Toshifumi Igarashi

Leaching of boron, arsenic and selenium from sedimentary rocks: II. pH dependence, speciation and mechanisms of release.

Sedimentary rocks excavated in Japan from road- and railway-tunnel projects contain relatively low concentrations of hazardous trace elements like boron (B), arsenic (As) and selenium (Se). However, these seemingly harmless waste rocks often produced leachates with concentrations of hazardous trace elements that exceeded the environmental standards. In this study, the leaching behaviors and release mechanisms of B, As and Se were evaluated using batch leaching experiments, sequential extraction and geochemical modeling calculations. The results showed that B was mostly partitioned with the residual/crystalline phase that is relatively stable under normal environmental conditions. In contrast, the majority of As and Se were associated with the exchangeable and organics/sulfides phases that are unstable under oxidizing conditions. Dissolution of water-soluble phases controlled the leaching of B, As and Se from these rocks in the short term, but pyrite oxidation, calcite dissolution and adsorption/desorption reactions became more important in the long term. The mobilities of these trace elements were also strongly influenced by the pH of the rock-water system. Although the leaching of Se only increased in the acidic region, those of B and As were enhanced under both acidic and alkaline conditions. Under strongly acidic conditions, the primarily release mechanism of B, As and Se was the dissolution of mineral phases that incorporated and/or adsorbed these elements. Lower concentrations of these trace elements in the circumneutral pH range could be attributed to their strong adsorption onto minerals like Al-/Fe-oxyhydroxides and clays, which are inherently present and/or precipitated in the rock-water system. The leaching of As and B increased under strongly alkaline conditions because of enhanced desorption and pyrite oxidation while that of Se remained minimal due to its adsorption onto Fe-oxyhydroxides and co-precipitation with calcite.

Subcritical crack growth in rocks in an aqueous environment.

Subcritical crack growth is one of the main causes of time-dependent fracturing in rock. In the present study, we investigated subcritical crack growth in rock in distilled water (pH = 5–7) and in an aqueous solution of sodium hydroxide (NaOHaq, pH = 12), comparing the results to those in air. We also investigated the effect of the pH in an aqueous environment. We used andesite and granite for all our tests. We determined the relationship between the crack velocity and the stress intensity factor using the double-torsion test under conditions of controlled temperature. We showed that crack velocities in water were higher than those in air, in agreement with other research results indicating that crack velocity increases in water. When we compared our results for NaOHaq with those for water, however, we found that the crack velocity at the same stress intensity factor did not change even though the pH of the surrounding environment was different. This result does not agree with the accepted understanding that hydroxide ions accelerate subcritical crack growth in rocks. We concluded that the pH at the crack tip influences subcritical crack growth, and not the bulk pH, which has little effect.

Leaching of boron, arsenic and selenium from sedimentary rocks: I. Effects of contact time, mixing speed and liquid-to-solid ratio.

Sedimentary rocks of marine origin excavated in tunnel projects were recently identified as potentially hazardous because they could release significant amounts of toxic trace elements when exposed to the environment. This study investigated the leaching characteristics of B, As, Se and the major coexisting ions under various conditions to identify the factors and processes controlling their evolution in the leachate. In addition, we evaluated whether the parameters of the currently used leachability test for excavated rocks were adequate. Although the leachabilities of B, As and Se similarly increased at longer contact times, only those of B and As were influenced by the mixing speed and/or liquid-to-solid ratio (L/S). The majority of trace elements dissolved in the leachate originated from the dissolution of soluble salts formed from seawater of the Cretaceous trapped during the formation of the sedimentary rocks. Moreover, the alkaline pH of the leachates could be attributed to the simultaneous dissolutions at varying degrees of the mineral components of the rocks as well as the precipitation of clay minerals. In the leaching test of excavated rocks for regulatory purposes, the best values of contact time and mixing speed should represent conditions of the highest trace element extractabilities, which in this study were found at longer contact times (>48 h) and the fastest mixing speed (200 rpm). The most appropriate L/S for the leaching test is 10 because it was around this L/S that the extractabilities and leaching concentrations of the trace elements were simultaneously observed at their highest values.

Prediction of groundwater contamination with 137Cs and 131I from the Fukushima nuclear accident in the Kanto district.

