Combined neutralization-adsorption system for the disposal of hydrothermally altered excavated rock producing acidic leachate with hazardous elements

Hydrothermally altered rock excavated in a tunnel project produces acidic leachate containing hazardous elements that include arsenic (As), lead (Pb), copper (Cu) and zinc (Zn). To mitigate this problem, this paper evaluated a combined neutralization-adsorption system that used readily available and cheap reagents like calcium carbonate (CaCO3) and partly-weathered volcanic ash. Batch neutralization experiments showed that CaCO3 was effective in raising the pH of the leachate around neutral while the batch adsorption experiments illustrated that the volcanic ash sample collected near the tunnel project area was highly capable of adsorbing arsenate (As[V]), Pb, Cu and Zn. Under column conditions, the amount of hazardous elements released from the rock increased by several folds and their breakthrough curves had flushing-out trends. The mechanisms of As and heavy metals release probably include the dissolution of soluble phases and pyrite oxidation. Addition of CaCO3 in the column experiments based on estimates from the batch results underestimated the amount of neutralizer needed to adjust the effluent pH to around 8, resulting only in slight increase of the pH. Nevertheless, the presence of CaCO3 drastically reduced the amount of hazardous elements released from the altered rock especially during the initial stages of the column experiments. Combining neutralization and adsorption effectively reduced the amount of As and heavy metals in the effluent throughout the duration of the column experiments, which is attributed to the slight neutralizing effect of volcanic ash that raised the pH around circumneutral as well as its rich Al and Fe oxyhydroxide/oxide contents. The combined system immobilized the hazardous elements through a combination of co-precipitation and adsorption reactions and showed potential as an alternative method for the disposal of altered rocks producing acidic leachate

Characterization and evaluation of arsenic and boron adsorption onto natural geologic materials, and their application in the disposal of excavated altered rock

Construction of tunnels in Hokkaido, Japan often excavates rocks containing substantial amounts of arsenic (As) and boron (B). When these rocks are exposed to the environment, As and B are leached out that could potentially contaminate the surrounding soil and groundwater. Natural geologic materials contain minerals like Al-/Feoxyhydroxides/oxides that have As and B adsorption capabilities. Because these materials are widespread and readily available, they could be utilized in the mitigation of As and B leached out from these sources. This paper describes the ability of three natural geologic materials (i.e., pumiceous tuffs, partly-weathered volcanic ashes and coastal marine sediments) to sequester As and B from aqueous solutions and the actual leachate of a hydrothermally altered rock. The adsorption of As fitted well with either the Langmuir or Freundlich isotherm while that of B followed the Henry-type model (linear). Among the samples, those containing substantial amorphous Al and Fe exhibited higher As adsorption. However, the distribution coefficient of B only had a moderate positive correlation with these amorphous phases. The best adsorbent among these natural geologic materials was utilized in the adsorption layer of the column experiments. Adsorption of As was more effective the thicker the adsorption layer, but this retardation was only temporary due to significant changes in the pH. In contrast, the adsorption layer only retarded the migration of B to a limited extent

Effects of Environmental Factors on the Leaching and Immobilization Behavior of Arsenic from Mudstone by Laboratory and In Situ Column Experiments

Hydrothermally altered rocks generated from underground/tunnel projects often produce acidic leachate and release heavy metals and toxic metalloids, such as arsenic (As). The adsorption layer and immobilization methods using natural adsorbents or immobilizer as reasonable countermeasures have been proposed. In this study, two sets of column experiments were conducted, of which one was focused on the laboratory columns and other on the in situ columns, to evaluate the effects of column conditions on leaching of As from excavated rocks and on adsorption or immobilization behavior of As by a river sediment (RS) as a natural adsorbent or immobilizer. A bottom adsorption layer consisting of the RS was constructed under the excavated rock layer or a mixing layer of the excavated rock and river sediment was packed in the column. The results showed that no significant trends in the adsorption and immobilization of As by the RS were observed by comparing laboratory and in situ column experiments because the experimental conditions did not influence significant change in the leachate pH which affects As adsorption or immobilization. However, As leaching concentrations of the in situ experiments were higher than those of the laboratory column experiments. In addition, the lower pH, higher Eh and higher coexisting sulfate ions of the leachate were observed for the in situ columns, compared to the results of the laboratory columns. These results indicate that the leaching concentration of As became higher in the in situ columns, resulting in higher oxidation of sulfide minerals in the rock. This may be due to the differences in conditions, such as temperature and water content, which induce the differences in the rate of oxidation of minerals contained in the rock. On the other hand, since the leachate pH affecting As adsorption or immobilization was not influenced significantly, As adsorption or immobilization effect by the RS were effective for both laboratory and in situ column experiments. These results indicate that both in situ and laboratory column experiments are useful in evaluating leaching and adsorption of As by natural adsorbents, despite the fact that the water content which directly affects the rate of oxidation is sensitive to weathering conditions

