Impact of Physico-Chemical Heterogeneity on Arsenic Sorption and Reactive Transport under Water Extraction.

Heterogeneity in physical and chemical properties is a common characteristic in a subsurface environment. This study investigated the effect of physico-chemical heterogeneity on arsenic (As) sorption and reactive transport under water extraction in a layered system with preferential flow paths. A flume experiment was performed to derive the spatio-temporal data of As reactive transport. The results indicated that the heterogeneous system significantly accelerated downward (vertical direction) As migration as a coupled effect of physical and chemical heterogeneity that led to fast As transport with low As sorption along the preferential flow paths. The results also indicated that such a heterogeneity effect was driven by water extraction that enhanced the downward groundwater flow along the preferential flow paths. Numerical simulations were performed by matching the experimental results to provide insights into the dominant processes controlling the As migration in the heterogeneous systems. The simulation results highlighted the importance of the kinetic oxidation of mineral-bonded Fe(II) to Fe(III) in the clay matrix that dynamically increased As sorption affinity and retarded As reactive transport. A coupled model of reactive transport along the preferential flow paths, sorption-retarded diffusion from the preferential flow paths into the clay matrixes, and reactions that change sorption affinity in the matrix was required to describe the As reactive transport systems with physico-chemical heterogeneities. The results have strong implications for understanding and modeling As downward migration from shallow to deep aquifers under groundwater pumping conditions in field systems with inherent heterogeneity.

Effects of geochemical and hydrodynamic transiency on desorption and transport of As in heterogeneous systems.

Spatial and temporal variations in groundwater As concentrations are mainly caused by changes in geochemical and hydrodynamic conditions. In this study, the effects of geochemical and hydrodynamic transiency on As desorption and transport in a layered heterogeneous system with preferential flow paths during continuous or intermittent water extraction were investigated. A flume desorption experiment was performed after an adsorption experiment lasting 99 d with competitive adsorption anions (phosphate) in the influent. The results indicated that although competitive adsorption between As and phosphate at the water/solid interface significantly promoted As desorption from solid materials, marked amounts of As desorbed slowly or were on irreversible sorption sites in the system. As adsorbed by the sand and clay near the preferential flow paths was preferentially released, while the release of As from the interiors of the clay zones was limited by diffusion. Water extraction accelerated As transport between the different layers, and this increased the overall rate of As release from zones limited by diffusion. Desorption rate of As in the layered system was fast initially, followed by a period of slow desorption rate that lasted months. The desorption hysteresis was due to slow desorption controlled by diffusion. The results provide important insights for understanding and modeling As desorption and transport in field systems.

Dynamics of dissolved organic matter and dissolved organic nitrogen during anaerobic/anoxic/oxic treatment processes.

With Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) and fluorescence spectroscopy, this study investigated the transformation of dissolved organic matter (DOM) and nitrogen (DON) during the widely-applied anaerobic/anoxic/oxic (A2O) processes to provide molecular insights into the removal, generation, and reduction of DOM/DON species in different biological treatment units. Results indicated that the anaerobic process decomposed the macromolecules of influent DOM/DON and decreased their mass. The anoxic process denitrified DON and generated DOM, as indicated by the decreased molecule number of CHON and CHONS and the increased CHO and CHOS species, as well as the increased overall DOM intensities. DOM mineralization and ammonia nitrogen-DON conversion occurred in the oxic process. Aromaticity and unsaturation degree increased slightly after the A2O processes, which was correlated with the relative abundance of Proteobacteria (positively) and Bacteroidetes (negatively). The results have strong implications to the understanding of DOM/DON dynamics in wastewater treatment plants.