reductive dechlorination of tetrachloroethene was assayed with a groundwater sample originally containing 6.3 × 103 copies mL-1 of Dehalococcoides 16S rRNA gene and 2 mg L-1 of iron. Supplementation with 28 mg L-1 of ferrous iron enhanced the reductive dechlorination of cis-dichloroethene (cis-DCE) and vinyl chloride in the presence of methanogens. The supplementation shortened the time required for complete dechlorination of 1 mg L-1 of tetrachloroethene to ethene and ethane from 84 to 49 d. Methanogens, such as Candidatus 'Methanogranum', Methanomethylovorans and Methanocorpusculum, were significantly more abundant in iron-supplemented cultures than in non-supplemented cultures (P < 0.01). Upon methanogen growth inhibition by 2-bromoethanesulfonate and in the absence of iron supplementation, cis-DCE was not dechlorinated. Further, iron supplementation induced 71.3% dechlorination of cis-DCE accompanied by an increase in Dehalococcoides 16S rRNA and dehalogenase vcrA gene copies but not dehalogenase tceA gene copies. These observations highlight the cooperative effect of iron and methanogens on the reductive dechlorination of chloroethenes by Dehalococcoides spp.

© 2020 Elsevier Ltd The Tohoku region of Japan is geologically diverse, with a long agriculture and mining history; however, little information about the origins and distribution mechanisms of elements in this region has been reported. This study aims to provide fundamental insights into the effects of geological features and anthropogenic activities on various elements, including toxic elements and rare-earth elements (REEs), in the Tohoku region. A geochemical database (2007, AIST) consisting of data for 53 elements in 485 river sediment samples from the region was used, and a data-driven method combining principal component analysis (PCA) was applied for analysis. GBs for numerous types of areas, including general areas (GGB), natural environments (NGB), high anthropogenic-influenced areas (AGB) and mineralised areas (MGB) were established; especially, MGB was newly proposed in this study to illuminate the role of ore deposits. Both PCA and GBs comparison results show that geological features (especially igneous rock distribution) were the most important factor affecting elemental distribution, rather than anthropogenic activities. In the PCA, the first principal component showed that REE resources were commonly associated with the distribution of granitic rocks and REE-bearing minerals. Anthropogenic contaminations from mining, urban, and anthropogenic areas played important roles as the origin of some toxic elements (e.g. Ni, Pb, Sb). Comparisons between these GBs effectively elucidated the enrichment of certain toxic elements (e.g., Hg, Sb) in ore deposit areas. This data-driven study not only clarified the origins of toxic elements, but also revealed the location of potential REE mineral resources in the Tohoku region.

<p>Arsenite-arsenate separation analysis technique using a commercial anion exchange resin column with quaternary ammonium cations as anion exchange groups was studied. The selection of the optimum conditions for the valence-dependent separation of inorganic arsenic and the influence of coexisting anions were examined experimentally. By calculation based on the first dissociation constants of arsenite and arsenate, the optimum pH range of the test solution for valence separation of arsenic was estimated to be 4.3 to 7.1. When the test solution adjusted to the above pH was passed through the column, the arsenic in the test solution was separated appropriately by valence, because the arsenite is not adsorbed and the arsenate is adsorbed on the resin. Also, the arsenate adsorbed on the resin could be easily recovered almost completely by using HCl or HNO₃. The strength of the inhibition effect of coexisting anions on the recovery of arsenic was clarified to be "CH₃COO^－ << Cl^－ < NO₃^－ < SO₄^2－". The arsenite-arsenate separation analysis technique proposed in this study separated and recovered arsenite and arsenate with an experimental error of about 6％under the experimental conditions.</p>

The stability and dispersion of naturally occurring As have been receiving increasing attention, because As is toxic and its contamination is a widespread problem in many countries. This study investigated As fractionation and speciation in organic sediments collected from different depositional settings to elucidate the existence of stable As in humic substances. Eleven organic sediment samples were collected from marine and terrestrial alluvial regions in Hokkaido prefecture, Japan, and the chemical fraction of As and species of humic substances were identified by sequential extraction. In addition, stable As bound in organic matter was evaluated by FT-IR spectroscopy. The As fraction mainly comprised inorganic substances, especially sulfur, iron, and manganese, and terrestrial sediments (lacustrine and inland deposits) were rich in sulfides and Fe and Al (hydr)oxides. When the residual fraction was excluded, the organic fraction of As was higher in seawater sediments than in terrestrial sediments. Among humic substances, cellulose, humic acid, and hydrophilic fulvic acid were clearly associated with As accumulation, and As speciation showed that the As was of organic origin. Cellulose, an organic compound of plant origin, was abundant in As=S and As (III)=O bonds, and As accumulation was higher in sulfur-rich peat sediments, corresponding with the physiological activities of As in plants. Hydrophilic fulvic acid and humic acid in these sediments, originating from small animals and microorganisms in addition to plants, denote higher As contents and abound in As (III, V)=C and C-H, CH3 bonds even in sulfur-rich sediments. The methylated As bonds reflect the ecological transition of organisms.