Oosporein Produced by Root Endophytic <i>Chaetomium cupreum</i> Promotes the Growth of Host Plant, <i>Miscanthus sinensis</i>, under Aluminum Stress at the Appropriate Concentration

Chaetomium cupreum, a root endophyte in Miscanthus sinensis, enhances Al tolerance in M. sinensis by changing aluminum (Al) localization and the production of a siderophore, oosporein, which chelates Al for detoxification. Oosporein has various functions, including insecticidal activity, phytotoxicity, antifungal activity, and a siderophore. In our study, we focused on the detoxification effect of oosporein as a siderophore and on the growth of M. sinensis under Al exposure. In addition, the phytotoxicity of oosporein to M. sinensis was confirmed to compare with those in Lactuca sativa and Oryza sativa as control plants. Under Al stress, oosporein promoted plant growth in M. sinensis seedlings at 10 ppm, which was the same concentration as that detected in M. sinensis roots infected with C. cupreum in our previous study. Oosporein also showed low phytotoxicity to M. sinensis compared with L. sativa at even high concentrations of oosporein. These results suggest that the concentration of oosporein in M. sinensis roots would be maintained at the appropriate concentration to detoxify Al and would promote M. sinensis growth under Al stress, although oosporein would show low phytotoxicity to the natural host plant, M. sinensis, compared with the non-host plant, L. sativa

Oosporein Produced by Root Endophytic Chaetomium cupreum Promotes the Growth of Host Plant, Miscanthus sinensis, under Aluminum Stress at the Appropriate Concentration

Chaetomium cupreum, a root endophyte in Miscanthus sinensis, enhances Al tolerance in M. sinensis by changing aluminum (Al) localization and the production of a siderophore, oosporein, which chelates Al for detoxification. Oosporein has various functions, including insecticidal activity, phytotoxicity, antifungal activity, and a siderophore. In our study, we focused on the detoxification effect of oosporein as a siderophore and on the growth of M. sinensis under Al exposure. In addition, the phytotoxicity of oosporein to M. sinensis was confirmed to compare with those in Lactuca sativa and Oryza sativa as control plants. Under Al stress, oosporein promoted plant growth in M. sinensis seedlings at 10 ppm, which was the same concentration as that detected in M. sinensis roots infected with C. cupreum in our previous study. Oosporein also showed low phytotoxicity to M. sinensis compared with L. sativa at even high concentrations of oosporein. These results suggest that the concentration of oosporein in M. sinensis roots would be maintained at the appropriate concentration to detoxify Al and would promote M. sinensis growth under Al stress, although oosporein would show low phytotoxicity to the natural host plant, M. sinensis, compared with the non-host plant, L. sativa

Leaching and Adsorption Behavior of Arsenic and Selenium from Excavated Mudstones Considering Their Chemical Species

Rocks generated from tunnel construction projects for roads and railways throughout Japan have often leached out hazardous trace elements, such as arsenic (As) and selenium (Se). In nature, the oxyanionic species of As and Se have a variety of chemical species, so speciation is one of the crucial factors in their migration through natural geologic media. In this study, column experiments consisting of four types of crushed rock samples containing As and Se, and a river sediment (RS) as an adsorbent obtained near the tunnel construction site were conducted to evaluate the leaching and adsorption behavior of arsenite (As (III) ), arsenate (As (V) ), selenite (Se (IV) ), and selenate (Se (VI) ). The results showed that the dominant speciation of As and Se in the effluent from the rock layer was As (V) and Se (VI), and that the addition of a bottom RS adsorption layer or the mixing of RS with the rock layer decreased the leaching concentrations of As (III), As (V), Se (IV), and Se (VI). Cumulative leachability (CL) for each speciation through the column experiments was calculated to evaluate the amounts of As and Se retained in RS. The calculated CL showed that the bottom RS layer or mixing of RS with the rock reduced the CL of As (III), As (V), Se (IV), and Se (IV) ranging from 60 to 89%, 73 to 89%, 9 to 75%, and 36 to 60%, respectively; however, mixing of RS with the rock layer was ineffective in decreasing CL of Se (VI). The reduction of CL may be due to adsorption and/or coprecipitation by iron and/or aluminum oxides contained in RS. These results indicated that utilization of RS for the bottom adsorption layer was effective in reducing As and Se concentrations irrespective of their speciation, although that of mixed with rock layer was effective only in reducing As concentrations irrespective of their speciation