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.

Simultaneous leaching of arsenite, arsenate, selenite and selenate, and their migration in tunnel-excavated sedimentary rocks: II. Kinetic and reactive transport modeling.

Predicting the fates of arsenic (As) and selenium (Se) in natural geologic media like rocks and soils necessitates the understanding of how their various oxyanionic species behave and migrate under dynamic conditions. In this study, geochemical factors and processes crucial in the leaching and transport of arsenite (AsIII), arsenate (AsV), selenite (SeIV) and selenate (SeVI) in tunnel-excavated rocks of marine origin were investigated using microscopic/extraction techniques, column experiments, dissolution-precipitation kinetics and one-dimensional reactive transport modeling. The results showed that evaporite salts were important because aside from containing As and Se, they played crucial roles in the evolution of pH and concentrations of coexisting ions, both of which had strong effects on adsorption-desorption reactions of As and Se species with iron oxyhydroxide minerals/phases. The observed leaching trends of AsV, AsIII, SeIV and SeVI were satisfactorily simulated by one-dimensional reactive transport models, which predict that preferential adsorptions of AsV and SeIV were magnified by geochemical changes in the columns due to water flow. Moreover, our results showed that migrations of AsIII, SeIV and SeVI could be predicted adequately by 1D solute transport with simple activity-K'd approach, but surface complexation was more reliable to simulate adsorption-desorption behavior of AsV.

Reproducibility of up-flow column percolation tests for contaminated soils.

Up-flow column percolation tests are used at laboratory scale to assess the leaching behavior of hazardous substance from contaminated soils in a specific condition as a function of time. Monitoring the quality of these test results inter or within laboratory is crucial, especially if used for Environment-related legal policy or for routine testing purposes. We tested three different sandy loam type soils (Soils I, II and III) to determine the reproducibility (variability inter laboratory) of test results and to evaluate the difference in the test results within laboratory. Up-flow column percolation tests were performed following the procedure described in the ISO/TS 21268-3. This procedure consists of percolating solution (calcium chloride 1 mM) from bottom to top at a flow rate of 12 mL/h through softly compacted soil contained in a column of 5 cm diameter and 30 ± 5 cm height. Eluate samples were collected at liquid-to-solid ratio of 0.1, 0.2, 0.5, 1, 2, 5 and 10 L/kg and analyzed for quantification of the target elements (Cu, As, Se, Cl, Ca, F, Mg, DOC and B in this research). For Soil I, 17 institutions in Japan joined this validation test. The up-flow column experiments were conducted in duplicate, after 48 h of equilibration time and at a flow rate of 12 mL/h. Column percolation test results from Soils II and III were used to evaluate the difference in test results from the experiments conducted in duplicate in a single laboratory, after 16 h of equilibration time and at a flow rate of 36 mL/h. Overall results showed good reproducibility (expressed in terms of the coefficient of variation, CV, calculated by dividing the standard deviation by the mean), as the CV was lower than 30% in more than 90% of the test results associated with Soil I. Moreover, low variability (expressed in terms of difference between the two test results divided by the mean) was observed in the test results related to Soils II and III, with a variability lower than 30% in more than 88% of the cases for Soil II and in more than 96% of the cases for Soil III. We also discussed the possible factors that affect the reproducibility and variability in the test results from the up-flow column percolation tests. The low variability inter and within laboratory obtained in this research indicates that the ISO/TS 21268-3 can be successfully upgraded to a fully validated ISO standard.

Short and long term release mechanisms of arsenic, selenium and boron from a tunnel-excavated sedimentary rock under in situ conditions.

Sedimentary rocks of marine origin excavated from tunnel construction projects usually contain background levels of hazardous trace elements, but when exposed to the environment, they generate leachates with concentrations of arsenic (As), selenium (Se) and boron (B) exceeding the WHO guideline for drinking water. In this study, the leaching of As, Se and B was evaluated under in situ conditions at various flow patterns, particle size distributions and column thicknesses. The results showed that these trace elements were leached out of the rock via short and long term mechanisms. In the short term, all three elements were rapidly and simultaneously released due to the dissolution of soluble evaporite salts formed from entrapped sea water of the Cretaceous. After their rapid release, however, these trace elements behaved differently as a result of their contrasting adsorption affinities onto minerals like clays and Fe-oxyhydroxides, which were further influenced by the pH, presence of coexisting ions and speciation of the trace elements. Selenium was quickly and easily transported out of the columns because it was mostly present as the very mobile selenate ion (Se[VI]). In comparison, the migration of As and B was hindered by adsorption reactions onto mineral phases of the rock. Boron was initially the least mobile among the three because of its preferential adsorption onto clay minerals that was further enhanced by the slightly alkaline pH and high concentrations of Ca(2+) and Na(+). However, it was gradually re-mobilized in the latter part of the experiments because it was only weakly adsorbed via outer sphere complexation reactions. In the long term, the rock continued to release substantial amounts of As, Se and B via pyrite oxidation and adsorption/desorption reactions, which were regulated by the temperature and rainfall intensity/frequency on site.