Characterizing the mechanisms by which natural microorganisms in soil decompose gasoline hydrocarbons is of fundamental importance for a better understanding of natural attenuation and/or for predicting contaminant transport and fate in soils. To examine whether and how gasoline hydrocarbons can be decomposed under general environmental conditions, the decomposition of 10 major components generally contained in commercially available gasoline was analyzed in three arbitrarily selected Japanese soil samples. Gasoline hydrocarbons, especially aromatic hydrocarbons, are easily adsorbed by the tested Japanese soils, with straight chain hydrocarbons decomposing faster than branched hydrocarbons. Saturated monocyclic hydrocarbons were less easily decomposed than unsaturated monocyclic hydrocarbons. Enhancement of microbial decomposition of gasoline hydrocarbons requires a continuous supply of oxygen together with nutrients for the microorganisms.

&nbsp;Although calcium-based adsorbents are expected as effective arsenic adsorbents, the spent adsorbents which removed arsenic from contaminated water would contain a great amount of arsenic. If they were dumped into environment without an appropriate treatment, arsenic leached from them might cause a secondary environmental pollution. Also, silicic acid leached from soils or cementitious solidification materials may affect the environmental stability of the spent adsorbents.<br>&nbsp;In this study, the leaching tests with silicic acid solutions on the spent calcium-based adsorbents (CaO and Ca(OH)₂) were carried out. The arsenic leaching ratios of spent Ca-based adsorbents were found to decrease as silicic acid concentration in liquid is higher. Calcium ions leached from the spent adsorbents can be considered to react with silicic acid components in the liquid to form calcium silicate species. Then, arsenic components leached from the spent adsorbents can be considered to be incorporated into the silicates during the above formation process. In addition, the average chemical compositions of the calcium silicates formed are considered to depend on the initial silicic acid concentration in the test solutions. In the cases of around 25 or 50～100 mg/L as the initial Si concentration, each of the average chemical composition formula was estimated to be Ca₂SiO₄ and CaSiO₃. On the other hand, in the case that initial Si concentration was relatively low (around 5 mg/L), the reaction in which silicic acid components adsorb directly onto the spent adsorbent surface (ion-exchange or chemical adsorption reaction) was inferred to be predominant.

&nbsp;1,4-dioxane is a toxic chemical substance which means to be difficult to take on-site soil investigation, compared with VOCs, because it has not been elucidated scientifically on geo-environmental behaviors. This study focuses on the partitioning and the distribution of 1,4-dioxane in soil, water and gas phases for inorganic soil and organic soils. The equilibrium concentrations in soil interlarded by 1,4-dioxane have been obtained under various conditions (pH, moisture content and water retention). The results showed that the distribution ratio of 1,4-dioxane to soil was 0.1 ~ 5.0%. However, under alkaline condition (pH 13), 1,4-dioxane could be distributed in the soil by an amount as much as 20%. The phrase soil water retention ability, 1,4-dioxane concentration largely changed due to the dilution of pore water in the soil with low organic content. Thus, it can be concluded that the majority of released 1,4-dioxane into the environment migrates to pore water in soil structure or into groundwater, unless it changed to a distinctive environmental conditions of high alkali and/or low water retention.

&nbsp;The adsorbents which removed arsenic from contaminated water would contain a large amount of arsenic. If the spent adsorbents were dumped into environment without an appropriate treatment, a secondary environmental pollution might be caused by arsenic leaching.<br>&nbsp;In this study, the leaching tests with silicic acid solution on the spent magnesium-based adsorbents (MgO, Mg(OH)₂ and two types of MgCO₃) were conducted and the experimental data obtained were examined. From the results, the spent Mg(OH)₂-based and MgCO₃-based adsorbents were found to leached arsenic more easily as silicic acid concentration in liquid is higher. On the other hand, the spent MgO-based adsorbent was found to leach little arsenic and maintain extremely high environmental stability. Therefore, MgO among them was concluded to be the most excellent arsenic adsorbent to be used under the conditions where silicic acid is generated in the leachates from soils, cement-based solidifying materials and so on.

Tsunami deposits accumulated on the Tohoku coastal area in Japan due to the impact of the Tohokuold earthquake. In the study reported in this paper, we applied principal component analysis (PCA) and cluster analysis (CA) to determine the concentrations of heavy metals in tsunami deposits that had been diluted with water or digested using 1 M HCl. The results suggest that the environmental risk is relatively low, evidenced by the following geometric mean concentrations: Pb, 16 mg kg(-1) and 0.003 ml L-1; As, 1.8 mg kg(-1) and 0.004 ml L-1; and Cd, 0.17 mg kg(-1) and 0.0001 ml L. CA was performed after outliers were excluded using PCA. The analysis grouped the concentrations of heavy metals for leaching in water and acid. For the acid case, the first cluster contained Ni, Fe, Cd, Cu, Al, Cr, Zn, and Mn; while the second contained Pb, Sb, As, and Mo. For water, the first cluster contained Ni, Fe, Al, and Cr; and the second cluster contained Mo, Sb, As, Cu, Zn, Pb, and Mn. Statistical analysis revealed that the typical toxic elements, As, Pb, and Cd have steady correlations for acid leaching but are relatively sparse for water leaching. Pb and As from the tsunami deposits seemed to reveal a kind of redox elution mechanism using 1 M HCl. (C) 2015 The Authors. Published by Elsevier Ltd.

