Mahmoud Wazne

Influence of Ca2+ and Suwannee River Humic Acid on aggregation of silicon nanoparticles in aqueous media

Silicon nanoparticles (NPs) have potential applications in many fields including microelectronics, biomedical imaging, and most recently energetics. Even though silicon NPs are thought to be harmless, their full impact on the environment and human health needs further investigation due to their potential increased use and recent toxicity data. Various techniques were used to characterize silicon NPs that are being considered for use in energetics. These techniques included dynamic light scattering (DLS), electron microscopy (EM), X-ray diffraction (XRD) and atomic force microscopy (AFM). Experiments were also conducted on the early stage aggregation kinetics of silicon NPs in the presence of Ca(2+) and Suwannee River Humic Acid (SRHA). The addition of SRHA in the presence of Ca(2+) resulted in increased attachment efficiencies and decreased critical coagulation concentration (from 0.4 to 0.1M). The enhanced aggregation was attributed to bridging generated by SRHA aggregates as evidenced by selected area electron diffraction (SAED) and energy dispersive spectroscopy (EDS). SAED verified the bridging to be amorphous phase comprised of humic substances rather than artifacts of silicon crystallites. Element distribution analyses were also used in the delineation of the silicon NP aggregation mechanisms in the absence and presence of SRHA.

Effects of natural organic matter on aggregation kinetics of boron nanoparticles in monovalent and divalent electrolytes

Nano boron is a promising new propellant being considered for military and civilian applications; however, the impact of its release on the environment is largely not known. The early stage aggregation kinetics of boron nanoparticles was investigated in the presence of two kinds of natural organic matter-Suwannee River humic acid (SRHA) and sodium alginate-by dynamic light scattering and transmission electron microscopy (TEM). The addition of SRHA caused the boron nanoparticles to stabilize and resulted in (1) decreased attachment efficiency for the reaction-controlled regime and (2) an increase in the critical coagulation concentration, in CaCl(2) and MgCl(2) solutions. The increase in the electrostatic repulsion is suggested as a main cause of the induced stabilization as indicated by the electrophoretic mobility measurements. Similar behavior was observed in the presence of alginate and MgCl(2). However, the attachment efficiency kept increasing in the presence of CaCl(2) and alginate with the increase in the electrolyte concentration and was greater than unity at>4mM CaCl(2). The destabilization was attributed to bridging of the nanoparticles by the alginate-Ca(2+) system. Results from this study suggest that various NOM and electrolytes play significant and differing roles in the aggregation of boron nanoparticles in natural aquatic environments.

Assessment of cement kiln dust (CKD) for stabilization/solidification (S/S) of arsenic contaminated soils.

A stabilization/solidification (S/S) process for arsenic (As) contaminated soils was evaluated using cement kiln dust (CKD). Laboratory-prepared slurries, made of either kaolinite or montmorillonite, and field soils spiked with either As(3+) or As(5+) were prepared and treated with CKD ranging from 10 to 25 wt%. Sodium arsenite and sodium arsenate at 0.1 wt% were used to simulate arsenite (As(3+)) and arsenate (As(5+)) source contamination in soils, respectively. The effectiveness of treatment was evaluated at curing periods of 1- and 7-days based on the toxicity characteristic leaching procedure (TCLP). As-CKD and As-clay-CKD slurries were also spiked at 10 wt% to evaluate As immobilization mechanism using X-ray powder diffraction (XRPD) analyses. Overall, the TCLP results showed that only the As(5+) concentrations in kaolinite amended with 25 wt% CKD after 1 day of curing were less than the TCLP regulatory limit of 5mg/L. Moreover, at 7 days of curing, all As(3+) and As(5+) concentrations obtained from kaolinite soils were less than the TCLP criteria. However, none of the CKD-amended montmorillonite samples satisfied the TCLP-As criteria at 7 days. Only field soil samples amended with 20 wt% CKD complied with the TCLP criteria within 1 day of curing, where the source contamination was As(5+). XRPD and scanning electron microscopy (SEM)-energy dispersive X-ray spectroscopy (EDX) results showed that Ca-As-O and NaCaAsO(4).7.5H(2)O were the primary phases responsible for As(3+) and As(5+) immobilization in the soils, respectively.

