Deciphering and Predicting Microscale Controls on Radon Production in Soils, Sediments and Rock

Soils, sediments and rock are natural sources of radon (Rn), which poses an ongoing threat to human health. Numerous studies have measured Rn release from bulk earth materials, yet few have examined microscale controls on Rn flux from solids (emanation), which is required to develop a process-based framework for predicting the rate and extent of production. Here, we use a novel closed loop flow-through system to measure Rn emanation from two crushed rock types with disparate physical and geochemical characteristics, shale and granitic pegmatite. We relate the extent of Rn emanation from each sample to microscale characteristics examined using conventional and synchrotron-based techniques, such as Rn parent radionuclide distribution within mineral grains, porosity, and surface area. Our results illustrate that the extent of Rn release from solids is primarily dependent on the position of parent radionuclides within host mineral grains relative to the “recoil range”—the maximum distance a daughter product (such as Rn) may traverse within a solid and into an adjacent pore owing to alpha-recoil—and is less dependent on the bulk parent radionuclide (e.g., radium) activity. We also present a simple model for predicting the emanation coefficient for pure solids based on mineralogical and physical parameters, which is an initial step toward developing a framework for predicting Rn efflux (exhalation) from soils. Keywords: radon; emanation; alpha-recoil; modeling; microscale characteristic

Calibration and assessment of electrochemical air quality sensors by co-location with regulatory-grade instruments

The use of low-cost air quality sensors for air pollution research has outpaced our understanding of their capabilities and limitations under real-world conditions, and there is thus a critical need for understanding and optimizing the performance of such sensors in the field. Here we describe the deployment, calibration, and evaluation of electrochemical sensors on the island of Hawai'i, which is an ideal test bed for characterizing such sensors due to its large and variable sulfur dioxide (SO 2 ) levels and lack of other co-pollutants. Nine custom-built SO 2 sensors were co-located with two Hawaii Department of Health Air Quality stations over the course of 5 months, enabling comparison of sensor output with regulatory-grade instruments under a range of realistic environmental conditions. Calibration using a nonparametric algorithm (k nearest neighbors) was found to have excellent performance (RMSE 0.997) across a wide dynamic range in SO 2 ( 2ppm). However, since nonparametric algorithms generally cannot extrapolate to conditions beyond those outside the training set, we introduce a new hybrid linear-nonparametric algorithm, enabling accurate measurements even when pollutant levels are higher than encountered during calibration. We find no significant change in instrument sensitivity toward SO 2 after 18 weeks and demonstrate that calibration accuracy remains high when a sensor is calibrated at one location and then moved to another. The performance of electrochemical SO 2 sensors is also strong at lower SO 2 mixing ratios ( < 25ppb), for which they exhibit an error of less than 2.5ppb. While some specific results of this study (calibration accuracy, performance of the various algorithms, etc.) may differ for measurements of other pollutant species in other areas (e.g., polluted urban regions), the calibration and validation approaches described here should be widely applicable to a range of pollutants, sensors, and environments.United States. Environmental Protection Agency (Grant RD-83618301

Geochemical conditions conducive for retention of trace elements and radionuclides during shale–fluid interactions

Produced water generated during unconventional oil and gas extractions contains a complex milieu of natural and anthropogenic potentially toxic chemical constituents including arsenic (As), chromium (Cr), and cadmium (Cd), naturally occurring radioactive materials (NORMs) including U and Ra, and a myriad of organic compounds. The human-ecological health risks and challenges associated with the disposal of produced water may be alleviated by understanding geochemical controls on processes responsible for the solubilization of potentially hazardous natural shale constituents to produced water. Here, we investigated, through a series of batch treatments, the leaching behavior of As, Se, Cu, Fe, Ba, Cr, Cd, and radioactive nuclides U, Ra from shale to produced water. Specifically, the effect of four major controls on element mobility was studied: (1) solution pH, (2) ionic strength of the solution, (3) oxic–anoxic conditions, and (4) an additive used in fracking fluid. The mobilization of metals and metalloids from shale was greatest in treatments containing sodium persulfate, an oxidant and a commonly used additive in fracture fluid. In the high ionic strength treatments, dissolved Ba concentrations increased 5-fold compared to low ionic strength treatments. Overall, anoxic conditions superimposed with low pH resulted in the largest increase of dissolved metals and radionuclides such as Ra. Overall, our results suggest that (1) limiting pore water acidification by injection of alkaline fluid in carbonate-low shale and (2) minimizing strong oxidizing conditions in shale formations may result in cost-effective in situ retention of produced water contaminants

Calibration and assessment of electrochemical air quality sensors by co-location with reference-grade instruments

The use of low-cost air quality sensors for air pollution research has outpaced our understanding of their capabilities and limitations under real-world conditions, and there is thus a critical need for understanding and optimizing the performance of such sensors in the field. Here we describe the deployment, calibration, and evaluation of electrochemical sensors on the island of Hawai`i, which is an ideal test bed for characterizing such sensors due to its large and variable sulfur dioxide (SO₂) levels and lack of other co-pollutants. Nine custom-built SO₂ sensors were co-located with two Hawaii Department of Health Air Quality stations over the course of 5 months, enabling comparison of sensor output with regulatory-grade instruments under a range of realistic environmental conditions. Calibration using a nonparametric algorithm (k nearest neighbors) was found to have excellent performance (RMSE  0.997) across a wide dynamic range in SO₂ ( 2 ppm). However, since nonparametric algorithms generally cannot extrapolate to conditions beyond those outside the training set, we introduce a new hybrid linear–nonparametric algorithm, enabling accurate measurements even when pollutant levels are higher than encountered during calibration. We find no significant change in instrument sensitivity toward SO₂ after 18 weeks and demonstrate that calibration accuracy remains high when a sensor is calibrated at one location and then moved to another. The performance of electrochemical SO₂ sensors is also strong at lower SO₂ mixing ratios (< 25 ppb), for which they exhibit an error of less than 2.5 ppb. While some specific results of this study (calibration accuracy, performance of the various algorithms, etc.) may differ for measurements of other pollutant species in other areas (e.g., polluted urban regions), the calibration and validation approaches described here should be widely applicable to a range of pollutants, sensors, and environments