It is important to understand the distribution mechanism of heavy metal elements in environmental systems, because the toxicities of various metals and metalloids significantly affect health risks. The heavy metals concentrations are controlled by a wide of variety environmental factors. This study aims to clarify main influence factors on the heavy metal distribution in sediment, soil, river in the Natori River, Sendai City. We firstly produced geochemical maps for heavy metal concentrations (As, Pb and Cr) of river sediment, neighboring soil (bulk component, soluble component in 1N HCl and in pure water) and river water. The heavy metals concentrations in river water increase from upper stream to down stream, whereas heavy metal concentrations in river sediments and soil vary little from upper stream to downstream. There are no anomalous distributions of heavy metals in the studied area, although many anthropogenic materials are found in sediment, soil and river water. The correspondence analysis was applied to investigate relationships of heavy-metal concentrations between sediment, soil and river water. The results indicate that the heavy metals (As, Pb Cr and Zn) in sediment, soil and river water are dominantly controlled by natural sedimentary processes, such as denudation and sedimentation. The proposed method could be further applied for other pollutants in various environment systems. From a viewpoint of risk assessment of heavy metals, it is suggested by the presence of closer relationship of heavy metals that contains the risk information of heavy metals.

Beneficial utilization of steel slag as an environmental remediation material of seawater damages by mixing with humic acid has been expected. To achieve it, environmental impact of the slag is required interms of leaching behavior of heavy metals.<br> This research applied a seawater leaching test by shaking and immersing the slag with humic acid. Furthermore, based on the concept of environmental safety quality required in the sea-area utilization, applicability of the slag is discussed. Experimental results showed that by the interaction of steel slag and humic acid, concentration of Cd, Pb, Cr and B decreased and could meet the environmental safety quality criteria. In conclusion, the possibility that the mixture of steel slag and humic acid cause sea-environment pollution proved to be significantly low.

The great tsunami that followed the 2011 off the Pacific coast of Tohoku Earthquake caused derangement of superficial sediments in coastal areas of Sendai Plain and Sendai Bay. Tsunami deposits were transported with flooded seawater in the form of mud, sand, or granules, and were deposited in the coastal region. These deposits record important information that facilitate determining the age and frequency of past tsunami events. The origins of tsunami deposits and the derangement of marine sediments are studied based on a chemical composition analysis of tsunami deposits, marine sediments, and samples of subsurface soil collected before the earthquake. The solubility of chemical components, such as of chromium, iron, nickel, copper, zinc, arsenic, and lead, in 1 M HCl was much higher for tsunami deposits than subsurface soils. The metal speciation and correlation of chemical composition indicate that the main origins of tsunami deposits are coastal marine sediments. The transformation of marine sediments to the coastal side, except Arahama offing, is also confirmed from active regional shifts of bacteria. These imply that the tsunami had a large effect on mobilizing marine sediments in the northern area of Sendai Bay, Nanakita River offing, Arahama offing, and Hiroura offing based on the extent of bacterial activity shift and chemical compositions of organic materials.

This study involved measurement of concentrations of dissolved and particulate radiocesium (Cs-134 and Cs-137) in river water, and determination of the quantitative relations between the amount of deposited Cs-137 and Cs-137 concentrations in river waters after the Fukushima Daiichi nuclear power plant accident. First, the current concentrations of dissolved and particulate Cs-134. Cs-137 were determined in a river watershed from 20 sampling locations in four contaminated rivers (Abukuma, Kuchibuto, Shakado, and Ota).
Distribution characteristics of different Cs-137 forms varied with rivers. Moreover, a higher dissolved Cs-137 concentration was observed at the sampling location where the Cs-137 deposition occurred much more heavily. In contrast, particulate Cs-137 concentration along the river was quite irregular, because fluctuations in suspended solids concentrations occur easily from disturbance and heavy precipitation. A similar tendency with dissolved Cs-137 distribution was observed for the Cs-137 concentration per unit weight of suspended solids.
Regression analysis between deposited Cs-137 and dissolved/particulate Cs-137 concentrations was performed for the four rivers. The results showed a strong correlation between deposited Cs-137 and dissolved Cs-137, and a relatively weak correlation between deposited Cs-137 and particulate Cs-137 concentration for each river. However, if the particulate Cs-137 concentration was converted to Cs-137 concentration per unit weight of suspended solid, the values showed a strong correlation with deposited Cs-137. (C) 2014 Elsevier Ltd. All rights reserved.