Aggregation and deposition behavior of boron nanoparticles in porous media

New kinds of solid fuels and propellants comprised of nanomaterials are making their way into civilian and military applications yet the impact of their release on the environment remains largely unknown. One such material is nano boron, a promising solid fuel and propellant. The fate and transport of nano boron under various aquatic systems was investigated in aggregation and deposition experiments. Column experiments were performed to examine the effects of electrolyte concentration and flow velocity on the transport of boron nanoparticles under saturated conditions, whereas aggregation tests were conducted to assess the effects of electrolytes on the aggregation of the boron nanoparticles. Aggregation tests indicated the presence of different reaction-controlled and diffusion-controlled regimes and yielded critical coagulation concentrations (CCC) of 200 mM, 0.7 mM and 1.5 mM for NaCl, CaCl(2), and MgCl(2), respectively. Aggregation and deposition experimental data corresponded with the classic Derjaguin-Landau-Verwey-Overbeek (DLVO) model and the constant attachment efficiency filtration model, respectively. Theoretical calculations indicated that both the primary and secondary energy minima play important roles in the deposition of nano boron in sand columns.

Application of an empirical transport model to simulate retention of nanocrystalline titanium dioxide in sand columns

Nanocrystalline titanium dioxide was injected into sand columns to simulate subsurface injection for creation of a permeable treatment barrier. Past usage of this material as an ex situ pilot scale treatment filter has shown that it has a high adsorption capacity for a number of heavy metals and therefore would be a good candidate for injection technology. Three suspension concentrations (50, 75 and 100 mg l(-1)) were pumped through packed sand columns at different flow velocities (3.0, 6.8 and 14.1 cm min(-1)). Little to no particles was detected in the effluent. Most of the nanoparticles remained in the sand columns, with an increasing then decreasing retained solids pattern. Application of a one-dimensional advection-dispersion flow model, that included two empirical kinetic terms to account for particle retention in the porous media, produced data fits that followed the general trend of the data, but did not truly capture the concentration maxima in the data sets. Discussion of these results highlights the limited ability of existing models to aid in predicting particle retention of non-ideal materials for engineering purposes.

Effects of particle size and acid addition on the remediation of chromite ore processing residue using ferrous sulfate

A bench-scale treatability study was conducted to assess the effects of particle size and acid addition on the remediation of chromite ore processing residue (COPR) using ferrous sulfate. The remediation scheme entailed the chemical reduction of hexavalent chromium [Cr(VI)] and the mitigation of swell potential. Leaching tests and the EQ3/6 geochemical model were used to estimate the acid dosage required to destabilize Cr(VI)-bearing and swell-causing minerals. The model predicted greater acid dosage than that estimated from the batch leaching tests. This indicated that mass transfer limitation may be playing a significant role in impeding the dissolution of COPR minerals following acid addition and hence hindering the remediation of COPR. Cr(VI) concentrations determined by alkaline digestion for the treated samples were less than the current NJDEP standard. However, Cr(VI) concentrations measured by X-ray absorption near edge structure (XANES) were greater than those measured by alkaline digestion. Greater Cr(VI) percentages were reduced for acid pretreated and also for smaller particle size COPR samples. Upon treatment, brownmillerite content was greatly reduced for the acid pretreated samples. Conversely, ettringite, a swell-causing mineral, was not observed in the treated COPR.

Leaching mechanisms of Cr(VI) from chromite ore processing residue.

Batch leaching tests, qualitative and quantitative x-ray powder diffraction (XRPD) analyses, and geochemical modeling were used to investigate the leaching mechanisms of Cr(VI) from chromite ore processing residue (COPR) samples obtained from an urban area in Hudson County, New Jersey. The pH of the leaching solutions was adjusted to cover a wide range between 1 and 12.5. The concentration levels for total chromium (Cr) and Cr(VI) in the leaching solutions were virtually identical for pH values >5. For pH values <5, the concentration of total Cr exceeded that of Cr(VI) with the difference between the two attributed to Cr(III). Geochemical modeling results indicated that the solubility of Cr(VI) is controlled by Cr(VI)-hydrocalumite and Cr(VI)-ettringite at pH >10.5 and by adsorption at pH <8. However, experimental results suggested that Cr(VI) solubility is controlled partially by Cr(VI)-hydrocalumite at pH >10.5 and by hydrotalcites at pH >8 in addition to adsorption of anionic chromate species onto inherently present metal oxides and hydroxides at pH <8. As pH decreased to <10, most of the Cr(VI) bearing minerals become unstable and their dissolution contributes to the increase in Cr(VI) concentration in the leachate solution. At low pH ( <1.5), Cr(III) solid phases and the oxides responsible for Cr(VI) adsorption dissolve and release Cr(III) and Cr(VI) into solution.

