A SEM and X-ray study for investigation of solidified/stabilized arsenic-iron hydroxide sludge

Despite the fact that the solidification/stabilization of arsenic containing wastes with Portland cement and lime has an extensively documented history of use, the physical and chemical phenomena as a result of the interaction between arsenic and cement components have not been fully characterized. The study investigates the behavior of synthesized arsenic-iron hydroxide sludge, the by-product of arsenic removal by coagulation with ferric chloride, in solidified/stabilized matrices as well as its binding mechanisms by exploring the cementitious matrices in the micro-scale by scanning electron microscopy equipped with energy dispersive X-ray spectrometer (SEM-EDS). It was revealed that arsenic can be chemically fixed into cementitious environment of the solidified/stabilized matrices by three important immobilization mechanisms; sorption onto C-S-H surface, replacing SO4(2-) of ettringite, and reaction with cement components to form calcium-arsenic compounds, the solubility limiting phases.     

Effect of TCE concentration and dissolved groundwater solutes on NZVI-promoted TCE dechlorination and H2 evolution

Nanoscale zero-valent iron (NZVI) is used to remediate contaminated groundwater plumes and contaminant source zones. The target contaminant concentration and groundwater solutes (NO3-, Cl-, HCO3-, SO4(2-), and HPO4(2-)) should affect the NZVI longevity and reactivity with target contaminants, but these effects are not well understood. This study evaluates the effect of trichloroethylene (TCE) concentration and common dissolved groundwater solutes on the rates of NZVI-promoted TCE dechlorination and H2 evolution in batch reactors. Both model systems and real groundwater are evaluated. The TCE reaction rate constant was unaffected by TCE concentration for [TCE] < or = 0.46 mM and decreased by less than a factor of 2 for further increases in TCE concentration up to water saturation (8.4 mM). For [TCE] > or = 0.46 mM, acetylene formation increased, and the total amount of H2 evolved at the end of the particle reactive lifetime decreased with increasing [TCE], indicating a higher Fe0 utilization efficiency for TCE dechlorination. Common groundwater anions (5mN) had a minor effect on H2 evolution but inhibited TCE reduction up to 7-fold in increasing order of Cl- < SO4(2-) < HCO3- < HPO4(2). This order is consistent with their affinity to form complexes with iron oxide. Nitrate, a NZVI-reducible groundwater solute, present at 0.2 and 1 mN did not affect the rate of TCE reduction but increased acetylene production and decreased H2 evolution. NO3- present at > 3 mM slowed TCE dechlorination due to surface passivation. NO3- present at 5 mM stopped TCE dechlorination and H2 evolution after 3 days. Dissolved solutes accounted for the observed decrease of NZVI reactivity for TCE dechlorination in natural groundwater when the total organic content was small (< 1 mg/L).     

Ionic strength and composition affect the mobility of surface-modified Fe0 nanoparticles in water-saturated sand columns

The surfaces of nanoscale zerovalent iron (NZVI) used for groundwater remediation must be modified to be mobile in the subsurface for emplacement. Adsorbed polymers and surfactants can electrostatically, sterically, or electrosterically stabilize nanoparticle suspensions in water, but their efficacy will depend on groundwater ionic strength and cation type as well as physical and chemical heterogeneities of the aquifer material. Here, the effect of ionic strength and cation type on the mobility of bare, polymer-, and surfactant-modified NZVI is evaluated in water-saturated sand columns at low particle concentrations where filtration theory is applicable. NZVI surface modifiers include a high molecular weight (MW) (125 kg/mol) poly(methacrylic acid)-b-(methyl methacrylate)-b-(styrene sulfonate) triblock copolymer (PMAA-PMMA-PSS), polyaspartate which is a low MW (2-3 kg/mol) biopolymer, and the surfactant sodium dodecyl benzene sulfonate (SDBS, MW = 348.5 g/mol). Bare NZVI with an apparent zeta-potential of -30 +/- 3 mV was immobile. Polyaspartate-modified nanoiron (MRNIP) with an apparent zeta-potential of -39 +/- 1 mV was mobile at low ionic strengths (< 40 mM for Na+ and < 0.5 mM for Ca2+), and had a critical deposition concentration (CDC) of approximately 770 mM Na+ and approximately 4 mM for Ca2+. SDBS-modified NZVI with a similar apparent zeta-potential (-38.3 +/- 0.9 mV) showed similar behavior (CDC approximately 350 mM for Na+ and approximately 3.5 mM for Ca2+). Triblock copolymer-modified NZVI had the highest apparent zeta-potential (-50 +/- 1.2 mV), the greatest mobility in porous media, and a CDC of approximately 4 M for Na+ and approximately 100s of mM for Ca2+. The high mobility and CDC is attributed to the electrosteric stabilization afforded by the triblock copolymer but not the other modifiers which provide primarily electrostatic stabilization. Thus, electrosteric stabilization provides the best resistance to changing electrolyte conditions likely to be encountered in real groundwater aquifers, and may provide transport distances of 10s to 100s of meters in unconsolidated sandy aquifers at injection velocities used for emplacement.     