We developed a rapid method for concentrating and measuring radiocesium (Cs-134 and Cs-137) dissolved in fresh water using nonwoven fabric impregnated with Prussian blue (PB) as a radiocesium absorber in combination with gamma-ray spectrometry using a germanium (Ge) detector. Utilizing this method, dissolved radiocesium in a 20-100 L freshwater sample could be concentrated within a period of 20-60min by passing the sample through 10-12 columns, connected in series, that had been fitted with nonwoven fabric disks impregnated with PB. Laboratory tests using water samples containing known amounts of radiocesium confirmed that the overall recovery rate of the isotope was 100%-108%, and that the first six columns recovered 84%-97% of the isotope. The detection limit of this method was determined to be 0.002 Bq/L with a sample of 100 L and measurement time of 43,200s. In comparison with traditional methods using ion-exchange resin, co-precipitation with ammonium phosphomolybdate, etc., our method has the advantages of reduced cost and a significantly shorter concentration time. Since water samples can be treated in short periods of time, it is now possible to conduct radiocesium pre-concentration in situ, thus eliminating the need to transport large-volume water samples to laboratories.

The steel slag/compost fertilizer containing soluble form of iron has been evaluated for restoring barren coastal ground. While humic substances in the compost have been believed to be carriers for supplying iron to such coastal land, they become coagulated and/or flocculated in seawater. Thus, the focus of the study was on seawater extractable organic matter (SWEOM) from the compost that could function as a chelator of iron. Structural features of a novel organic fraction from the compost, SWEOM, were characterized by TMAH-py-GC/MS and the result were compared with those for humic (HA) and fulvic (FA) acids from the same origin. The TMAH-py-GC/MS analyses provided information on the structural characteristics for HA, FA and SWEOM. FA contained high amount of nitrogen-containing pyrolysate compounds, which were likely derived from saccharides and RNA. The large amounts of methoxybenzenes and hydroxybenzenes, which were originated from lignin, were also identified in the HA. For SWEOM, the percentages of fatty acid pyrolysate compounds were significantly larger than the corresponding values for HA and FA. An acidic functional group analysis indicated that the levels of carboxylic groups in SWEOM were lower than those in HA and FA, suggesting that the fatty acid pyrolysate compounds were produced as the result of the cleavage of ester-linkages. (C) 2012 Elsevier B.V. All rights reserved.

Alterations in the structural features of humic acids (HAS) in a steel slag-compost fertilizer for supplying soluble Fe(II) to barren ground in coastal areas were monitored during a 6-month period of fertilization. HAs, the major organic fractions in the fertilizer, were extracted at different periods of time (2, 4 and 6 months) in the absence and presence of steel slag. To focus on the polymeric structure of the HA-backbone and the organic fractions, which are sorbed onto the HA-polymeric matrix (e.g., lipids), the extracted HA samples were analyzed by pyrolysis-gas chromatography/mass spectrometry under conditions where the sample is methylated with tetramethylammonium hydroxide (TMAH-py-GC/MS). The structural features analyzable by TMAH-py-GC/MS for the HA were dramatically altered in the presence of steel slag during the fertilization period. The major modification involved a decrease in phenolic moieties and a significant increase in the sulfur-containing pyrolysate compounds. These results indicate that the steel slag has a significant effect in altering the structure of HA in the fertilizer. TMAH-py-GC/MS analysis of the HAs indicated that the sulfur in the HAs was present in an organic form and not as elemental sulfur. Significant increases in the levels of biomarker fatty acids (iso- and anteiso-C-15:0 and C-17:0 carboxylic acids), which are related to the activity of sulfate reducing bacteria, suggests that the significant alterations in the HA structures in the presence of steel slag can be attributed to the sulfurization of organic matter in the fertilizer to form hydrogen polysulfides by the reduction of sulfate ions in seawater and/or steel slag via microbial processes. (C) 2012 Elsevier B.V. All rights reserved.

We have surveyed tsunami flooding areas from Aomori to Chiba prefecture to identify various kinds of geological and geochemical evidences occurred by Tsunami disaster. As a result, it was found that tsunami sediments have layering structure of several hits in a couple of hours. The lands are covered by almost sandy sediments with some layers of silt and mud or clay minerals, which have relatively higher content of organic substances and sulfur. Soils and sediments originated from tsunami contain relatively higher concentration of arsenic and lead elements, compared with natural background. This suggests that the sediments were transported from offshore marine mud with anaerobic environment. In some cases, risk mitigation will be necessary for safe land utilization. Copyright © 2012 by the International Society of Offshore and Polar Engineers (ISOPE).

Understanding the transport and fate of gasoline components in soils is of fundamental importance for protecting human health from possible risks. A series of column experiments were performed to investigate the effects of soil organic matter, on the transport of total petroleum hydrocarbons (TPH) and the paraffin (n-paraffin and isoparaffin), olefin, naphthene, and aromatic (PONA) components in 2 typical Japanese soils. The results of this study illustrated the following observations: 1) The remaining mass of regular gasoline in a soil is time-dependent. 2) The major degradation mechanism of regular gasoline in soils would be volatilization. 3) The sorption of regular gasoline by soil organic matter might be one of the major reasons that causes regular gasoline remaining in Kuroboku soil. 4) Aromatic and isoparrafine components are tended to remain in soils. © 2012 Nova Science Publishers, Inc.

