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M.J. Piana

Publications and source records attributed to M.J. Piana.

2 recordsLinked to original sources

Potential artifacts in interpretation of differential breakthrough of colloids and dissolved tracers in the context of transport in a zero-valent iron permeable reactive barrier

Many published studies have used visual comparison of the timing of peak breakthrough of colloids versus conservative dissolved tracers (hereafter referred to as dissolved tracers or tracers) in subsurface media to determine whether they are advected differently, and to elucidate the mechanisms of differential advection. This purely visual approach of determining differential advection may have artifacts, however, due to the attachment of colloids to subsurface media. The attachment of colloids to subsurface media may shift the colloidal peak breakthrough to earlier times, causing an apparent "faster" peak breakthrough of colloids relative to dissolve tracers even though the transport velocities for the colloids and the dissolved tracers may actually be equivalent. In this paper, a peak shift analysis was presented to illustrate the artifacts associated with the purely visual approach in determining differential advection, and to quantify the peak shift due to colloid attachment. This peak shift analysis was described within the context of microsphere and bromide transport within a zero-valent iron (ZVI) permeable reactive barrier (PRB) located in Fry Canyon, Utah. Application of the peak shift analysis to the field microsphere and bromide breakthrough data indicated that differential advection of the microspheres relative to the bromide occurred in the monitoring wells closest to the injection well in the PRB. It was hypothesized that the physical heterogeneity at the grain scale, presumably arising from differences in inter- versus intra-particle porosity, contributed to the differential advection of the microspheres versus the bromide in the PRB. The relative breakthrough (RB) of microspheres at different wells was inversely related to the ionic strength of ground water at these wells, in agreement with numerous studies showing that colloid attachment is directly related to solution ionic strength.

Ground Water↗

Mechanisms of uranium interactions with hydroxyapatite: Implications for groundwater remediation

The speciation of U(VI) sorbed to synthetic hydroxyapatite was investigated using a combination of U L III -edge XAS, synchrotron XRD, batch uptake measurements, and SEM-EDS. The mechanisms of U(VI) removal by apatite were determined in order to evaluate the feasibility of apatite-based in-situ permeable reactive barriers (PRBs). In batch U(VI) uptake experiments with synthetic hydroxyapatite (HA), near complete removal of dissolved uranium (>99.5%) to <0.05 μM was observed over a range of total U(VI) concentrations up to equimolar of the total P in the suspension. XRD and XAS analyses of U(VI)-reacted HA at sorbed concentrations ≤4700 ppm U(VI) suggested that uranium(VI) phosphate, hydroxide, and carbonate solids were not present at these concentrations. Fits to EXAFS spectra indicate the presence of Ca neighbors at 3.81 Å. U-Ca separation, suggesting that U(VI) adsorbs to the HA surfaces as an inner-sphere complex. Uranium(VI) phosphate solid phases were not detected in HA with 4700 ppm sorbed U(VI) by backscatter SEM or EDS, in agreement with the surface complexation process. In contrast, U(VI) speciation in samples that exceeded 7000 ppm sorbed U(VI) included a crystalline uranium(VI) phosphate solid phase, identified as chernikovite by XRD. At these higher concentrations, a secondary, uranium(VI) phosphate solid was detected by SEM-EDS, consistent with chernikovite precipitation. Autunite formation occurred at total U:P molar ratios ≥0.2. Our findings provide a basis for evaluating U(VI) sorption mechanisms by commercially available natural apatites for use in development of PRBs for groundwater U(VI) remediation.

Environmental Science & Technology↗