Amy T. Kan

The effect of nanocrystalline magnetite size on arsenic removal

Abstract Higher environmental standards have made the removal of arsenic from water an important problem for environmental engineering. Iron oxide is a particularly interesting sorbent to consider for this application. Its magnetic properties allow relatively routine dispersal and recovery of the adsorbent into and from groundwater or industrial processing facilities; in addition, iron oxide has strong and specific interactions with both As(III) and As(V). Finally, this material can be produced with nanoscale dimensions, which enhance both its capacity and removal. The objective of this study is to evaluate the potential arsenic adsorption by nanoscale iron oxides, specifically magnetite (Fe3O4) nanoparticles. We focus on the effect of Fe3O4 particle size on the adsorption and desorption behavior of As(III) and As(V). The results show that the nanoparticle size has a dramatic effect on the adsorption and desorption of arsenic. As particle size is decreased from 300 to 12 nm the adsorption capacities for both As(III) and As(V) increase nearly 200 times. Interestingly, such an increase is more than expected from simple considerations of surface area and suggests that nanoscale iron oxide materials sorb arsenic through different means than bulk systems. The desorption process, however, exhibits some hysteresis with the effect becoming more pronounced with small nanoparticles. This hysteresis most likely results from a higher arsenic affinity for Fe3O4 nanoparticles. This work suggests that Fe3O4 nanocrystals and magnetic separations offer a promising method for arsenic removal.

Adsorption/Desorption hysteresis in organic pollutant and soil/sediment interaction.

Adsorption and desorption of pollutants to soil and sediment materials are major fate mechanisms. The hypothesis that adsorption and desorption are reversible processes has been tested. The organic pollutants naphthalene, phenanthrene, and p-dichlorobenzene have been studied in the laboratory using batch reactors at room temperature from a few hours to over 2 months. The adsorption experiments were at equilibrium within 1-4 days and could be modeled using simple linear isotherms with K p values consistent with published K oc and K ow relationships. Desorption experiments were conducted with the contaminated sediments by successive dilutions

Transport of Fullerene Nanoparticles (nC60) in Saturated Sand and Sandy Soil: Controlling Factors and Modeling

Understanding subsurface transport of fullerene nanoparticles (nC(60)) is of critical importance for the benign use and risk management of C(60). We examined the effects of several important environmental factors on nC(60) transport in saturated porous media. Decreasing flow velocity from approximately 10 to 1 m/d had little effect on nC(60) transport in Ottawa sand (mainly pure quartz), but significantly inhibited the transport in Lula soil (a sandy, low-organic-matter soil). The difference was attributable to the smaller grain size, more irregular and rougher shape, and greater heterogeneity of Lula soil. Increasing ionic strength and switching background solution from NaCl to CaCl(2) enhanced the deposition of nC(60) in both sand and soil columns, but the effects were more significant for soil. This was likely because the clay minerals (and possibly soil organic matter) in soil responded to changes of ionic strength and species differently than quartz. Anions in the mobile phase had little effect on nC(60) transport, and fulvic acid in the mobile phase (5.0 mg/L) had a small effect in the presence of 0.5 mM Ca(2+). A two-site transport model that takes into account both the blocking-affected attachment process and straining effects can effectively model the breakthrough of nC(60).

pH-dependent effect of zinc on arsenic adsorption to magnetite nanoparticles.

UNLABELLED The effect of Zn(2+) on both the kinetic and equilibrium aspects of arsenic adsorption to magnetite nanoparticles was investigated at pH 4.5-8.0. At pH 8.0, adsorption of both arsenate and arsenite to magnetite nanoparticles was significantly enhanced by the presence of small amount of Zn(2+) in the solution. With less than 3 mg/L of Zn(2+) added to the arsenic solution prior to the addition of magnetite nanoparticles, the percentage of arsenic removal by magnetite nanoparticles increased from 66% to over 99% for arsenate, and from 80% to 95% for arsenite from an initial concentration of ∼100 μg/L As at pH 8.0. Adsorption rate also increased significantly in the presence of Zn(2+). The adsorption-enhancement effect of Zn(2+) was not observed at pH 4.5-6.0, nor with ZnO nanoparticles, nor with surface-coated Zn-magnetite nanoparticles. The enhanced arsenic adsorption in the presence of Zn(2+) cannot be due to reduced negative charge of the magnetite nanoparticles surface by zinc adsorption. Other cations, such as Ca(2+) and Ag(+), failed to enhance arsenic adsorption. Several potential mechanisms that could have caused the enhanced adsorption of arsenic have been tested and ruled out. Formation of a ternary surface complex by zinc, arsenic and magnetite nanoparticles is a possible mechanism controlling the observed zinc effect. Zinc-facilitated adsorption provides further advantage for magnetite nanoparticle-enhanced arsenic removal over conventional treatment approaches. SYNOPSIS Arsenic adsorption to magnetite nanoparticles at neutral or slightly basic pH can be significantly enhanced with trace amount of Zn(2+) due to the formation of a ternary complex.