In order to determine whether natural attenuation of chlorinated ethenes by microbial activity occurs in aquitards, sediments at a site contaminated with tetrachloroethene were vertically studied by drilling. The distribution of microbes (Dehalococcoides group and anaerobic hydrogen producers) and the ability of the sediments to sustain microbial dechlorination were determined in an aquitard as well as in an aquifer. Close-spaced sampling revealed the existence of large populations of Dehalococcoides and H(2)-producing bacteria, especially in the organic-rich clayey aquitard rather than in the aquifer. The vinyl chloride reductase gene was also detected in the clay layer. Furthermore, incubation experiments indicated that the clay sediment could sustain transformations of tetrachloroethene at least to vinyl chloride. In contrast, no significant transformation was observed in the aquifer sand. Our results indicate that dechlorination of tetrachloroethene by bacteria can take place in an organic-rich clayey aquitard, and that organic-rich clay may also be important in the natural attenuation in an adjacent aquifer, possibly supplying a carbon source or an electron donor. (C) 2011 Elsevier B.V. All rights reserved.

The combination of steel slag and humic acids has an important role that the migration of essential elements, particularly iron and nutrients can be promoted in the aquatic environment. Humic substances such as fulvic acid and humic acids have functions of the formation of chemical complex with metal elements in the environment. Especially in the structure of fulvic acid, iron and humic matter have relatively strong linkage to form a chemical structure of iron-fulvic substances which can dissolve in water phase and be easily taken in plants and organisms as an essential element of iron. A kind of humic substances is considered to be very effective to rehabilitate the ecological situation around coastal environment. In this paper we present the methodology of chemical analysis for complex formation between divalent iron and humic substances, obtained from soils, sediments, plants, woods and coal materials. The necessary conditions of eluting humic substances into aquatic environment were experimentally examined using the natural substances modified by pH and Redox control. The properties of long-term stability of humic substances were also investigated under the condition of fresh water and sea water environments. In addition a trial of risk assessment using the original assessment tool was carried out to reveal safer features of this technology. Thus the acceptability of the technology using steel slag and humic substances is discussed on the basis of experimental and risk assessment results.

Understanding the volatilization properties of gasoline components in soils is of fundamental importance in the field of geoenvironments. A series of experiments were performed to investigate the effects of temperature, soil water content, soil organic matter content, as well as mean particle size on volatilization rate of total petroleum hydrocarbons (TPH) and the paraffin (n-paraffin and isoparaffin), olefin, naphthene, and aromatic (PONA) components in four typical Japanese soils. The results of this study can be summarized as follows. (1) Volatilization rate of gasoline in a soil is concentration-dependent; extensive volatilization occurs above a certain threshold, while volatilization becomes very slow below this threshold. (2) Compared to other factors, temperature and soil organic matter content have greater effects on volatilization rate of gasoline in soils. The volatilization rate is proportional to temperature, but inversely related to soil organic matter content. (3) The characteristics of time-dependent decreases of TPH and PONA components in soils are similar. The volatilization rate of olefin is higher than those of other components. In addition, volatilization of olefin is also more sensitive to temperature as well as organic matter content.

There is no question about the importance of understanding the fate of oil pollutants and the risks of individual components of gasoline to human health. To investigate the effects of major environmental factors on the volatilization of regular gasoline from unsaturated soils, a series of experiments were organized and performed on four typical Japanese soils under different temperature, soil organic matter content, and water content conditions. Quantitative assessment of risks of each residual gasoline component to human health was pioneered using the experimental results and a self-developed software program, Geo-Environmental Risk Assessment System (GERAS). Results of this study illustrated that (1) temperature and soil organic matter had significant effects on volatilization and thus on the residual concentrations of gasoline components remaining in unsaturated soils. These residual concentrations were positively related to the amount of soil organic matter, but inversely related to temperature. (2) Risks of residual gasoline components remaining in soils depended on exposure pathway, gasoline component, and carbon numbers. Risks of respiratory exposure due to vapor inhalation were generally higher than the risks of oral exposure due to intake of crops and water. (3) Although residual concentrations of gasoline components remaining in soils with high organic matter contents were high, their risks to human health were low. This is because high organic matter content has strong sorptivity for gasoline components, resulting in less vapor inhalation, less intake from water, and low bioavailability for crops.