We measured the concentrations of (131)I, (134)Cs, and (137)Cs released from the Fukushima nuclear accident in soil and rainwater samples collected March 30-31, 2011, in Ibaraki Prefecture, Kanto district, bordering Fukushima Prefecture to the south. Column experiments revealed that all (131)I in rainwater samples was adsorbed onto an anion-exchange resin. However, 30% of (131)I was not retained by the resin after it passed through a soil layer, suggesting that a portion of (131)I became bound to organic matter from the soil. The (137)Cs migration rate was estimated to be approximately 0.6 mm/y in the Kanto area, which indicates that contamination of groundwater by (137)Cs is not likely to occur in rainwater infiltrating into the surface soil after the Fukushima accident.

Removal of Arsenic, Boron, and Selenium from Excavated Rocks by Consecutive Washing

This paper describes the leaching behavior and release mechanisms of arsenic (As), boron (B), and selenium (Se) from excavated rocks using sequential extraction for solid-phase fractionation, batch experiments with pH variation, and consecutive batch experiments with changes in the solid–liquid mixing ratios. Arsenic in the excavated rock was mostly found with the sulfides/organic matter fraction while majority of the leachable B and Se were associated with the exchangeable phases. The leaching of As was strongly pH dependent, Se was pH dependent only around the acidic region, and B was pH independent. Consecutive washing technique with deionized water effectively lowered the B and Se concentrations in the leachate below the drinking water standards of Japan, but was inefficient in the removal of As. Arsenic exhibited non-conservative leaching behavior and its movement was affected by processes like dissolution, precipitation, and pyrite oxidation. In contrast, B and Se behaved more conservatively, resulting in their easy removal from the excavated rock by simple washing and dilution.

Estimation of pyrite oxidation rate by sulfate ion discharged from a catchment

Abstract The in situ rate of pyrite oxidation was estimated at a proposed dam site by measurements of the amount of SO 4 2− discharged from the site to evaluate the impact of the dam on the surrounding environment. The SO 4 2− concentrations and flows of streams were simultaneously measured. The results showed that the SO 4 2− concentration depended on the sampling location, and that the tributaries with high SO 4 2− concentration corresponded to the distribution of pyrite-bearing rocks. The total amount of SO 4 2− discharged at the site was calculated at approximately 7.5 Mg/km 2 /year, based on an integral of the product of the SO 4 2− concentration and stream flow with respect to time. The origins of the discharged SO 4 2− could be divided into two categories: 60% from pyrite-bearing rocks and 40% from wet deposits at the site. Therefore, the rate of the pyrite oxidation at the site was calculated to be approximately 2.8 Mg/km 2 /year. The total amounts of SO 4 2− discharged from the acid water-producing areas located upstream and downstream of the site were calculated as 13–27 Mg/km 2 /year. The resultant weathering rate was estimated as 0.03–0.28 mm/year by considering the dry density and the pyrite content of these areas.

Simultaneous leaching of arsenite, arsenate, selenite and selenate, and their migration in tunnel-excavated sedimentary rocks: I. Column experiments under intermittent and unsaturated flow

Rocks excavated in tunnel construction projects for roads and railways throughout Japan often leached out hazardous trace elements like arsenic (As) and selenium (Se) upon their exposure to the environment. In nature, the various oxyanionic species of As and Se not only coexist but also exhibit contrasting adsorption-desorption behaviors, so speciation is a crucial factor in their migration through natural geologic media. In this study, the leaching and transport of arsenite (AsIII), arsenate (AsV), selenite (SeIV) and selenate (SeVI) in four tunnel-excavated rocks from the Cretaceous-Paleocene Yezo forearc basin were investigated using laboratory column experiments supplemented by batch leaching experiments. The single- and consecutive-batch leaching results revealed that AsIII, AsV, SeIV and SeVI were released simultaneously, which could be attributed to the rapid dissolution of trace evaporite salts found in the rocks. Arsenic in the leachates was also predominated by AsV while SeIV and SeVI concentrations were nearly equal, which are both consistent with predictions of equilibrium Eh-pH diagrams. Under intermittent and unsaturated flow, however, periods when AsIII and SeVI predominated in the effluents were observed. Spatial distributions of As and Se species with depth at the end of the column experiments suggest that migrations of AsIII, AsV and SeIV were delayed, the extent of which depended on the rock. These results indicate that migration and speciation of As and Se in the rocks are controlled by preferential adsorption-desorption reactions, the effects of which were most probably magnified by changes in the pH and concentrations of coexisting ions due to intermittent and unsaturated flow.