Particle size and pH effects on remediation of chromite ore processing residue using calcium polysulfide (CaS5)

A long-term bench scale treatability study was performed to assess the ability to remediate chromite ore processing residue (COPR) using calcium polysulfide (CaS(5)). COPR materials were characterized with respect to particle size, pH, curing period and mineralogy. A stoichiometric ratio of sulfide species to hexavalent chromium (Cr(6+)) of 2 was used for the long-term treatment of COPR. The effectiveness of CaS(5) treatment was assessed using the toxicity characteristic leaching procedure (TCLP), alkaline digestion, and X-ray absorption near edge structure (XANES) analyses. The formation of ettringite, known as a heaving agent, was investigated following the treatment of CaS(5), using X-ray powder diffraction (XRPD) and scanning electron microscopy (SEM) along with an energy dispersive X-ray spectroscopy (EDX). Overall, after a curing period of 18 months, the TCLP total chromium (Cr) and alkaline digestion (Cr(6+)) results obtained from the treatability study showed that the concentrations were lower than 5 mg L(-1) and 9 mg kg(-1), respectively. However, XANES results obtained from samples cured for 18 months showed that all of the treated samples had higher Cr(6+) concentrations than shown using alkaline digestion. The lowest XANES Cr(6+) concentration of 610.2 mg kg(-1) was obtained from the sample with a particle size less than 0.075 mm and a pH value of 9. Particle size reduction prior to the addition of the reductant, along with pH reduction was found to be strongly associated with the treatment performance. Ettringite formation, due to pH increase over time in the samples, where the initial pH was adjusted to 9, was verified by XRPD and SEM-EDX analyses, indicating that a pH less than 9 should be maintained to avoid ettringite formation.

Investigation of Barium Treatment of Chromite Ore Processing Residue (COPR) 031

Barium addition to chromite ore processing residue (COPR) was investigated in order to address (a) the pronounced heaving phenomena that are associated with mainly the presence of ettringite and (b) hexavalent chromium leaching. Sulfate was added to representative samples of grey-black (GB) and hard-brown (HB) COPR to simulate worst-case conditions of sulfate influx and ettringite formation. Both the X-ray powder diffraction (XRPD) and the modeling results showed that ettringite is a thermodynamically favored reaction in COPR. The subsequent addition of barium lead to the formation of both barite and barium chromate, observed as solid solution between the two phases. Modeling results confirmed that barium sulfate is the more stable species that will dissolve ettringite and that barium chromate will also dissolve COPR chromate phases when sulfate is depleted. The Toxicity Characteristic Leaching Procedure (TCLP) test on GB samples showed that the optimal stoichiometry to maintain Cr and Ba TCLP concentrations below the U.S. Environmental Protection Agency regulatory limit of 5 and 100 ppm, respectively, lies between 1:1 (Ba to sulfate plus chromate ratio) and 1.5:1. The respective optimal stoichiometry for the HB COPR was found to be higher, between 2:1 and 5:1. Considering that COPR is actually a Cr-contaminated cement form, a further area of research is the identification of barium-containing wastes (i.e., heavy-metal sludges, contaminated soils, etc.) that would be suitable for combination with COPR; in this way, an environmentally sustainable yet cost-effective treatment application can be realized.

Remediation of chromite ore processing residue using ferrous sulfate and calcium polysulfide

Batch tests were conducted to assess the potential use of ferrous sulfate and calcium polysulfide for the remediation of chromite ore processing residue (COPR). The remediation process entails addition of ferrous sulfate or calcium polysulfide to chemically reduce hexavalent chromium [Cr(VI)] to trivalent chromium [Cr(III)] in slurry form and pH adjustment to precipitate Cr(III) as chromium hydroxide. The present study investigates the effects of COPR particle size, treatment pH, and chemical dosage on the performance of the treatment. Smaller particle size resulted in increases in alkaline digestion and Toxicity Characteristic Leaching Procedure (TCLP) Cr(VI) concentrations for the untreated samples. The chemical reduction of Cr(VI) with ferrous iron and sulfides was non-stoichiometric. Four times the stoichiometric amount of ferrous iron of two times the stoichiometric amount of polysulfide were needed to meet both the New Jersey Department of Environmental Protection (NJDEP) regulatory limit of 240 mg/kg for Cr(VI) and EPA TCLP regulatory limit of 5 mg/L for chromium [C,r]. pH adjustment was necessary to prevent the formation of ettringite, a swell causing mineral, upon the introduction of sulfate to the COPR material via ferrous sulfate or calcium polysulfide. The slow hydration of some COPR minerals caused the pH of the treated COPR to creep upward during the curing period. However, when sufficient acid was added, the pH value was controlled at less than 9.27 for a curing period of 1.5 years, which prevented the formation of ettringite.