Non-destructive measurements of contaminated soil core samples are desirable prior to destructive measurements because they allow obtaining gross information from the core samples without touching harmful chemical species. Medical X-ray computed tomography (CT) and time-domain low-field nuclear magnetic resonance (NMR) relaxometry were applied to non-destructive measurements of sandy soil core samples from a real site contaminated with heavy oil. The medical CT visualized the spatial distribution of the bulk density averaged over the voxel of 0.31 x 0.31 x 2 mm(3). The obtained CT images clearly showed an increase in the bulk density with increasing depth. Coupled analysis with in situ time-domain reflectometry logging suggests that this increase is derived from an increase in the water volume fraction of soils with depth (i.e., unsaturated to saturated transition). This was confirmed by supplementary analysis using high-resolution micro-focus X-ray CT at a resolution of similar to 10 mu m, which directly imaged the increase in pore water with depth. NMR transverse relaxation waveforms of protons were acquired non-destructively at 2.7 MHz by the Carr-Purcell-Meiboom-Gill (CPMG) pulse sequence. The nature of viscous petroleum molecules having short transverse relaxation times (T2) compared to water molecules enabled us to distinguish the water-saturated portion from the oil-contaminated portion in the core sample using an M (0)-T2 plot, where M (0) is the initial amplitude of the CPMG signal. The present study demonstrates that non-destructive core measurements by medical X-ray CT and low-field NMR provide information on the groundwater saturation level and oil-contaminated intervals, which is useful for constructing an adequate plan for subsequent destructive laboratory measurements of cores.

It is demanded more convenient survey methods for soil pollution by oils and techniques for toxicity evaluation of petroleum hydrocarbons. The quantitative bioassay using luminous bacteria has not been established. The accumulation of data obtained under scientific condition setting is required.<BR>Firstly, methanol, ethanol and n-propanol which are both moderate hydrophilic and oleophilic, were examined whether they are adequate as the extraction solvent for soil polluted by oils. From the results in bioassay test using luminous bacteria, methanol was selected as the most suitable extraction solvent from them.<BR>Secondly, the acute toxicity evaluation and the detection limit of gasoline, heating oil, light oil, benzene, toluene, n-hexane and carbon disulfide were experimentally examined. The severity of toxicity on luminous bacteria by each 100 vol% of them (without solvent) except n-hexane was carbon disulfide > toluene > gasoline > benzene > methanol > heating oil > light oil. Although the toxicities of 100 vol% of heating oil, light oil and n-hexane were weaker than that of methanol, the use of methanol as the solvent improved the detection sensitivity for them and was possible to detect the toxicity of them by luminous bacteria. The appropriate reaction time for toxicity evaluation or screening may be 15 to 45 minutes. The severity of toxicity on luminous bacteria evaluated using methanol solvent was gasoline > n-hexane > heating oil > toluene > carbon disulfide > benzene > light oil. Also, this study showed potential for quantitatively evaluating in the ranges of 0.02 to 1 vol% of gasoline and heating oil, 0.1 to 5 vol% of light oil and carbon disulfide, 0.2 to 5 vol% of benzene, 0.1 to 1.0 of toluene and 0.05 to 0.5 vol% of n-hexane in methanol solvent (extractant).

Some of the natural origin heavy metal is sourced from alteration region accompanied by ore deposits and mineral vein. In this research, we investigate heavy metal contents and leaching ability of hydrothermal alteration zone, targeted on Osaru River basin located in southern part of Hokkaido, Japan. Several hydrothermal alteration zone and ore deposits are distributed in the tributary of Osaru River. A lots of Zn, As, Pb, Cu, Ni-enriched rock samples are observed in hydrothermal alteration region. Although especially high heavy metal contents are observed near hydrothermal alteration area, subsurface soils near alteration region does not reflect on metal-rich chemical composition of hydrothermal alteration zone. High leaching arsenic subsurface soils are detected only downstream part of main Osaru River basin composed of fluvial sediments. The arsenic transport from alteration zone is controlled by secondary adsorption to the metal-oxides, -hydroxides, or the other clay minerals in hydrothermal alteration zone. The arsenic leaching potential from alteration zone to the river depends on alteration aspect and environment, and especially, subsurface alteration zone including ferrihydrite and goethite distributed near riverside have high leaching potential.

In developing risk assessment technology for soil contamination, it is essential to carry out a wide range of fundamental research and to synthesize the results into a single system. We have carried out an integrated research project for a comprehensive risk assessment system; this project includes fundamental knowledge, database formulation, commercialization of technology, and the introduction of the research results to a social system. In this paper, we present a scenario in Synthesiology, the integration of each part of the research results, and discuss the spiral processes involved in the implementation of risk assessment.

Reacently, contaminated soil by mineral oil has been the biggest environmental issue, and remediation technologies have developed. In these technologies, bioremediation is effective to decompose mineral oil. However evaluation of risk for human health has not been carried out through bioremediation process. This study investigate that the change of risk though the bioremediation process evaluate using a risk analyizing system.

The degradation behavior of chlorinated solvents were difference between each sites and classified in three types; (A) degradation with by-products, (B) degradation without by products, (C) non-degradation. The chemical components in the groundwater of the degradation type (A) showed lower redox potential (ORP), dissolved oxygen (DO) and higher heavy metals such as iron and manganese. These anaerobic reducing ambient is suitable for the bacteria concerned with the reductive dechlorination. Further, there is a possibility that chlorinated solvents are dechlorinated by catalysis, for example pyrite, containing within the soil. The chemical components in groundwater showed higher ORP, DO (degradation type (13)). Since the contaminant at the site YO was PCE which was not degraded by aerobic microorganisms, the reason for the natural attenuation might be dispersion or dilution. Although the higher ORP, DO were detected at degradation type (C), the VOC (TCE) was not attenuated at the site HK. This suggest that the dense non-aqueous phase liquids (DNAPLs) exist in the soil or groundwater, or the biochemical activity is low in this condition due to lower temperature.