Inhibition of calcium carbonate precipitation in NaCl brines from 25 to 90°C

Abstract The nucleation induction period of CaCO3 in NaCl brines in the absence and presence of scale inhibitors was experimentally measured at temperatures from 25 to 90°C. A semi-empirical mathematical inhibitor model is presented for the CaCO3 scale control in industrial processes based upon nucleation theory and experimental observations. Results show that the minimum inhibitor dosage (Cinh) may be obtained from: Cinh=f(s)/binh log [tinh/t0], where tinh is the inhibition time, e.g., 20 min, t0 is the nucleation induction period in the absence of inhibitors, binh is the inhibitor efficiency, and f(s) is the safety factor, e.g., 2. Important factors for the kinetics of both nucleation and inhibition have been incorporated in this model including the calcite saturation index (SI), temperature (T), and the molar ratio of Ca to HCO3 alkalinity (R). In this paper, model parameters are presented for commonly used inhibitors, including 1-hydroxyethylidene-1,1-diphosphonic-acid (HEDP) and nitrilotri(methylene phosphonic) acid (NTMP). Results show that HEDP and NTMP are the best inhibitors for calcite scaling in the systems examined.

Engineered nanoparticles for hydrocarbon detection in oil-field rocks

Polyvinyl alcohol functionalized oxidized carbon black efficiently carries a hydrophobic compound through a variety of oil-field rock types and releases the compound when the rock contains hydrocarbons.

Mechanisms of Mineral Scale Inhibition

An extensive study of adsorption and desorption isotherms of four phosphonates on barite or calcite are tested for a wide range of solution conditions (0 to I M NaCl, 0 to 0.1 M Ca, 0 to 0.33 M sulfate, and 4.6 to 6.4 pH). From these adsorption/desorption observations, it is proposed that the primary driving force for adsorption is related to simple hydrophobic repulsion from solution of a macroneutral molecule and not, as is generally presumed, some specific inhibitor-surface interaction. From the nucleation study, it is observed that the inhibitor needed to completely inhibit barite formation is approximately equal to 16% surface coverage. Air equation to predict minimum inhibitor need is proposed based on this model and is compared with field observations. The range of predicted inhibitor concentrations is quite similar to what is observed in the field as a minimum effective dose even though it was derived by a completely independent calculation method.

A sorption kinetics model for arsenic adsorption to magnetite nanoparticles

IntroductionArsenic is a well known water contaminant that causes toxicological and carcinogenic effects. In this work magnetite nanoparticles were examined as possible arsenic sorbents. The objective of this work was to develop a sorption kinetics model, which could be used to predict the amount of arsenic adsorbed by magnetite nanoparticles in the presence of naturally occurring species using a first-order rate equation, modified to include adsorption, described by a Langmuir isotherm.DiscussionArsenate and arsenite adsorption to magnetite nanoparticles was studied, including the effect of naturally occurring species (sulfate, silica, calcium magnesium, dissolved organic matter, bicarbonate, iron, and phosphate) on adsorption.ConclusionThe model accurately predicts adsorption to magnetite nanoparticles used in a batch process to remove arsenic from spiked Houston, TX tap water, and contaminated Brownsville, TX groundwater.

Scale Prediction and Inhibition for Oil and Gas Production at High Temperature/High Pressure

With the advance of new exploration and production technologies, oil and gas production has gone to deeper and tighter formations than ever before. These developments have also brought challenges in scale prediction and inhibition, such as the prevention of scale formation at high temperatures (150–200 C), pressures (1,000–1,500 bar), and total dissolved solids (TDS) (>300,000 mg/L) commonly experienced at these depths. This paper will discuss (1) the challenges of scale prediction at high temperatures, pressures, and TDS; (2) an efficient method to study the nucleation kinetics of scale formation and inhibition at these conditions; and (3) the kinetics of barite-crystal nucleation and precipitation in the presence of various scale inhibitors and the effectiveness of those inhibitors. In this study, nine scale inhibitors have been evaluated at 70–200 C to determine if they can successfully prevent barite precipitation. The results show that only a few inhibitors can effectively inhibit barite formation at 200 C. Although it is commonly believed that phosphonate scale inhibitors may not work for high-temperature inhibition applications, the results from this study suggest that barite-scale inhibition by phosphonate inhibitors was not impaired at 200 C under strictly anoxic condition in NaCl brine. However, phosphonate inhibitors can precipitate with Ca2þ at high temperatures and, hence, can reduce efficiency. In addition, the relationships of scale inhibition to types of inhibitors and temperature are explored in this study. This paper addresses the limits of the current predition of mineral solubility at high-temperature/high-pressure (HT/HP) conditions and sheds light on inhibitior selection for HT/HP application. The findings from this paper can be used as guidelines for applications in an HT/HP oilfield environment.

Highly stable carbon nanoparticles designed for downhole hydrocarbon detection

Sulfated polyvinyl alcohol functionalized carbon black, stable under high temperature and high salinity conditions, efficiently carries a hydrophobic compound through a variety of oil-field rock types and releases the compound when the rock contains hydrocarbons.