Groundwater monitoring of an open-pit limestone quarry: groundwater characteristics, evolution and their connections to rock slopes

Groundwater flow and its geochemical evolution in mines are important not only in the study of contaminant migration but also in the effective planning of excavation. The effects of groundwater on the stability of rock slopes and other mine constructions especially in limestone quarries are crucial because calcite, the major mineral component of limestone, is moderately soluble in water. In this study, evolution of groundwater in a limestone quarry located in Chichibu city was monitored to understand the geochemical processes occurring within the rock strata of the quarry and changes in the chemistry of groundwater, which suggests zones of deformations that may affect the stability of rock slopes. There are three distinct geological formations in the quarry: limestone layer, interbedded layer of limestone and slaty greenstone, and slaty greenstone layer as basement rock. Although the hydrochemical facies of all groundwater samples were Ca-HCO3 type water, changes in the geochemical properties of groundwater from the three geological formations were observed. In particular, significant changes in the chemical properties of several groundwater samples along the interbedded layer were observed, which could be attributed to the mixing of groundwater from the limestone and slaty greenstone layers. On the rainy day, the concentrations of Ca2+ and HCO3− in the groundwater fluctuated notably, and the groundwater flowing along the interbedded layer was dominated by groundwater from the limestone layer. These suggest that groundwater along the interbedded layer may affect the stability of rock slopes.

A Proposed Method to Estimate In Situ Dissolved Gas Concentrations in Gas-Saturated Groundwater

Gas-saturated groundwater forms bubbles when brought to atmospheric pressure, preventing precise determination of its in situ dissolved gas concentrations. To overcome this problem, a modeling approach called the atmospheric sampling method is suggested here to recover the in situ dissolved gas concentrations of groundwater collected ex situ under atmospheric conditions at the Horonobe Underground Research Laboratory, Japan. The results from this method were compared with results measured at the same locations using two special techniques, the sealed sampler and pre-evacuated vial methods, that have been developed to collect groundwater under its in situ conditions. In gas-saturated groundwater cases, dissolved methane and inorganic carbon concentrations derived using the atmospheric sampling method were mostly within ±4 and ±10%, respectively, of values from the sealed sampler and pre-evacuated vial methods. In gas-unsaturated groundwater, however, the atmospheric sampling method overestimated the in situ dissolved methane concentrations, because the groundwater pressure at which bubbles appear (Pcritical ) was overestimated. The atmospheric sampling method is recommended for use where gas-saturated groundwater can be collected only ex situ under atmospheric conditions.

Modeling and Evaluating the Performance of River Sediment on Immobilizing Arsenic from Hydrothermally Altered Rock in Laboratory Column Experiments with Hydrus-1D

Large volumes of excavated rock are produced as a result of road and railway tunnel construction in Hokkaido, Japan. Due to the geological condition of this region, these rocks have often undergone hydrothermal alterations, causing them to contain elevated amounts of hazardous elements including arsenic (As). Therefore, these excavated rocks are potentially hazardous waste, and proper disposal methods are required. In this article, performance of unsaturated river sediment on immobilizing As from hydrothermally altered rock is evaluated using laboratory column experiments and Hydrus-1D. The results reveal that the river sediment significantly reduces As migration. Arsenic retarded by river sediment was observed in three patterns. The first was an adsorption onto minerals originally contained in the river sediment. The next pattern was a combination of reduction of As generation by oxidation of As bearing-minerals, irreversible adsorption, and adsorption onto newly precipitated Fe oxy-hydroxide/oxide. The last pattern led to a further depletion of As leached from the rock layer due to a shift in the majority of the As generation mechanism from dissolution to oxidation in combination with a low concentration of oxygen in the rock layer. These patterns were satisfactorily evaluated by a Hydrus-1D model with reversible and irreversible adsorptions. The information from this work is effective in designing and establishing a reasonable technique for the disposal of hydrothermally altered rocks.