Experimental studies of dehalogenation for chlorinated benzenes were conducted using iron sulfide (FeS2) at 25 degrees C in pure water. Chlorinated benzenes are used as a model sample of persistent organic pollutants (POPs) and evaluate the dechlorination ability of natural metallic minerals for POPs. A total of 90% of chlorinated benzenes are dechlorinated after a mere 10 days for mono-, di-, tri-chlorobenzenes and 1,2,3,4-, 1,2,3,5-tetrachlorobenzenes. Their dechlorination abilities are not sensitive to the difference in isomers. The other 1,2,4,5-tetrachlorobenzene, pentachlorobenzene and hexachlorobenzene are also dechlorinated at about 10 to 30% after 10 days. This dehalogenation is only utilized in the dissolution of natural metallic minerals. Metallic minerals such as iron sulfide are expected to have sufficient remediation ability not only for chemical treatment but also as a natural depollution mineral.

Methane hydrate is one of the potential resources of natural gas in the near future, because a large amount of reservoir exists in marine sediments and permafrost regions worldwide. It is very important to investigate physical phenomena in hydrate reservoirs, especially for developing an extraction system for gas hydrates, and in considering the environmental impacts by the development.<BR>In this study, we carried out an experimental research on hot water injection process as one of the thermal stimulation methods, using a special-type apparatus designed for simulating hydrate reservoir. As a result of the experiments, it was found that the dissociation process by hot water injection consisted of the following four stages, such as (1) displacement of free methane gas due to water injection, (2) additional hydrate formation at downstream zone due to migration of dissociated gas and water, (3) actual dissociation, (4) completion of dissociation. In addition, the permeability of the hydrate reservoir was observed as a function of time that, tended to decrease during the additional hydrate formation period and increase during the actual hydrate dissociation period. Based on experimental data of temperature distribution during dissociation, the reservoir could be divided into three zones from upstream edge, and dissociation zone was extremely narrow area depending on the dissociation rate. Furthermore, we discussed the effect of injected water temperature, reservoir pressure and hydrate saturation on the movement of dissociation front and gas production behavior.

In order to obtain fundamental data for the evaluation of permeability in methane hydrate reservoir, we have conducted experimental and analytical studies on the behavior of formation and dissociation of methane hydrate in porous media and the change in permeability in the process of formation and dissociation. The experimental apparatus for permeability measurement was originally designed and manufactured. Very uniform methane hydrate reservoir was achieved by the method of gas injection into sand column. The artificial sample of sand column with methane hydrate was satisfactory for the experiment of absolute permeability measurement. As a result of the experiment, it was found that the formation rate of methane hydrate in porous media depends on the particle size distribution of sands composing porous media. The interfacial condition between methane gas and pore water was an essential parameter of formation. In an experiment of dissociation of hydrate by the injection of hot water, the increase of permeability in methane hydrate reservoir was observed as a function of time. The large decrease in permeability was also obtained as a result of reformation due to flow of dissociated gas in porous media. The apparent absolute permeability drastically decreased as the hydrate saturation in sand column becomes lower. The values of the permeability in the case of hydrate saturation 40 % were 1/30 to 1/50 compared with the original values without any hydrate formation in porous media.

The influence of high concentrations of ferric ions on the biochemical activity of Acidithiobacillus ferrooxidans was studied using intact cells. The specific oxidation rate of ferrous ions decreased with increasing ferric ion concentration. Lineweaver-Burk plots revealed typical competitive inhibition kinetics, because the slopes varied with the ferric ion concentration. A linear relationship between the slope and the square of the ferric ion concentration revealed that the iron-oxidizing enzyme system of A. ferrooxidans was competitively inhibited by about two molecules of ferric ion. The kinetic equation based on this inhibition model agreed with the experimental observation at a high ferric ion concentration where the bacterium is usually exposed in bioleaching and biooxidation plants.

The exposure rates, the distribution of exposure paths and the risk level of inorganic arsenic containing in soil and groundwater in Japan have been evaluated by using originally developed risk assessment model.<BR>Major exposure path for human to arsenic in Japan was food intake. The average total exposure rate was estimated about 4×10^-1 to 5×10^-1 (95% confidence interval (CI)), which revealed that the skin cancer risk resulting from oral intake was about 6×10^-4 to 7×10^-4 (95%CI) and the lung cancer risk resulting from inhalation intake was about 2×10^-4 to 2×10^-3 (95%CI). The total exposure rates from soil and groundwater paths were about 3×10^-3 to 5×10^-2 (95%CI), which revealed that the average oral and inhalation cancer risk (95%CI) was evaluated at 4×10a^-6 to 8×10^-5 and 1×10^-5 to 2×10^-4, respectively.<BR>The contaminated area where soil concentration was higher than Japanese criteria of total content in soil (150mg/kg) had the oral cancer risk more than 5×10^-4 to 1×10^-3 (95%CI) and the inhalation cancer risk 2×10^-3. The risk level of contaminated area exceeded groundwater criteria (10μg/l ) was estimated at about 3×10^-5 to 8×10^-5 (95%CI).