Technological and policy innovations toward cleaner development

Clean Technologies and Environmental Policy -     

Transport and deposition of polymer-modified Fe0 nanoparticles in 2-D heterogeneous porous media: effects of particle concentration, Fe0 content, and coatings

Concentrated suspensions of polymer-modified Fe(0) nanoparticles (NZVI) are injected into heterogeneous porous media for groundwater remediation. This study evaluated the effect of porous media heterogeneity and the dispersion properties including particle concentration, Fe(0) content, and adsorbed polymer mass and layer thickness which are expected to affect the delivery and emplacement of NZVI in heterogeneous porous media in a two-dimensional (2-D) cell. Heterogeneity in hydraulic conductivity had a significant impact on the deposition of NZVI. Polymer modified NZVI followed preferential flow paths and deposited in the regions where fluid shear is insufficient to prevent NZVI agglomeration and deposition. NZVI transported in heterogeneous porous media better at low particle concentration (0.3 g/L) than at high particle concentrations (3 and 6 g/L) due to greater particle agglomeration at high concentration. High Fe(0) content decreased transport during injection due to agglomeration promoted by magnetic attraction. NZVI with a flat adsorbed polymeric layer (thickness ～30 nm) could not be transported effectively due to pore clogging and deposition near the inlet, while NZVI with a more extended adsorbed layer thickness (i.e., ～70 nm) were mobile in porous media. This study indicates the importance of characterizing porous media heterogeneity and NZVI dispersion properties as part of the design of a robust delivery strategy for NZVI in the subsurface.     

Polymer-modified Fe0 nanoparticles target entrapped NAPL in two dimensional porous media: effect of particle concentration, NAPL saturation, and injection strategy

Polymer-modified nanoscale zerovalent iron (NZVI) particles are delivered into porous media for in situ remediation of nonaqueous phase liquid (NAPL) source zones. A systematic and quantitative evaluation of NAPL targeting by polymer-modified NZVI in two-dimensional (2-D) porous media under field-relevant conditions has not been reported. This work evaluated the importance of NZVI particle concentration, NAPL saturation, and injection strategy on the ability of polymer-modified NZVI (MRNIP2) to target the NAPL/water interface in situ in a 2-D porous media model. Dodecane was used as a NAPL model compound for this first demonstration of source zone targeting in 2-D. A driving force for NAPL targeting, the surface activity of MRNIP2 at the NAPL/water interface was verified ex situ by its ability to emulsify NAPL in water. MRNIP2 at low particle concentration (0.5 g/L) did not accumulate in or near entrapped NAPL, however, MRNIP2 at moderate and high particle concentrations (3 and 15 g/L) did accumulate preferentially at entrapped NAPL, i.e., it was capable of in situ targeting. The amount of MRNIP2 that targets a NAPL source depends on NAPL saturation (S(n)), presumably because the saturation controls the available NAPL/water interfacial area and the flow field through the NAPL source. At effective S(n) close or equal to 100%, MRNIP2 bypassed NAPL and accumulated only at the periphery of the entrapped NAPL region. At lower S(n), flow also carries MRNIP2 to NAPL/water interfaces internal to the entrapped NAPL region. However, the mass of accumulated MRNIP2 per unit available NAPL/water interfacial area is relatively constant (～0.8 g/m(2) for MRNIP2 = 3 g/L) from S(n) = 13 to ～100%, suggesting that NAPL targeting is mostly controlled by MRNIP2 sorption onto the NAPL/water interface.     

Aggregation and sedimentation of aqueous nanoscale zerovalent iron dispersions

Nanoscale zerovalent iron (NZVI) rapidly transforms many environmental contaminants to benign products and is a promising in-situ remediation agent. To be effective, NZVI should form stable dispersions in water such that it can be delivered in water-saturated porous media to the contaminated area. Limited mobility of NZVI has been reported, however, attributed to its rapid aggregation. This study uses dynamic light scattering to investigate the rapid aggregation of NZVI from single nanoparticles to micrometer size aggregates, and optical microscopy and sedimentation measurements to estimate the size of interconnected fractal aggregates formed. The rate of aggregation increased with increasing particle concentration and increasing saturation magnetization (i.e., the maximum intrinsic magnet moment) of the particles. During diffusion limited aggregation the primary particles (average radius = 20 nm) aggregate to micrometer-size aggregates in only 10 min, with average hydrodynamic radii ranging from 125 nm to 1.2 microm at a particle concentration of 2 mg/L (volume fraction(phi= 3.2 x 10(-7)) and 60 mg/L (phi = 9.5 x 10(-6)), respectively. Subsequently, these aggregates assemble themselves into fractal, chain-like clusters. At an initial concentration of just 60 mg/L, cluster sizes reach 20-70 microm in 30 min and rapidly sedimented from solution. Parallel experiments conducted with magnetite and hematite, coupled with extended DLVO theory and multiple regression analysis confirm that magnetic attractive forces between particles increase the rate of NZVI aggregation as compared to nonmagnetic particles.     

