No abstract

Since 1970, a series of systematic investigations have been performed on three modes of moving reaction boundaries (MRBs), viz. moving precipitate boundary (MPB), moving neutralization boundary (MNB) and moving chelation boundary (MCB). So far, there has not been any review on them. Herein, we firstly review the MPB with respect to its velocity, product concentration, elution displacement, stacking effect, separation effect, judgment expressions and related procedures. We then make a review on the MNB about its theory, demonstration, improvement, and uses in isoelectric focusing (IEF), sample stacking, MNB-based stacking mechanisms and relevant computer simulations. We further give a review on the MCB regarding the relevant theory, verifications, and applications in EDTA-based sweeping and computer simulation. Finally, we give an outlook on the MRB study. More than 150 references are cited.

Land application of biochar is increasingly being considered for potential agronomic and environmental benefits, e.g., enhancing carbon sequestration, nutrient retention, water holding capacity, and crop productivity; and reducing greenhouse gas emissions and bioavailability of environmental contaminants. However, little is known about the transport of biochar particles in the aqueous environment, which represents a critical knowledge gap because biochar particles can facilitate the transport of adsorbed contaminants. In this study, column experiments were conducted to investigate biochar particle transport and retention in water-saturated quartz sand. Specific factors considered included biochar feedstocks (wheat straw and pine needle), pyrolysis temperature (350 and 550 °C), and particle size (micrometer-particle (MP) and nanoparticle (NP)). Greater mobility was observed for the biochars of lower pyrolysis temperatures and smaller particle sizes. Extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) calculations that considered measured zeta potentials and Lewis acid-base interactions were used to better understand the influence of pyrolysis temperature on biochars particle transport. Most biochars exhibited attractive acid-base interactions that impeded their transport, whereas the biochar with the greatest mobility had repulsive acid-base interaction. Nonetheless, greater retention of the MPs than that of the NPs was in contrast with the XDLVO predictions. Straining and biochar surface charge heterogeneity were found to enhance the retention of biochar MPs, but played an insignificant role in the biochar NP retention. Experimental breakthrough curves and retention profiles were well-described using a two-site kinetic retention model that accounted for depth-dependent retention at one site. Modeled first-order retention coefficients on both sites 1 and 2 increased with increasing pyrolysis temperature and particle size.

Removal of arsenic (As) from water supplies is needed to reduce As exposure through drinking water and food consumption in many regions of the world. Magnetite nanoparticles (MNPs) are promising and novel adsorbents for As removal because of their great adsorption capacity for As and easy separation. This study aimed to investigate the adsorption mechanism of arsenate, As(V), and arsenite, As(III), on MNPs by macroscopic adsorption experiments in combination with thermodynamic calculation and microspectroscopic characterization using synchrotron-radiation-based X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Adsorption reactions are favorable endothermic processes as evidenced by increased adsorption with increasing temperatures, and high positive enthalpy change. EXAFS spectra suggested predominant formation of bidentate binuclear corner-sharing complexes ((2)C) for As(V), and tridentate hexanuclear corner-sharing ((3)C) complexes for As(III) on MNP surfaces. The macroscopic and microscopic data conclusively identified the formation of inner-sphere complexes between As and MNP surfaces. More intriguingly, XANES and XPS results revealed complex redox transformation of the adsorbed As on MNPs exposed to air: Concomitant with the oxidation of MNPs, the oxidation of As(III) and MNPs was expected, but the observed As(V) reduction was surprising because of the role played by the reactive Fe(II).

No abstract

Little is known about how low levels of surfactants can affect the colloidal stability of single-walled carbon nanotubes (SWNTs) and how surfactant-wrapping of SWNTs can impact ecological exposures in aqueous systems. In this study, SWNTs were suspended in water with sodium dodecylsulfate (SDS) as a surface-active dispersing agent. The effect of SDS concentration on SWNT suspension stability was investigated with time-resolved dynamic light scattering (TRDLS) initial aggregation studies utilizing both monovalent (Na(+)) and divalent (Ca(2+)) cations. The critical coagulation concentration (CCC) values increased with SDS concentration for the Na(+) treatments, but the Ca(2+) treatments were less sensitive to SDS concentration changes. Longer term stability studies with SDS concentrations orders of magnitude below the SDS critical micelle concentration demonstrated that SWNTs remained suspended for over six weeks in a surface water. Transport studies in a freshwater sediment similarly showed a SDS concentration-dependent mobility of SDS-wrapped SWNTs in that SWNTs showed a relatively greater retention at lower SDS concentrations (0.001%-0.05% w/v) than at a higher SDS concentration (0.1%). It is hypothesized that the stability and mobility of SWNT suspensions is directly related to the surface coverage of SDS on the SWNT surface that simultaneously increases electrosteric repulsion and decreases surface chemical heterogeneity. Overall, these studies demonstrate that low levels of surfactant are effective in stabilizing and mobilizing SWNTs in environmental media.

No abstract

Colloids play an important role in facilitating transport of adsorbed contaminants in soils. Recent studies showed that under saturated conditions colloid retention was a function of its concentration. It is unknown if this is the case under unsaturated conditions. In this study, the effect of colloid concentration on colloid retention was investigated in unsaturated columns by increasing concentrations of colloid influents with varying ionic strength. Colloid retention was observed in situ by bright field microscopy and quantified by measuring colloid breakthrough curves. In our unsaturated experiments, greater input concentrations resulted in increased colloid retention at ionic strength above 0.1 mM, but not in deionized water (i.e., 0 mM ionic strength). Bright field microscope images showed that colloid retention mainly occurred at the solid-water interface and wedge-shaped air-water-solid interfaces, whereas the retention at the grain-grain contacts was minor. Some colloids at the air-water-solid interfaces were rotating and oscillating and thus trapped. Computational hydrodynamic simulation confirmed that the wedge-shaped air-water-solid interface could form a "hydrodynamic trap" by retaining colloids in its low velocity vortices. Direct visualization also revealed that colloids once retained acted as new retention sites for other suspended colloids at ionic strength greater than 0.1 mM and thereby could explain the greater retention with increased input concentrations. Derjaguin-Landau-Verwey-Overbeek (DLVO) energy calculations support this concept. Finally, the results of unsaturated experiments were in agreement with limited saturated experiments under otherwise the same conditions.