We have developed the geo-environmental risk assessment model for heavy metals, which are considered both soil properties and exposure factors specific to Japanese situations. The exposure rates, the distribution of exposure paths and the risk level of soil content to the human have been evaluated by using this model.<BR>Since the Japanese soil have the specific properties, i.e. high pH, high fraction of organic carbon content and high fraction of clay content, it is difficult to transport into the groundwater and the crops in comparison with other kinds of soil. The exposure rates of children are higher than those of adults. Especially, infants aged 1 to 2 are much exposed to the heavy metals. The major exposure paths of the human are different due to the kind of heavy metal. The human are mainly exposed to lead and chromium from direct ingestion of soil, whereas they are mainly exposed to selenium and cupper from intake of drinking water. The soil contents of exposure limit are estimated at 37 mg / kg for arsenic, 26 mg / kg for cadmium, 620 mg / kg for chromium, 4,600 mg / kg for cupper, 4.0 mg / kg for mercury, 120 mg / kg for lead and 1.6 mg / kg for selenium.

The reduction reaction of selenate ion by TiO₂ photocatalyst in the presence of sulfate ion was studied. Sodium selenate solution was used in the experiments. The selenium concentration of this solution was 10 to 100 ppm as selenium (1.27×10^-1 to 1.27 mmol / dm³), and 1.27 to 1.27×10 mmol / dm³ of sodium sulfate and 2.5×10 mmol / dm³ of formic acid were added to it.<BR>The rate of the reduction reaction of selenate ion by the TiO₂ photocatalyst became smaller by the presence of the sulfate ion. However, the reduction reaction of selenate ion proceeded until the remaining total selenium concentration became under 0.1 ppm. Reduced selenate ion became hydrogen selenide via amorphous selenium, and trapped by the CuSO₄ solution gas trap. On the contrary, sulfate ion was not reduced by the TiO₂ photocatalyst. The rate of the reduction reaction of selenate ion to amorphous selenium depended on the amount of adsorbed selenate ion (C_SeA) and was expressed as a dimensional function of C_SeA. The amount of adsorbed selenate ion on the TiO₂ photocatalyst was decreased with increase of the amount of sulfate ion, and was expressed as the competitive Langumuir isotherm. This is the reason why the rate of the reduction of selenate ion becomes smaller by the presence of sulfate ion.

Biochemical activities of Thiobacillus ferrooxidans in the presence of activated carbon were studied under the shaking and stationary conditions using the 9K medium at pH 1.5. In the shaking condition, the biochemical activities of the bacterium were lower in the presence of activated carbon than in the absence. On the contrary, the activities were higher under the stationary condition. In the shaking condition, the bacteria were adsorbed onto the activated carbon according to the Langmuir isotherm. The adsorbed cells became inactive with regard to their ferrous ion-oxidizing and growth. Under the stationary condition, the oxidation rate of ferrous ion was higher in the presence of activated carbon than in the absence, because the cells gathered to the gas-liquid interface in the presence of activated carbon.<br>

This paper describes an inhibition of oxidation and growth of Thiobacillus ferrooxidans by chloride ion and the effect of diatomaceous earth against its inhibition. <br> Ferrous ion oxidation experiment in the absence of nutrient salts was carried out with various amount of chloride ion. The assay solution of this experiment contained only ferrous sulfate and magnesium sulfate (pH 1.5), and no bacteria grew in this condition. The oxidation of ferrous ion was inhibited by the chloride ion, and was subjected to the competitive inhibition from the Lineweaver-Burg plot. The addition of the diatomaceous earth in assay solution had no effect on the bacterial oxidation.<br> The growth of T. ferrooxidans in 9 K medium was also inhibited by the chloride ion. The growth kinetics of this bacterium in the presence of chloride ion were described with the modified Monod type equation including the term of inhibitor concentration. The growth inhibition reduced by the addition of diatomaceous earth in the medium. The oxidation rate in the presence of diatomaceous earth was much faster than that in the absence of it in high concentration of chloride ion. The growth inhibition constant of adsorbed bacteria was about 60 % larger than that of free bacteria, which was the reason the oxidation of ferrous ion in the presence of diatomaceous earth was faster. <br> The adsorption amount of T. ferrooxidans onto the diatomaceous earth was almost constant in this experimental range of the chloride ion. <br>

Diatomaceous earth is an effective carrier with a large surface area on which Thiobacillus ferrooxidans adsorbs, and enhances the oxidation rate of ferrous ions by the bacterium. The adsorption of T.ferroxidans on diatomaceous earth was expressed by the Henry isotherm, and reached equilibrium within five minutes. The enhancement was due to an increase in the growth rate of the adsorbed cells, which were so active that their specific growth rate calculated using a Monod-type equation was higher than that of the free cells in the liquid phase.