Leaching Behaviors of Arsenic from Arsenic-Iron Hydroxide Sludge during TCLP

The toxicity characteristic leaching procedure (TCLP) is normally used to evaluate if sludge should be managed as hazardous waste. This study examines immobilization mechanisms of arsenic onto arsenic-iron hydroxide sludge, the byproduct of arsenic removal by coagulation with ferric chloride. The leaching mechanism of arsenic from the sludge due to the TCLP is also investigated. Microscopic characterization techniques including scanning electron microscopy equipped with energy dispersive spectroscopy (SEM-EDS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FT-IR) were employed to characterize the sludge samples with the As-to-Fe ratios of 0.07 to 0.15 before and after the TCLP. SEM-EDS and FT-IR results suggested that arsenic-iron hydroxide sludge be ferric hydroxide, whose surface is inner or outer spherically sorbed by arsenic, rather than the precipitate of insoluble iron-arsenic compounds such as Fe(AsO)4. This is also confirmed by XRD results, which revealed that none of such crystalline iron-arsenic compounds were detected in the arsenic-iron hydroxide sludge. Therefore, adsorption among other possible arsenic immobilization mechanisms, namely, precipitation, coprecipitation, and occlusion, is supposed to play the major role. Due to the TCLP, the arsenic concentrations ranging from 0.26 to 2.54?mg/L were leached out of the sludge samples with the As-to-Fe ratios ranging from 0.07 to 0.15, respectively. The changes of FT-IR patterns of the sludge after the TCLP suggested that during the TCLP, desorption and resorption of arsenic occurs. The relationship between arsenic in TCLP leachate and that remaining in the leached sludge can be modeled by Langmuir isotherm, an adsorption isotherm. This indicates that desorption and resorption of arsenic onto the leached sludge is the main phenomenon controlling arsenic leachability due to the TCLP.     

XRD and Unconfined Compressive Strength Study for a Qualitative Examination of Calcium–Arsenic Compounds Retardation of Cement Hydration in Solidified/Stabilized Arsenic–Iron Hydroxide Sludge

This study investigates the adverse effects of synthesized arsenic–iron hydroxide sludge, the by-product of arsenic removal by coagulation with ferric chloride, on unconfined compressive strength (UCS) and cement hydration of solidified/stabilized matrices. The results from both UCS tests and X-ray diffraction (XRD) implied that synthesized arsenic–iron hydroxide sludge might not be chemically inert in a cementitious environment, which could account for the retardation of cement hydration. The culprit for this retardation is likely to be the multiphase formation of calcium arsenic compounds suggested by the strong peak at 7.90?? (11.2°?2θ). This peak appeared when more than 20 and 13% of arsenic–iron hydroxide sludge were added to the solidification/stabilization (S/S) process of cement–water and cement-hydrated lime–water systems, respectively. The proposed mechanisms for the retardation of cement hydration by calcium–arsenic compounds are calcium complexation and, subsequently, surface precipitation due to the interaction between desorbed arsenate and hydration by-products in a cement porewater environment. The extent of the hydration retardation is qualitatively determined by the semiquantitative comparison of Ca3SiO5 and Ca2SiO4 remaining after 28?days of hydration between the control S/S samples and that with various doses of the sludge added. When 20 and 33% of the sludge were added into the S/S matrices, the remaining Ca3SiO5 and Ca2SiO4 were more than that of the control sample by factors of 2 and 3.2, respectively.     

Adsorbed triblock copolymers deliver reactive iron nanoparticles to the oil/water interface

Reactive zero valent iron nanoparticles can degrade toxic nonaqueous phase liquids (NAPL) rapidly in contaminated groundwater to nontoxic products in situ, provided they can be delivered preferentially to the NAPL/water (oil/water) interface. This study demonstrates the ability of novel triblock copolymers to modify the nanoiron surface chemistry in a way that both promotes their colloidal stability in aqueous suspension and drives their adsorption to the oil/water interface. The ability of the copolymers to drive adsorption is demonstrated by the ability of copolymer-modified iron nanoparticles, but not the unmodified iron nanoparticles, to stabilize oil-in-water emulsions.