Achintya N. Bezbaruah

Entrapment of iron nanoparticles in calcium alginate beads for groundwater remediation applications

Zero-valent iron nanoparticles (nZVI) have been successfully entrapped in biopolymer, calcium (Ca)-alginate beads. The study has demonstrated the potential use of this technique in environmental remediation using nitrate as a model contaminant. Ca-alginate beads show promise as an entrapment medium for nZVI for possible use in groundwater remediation. Based on scanning electron microscopy images it can be inferred that the alginate gel cluster acts as a bridge that binds the nZVI particles together. Kinetic experiments with 100, 60, and 20mg NO(3)(-)-NL(-1) indicate that 50-73% nitrate-N removal was achieved with entrapped nZVI as compared to 55-73% with bare nZVI over a 2-h period. The controls ran simultaneously show little NO(3)(-)-N removal. Statistical analysis indicates that there was no significant difference between the reaction rates of bare and entrapped nZVI. The authors have shown for the first time that nZVI can be effectively entrapped in Ca-alginate beads and no significant decrease in the reactivity of nZVI toward the model contaminant (nitrate here) was observed after the entrapment.

UPTAKE AND TRANSLOCATION OF TI FROM NANOPARTICLES IN CROPS AND WETLAND PLANTS

Bioavailability of engineered metal nanoparticles affects uptake in plants, impacts on ecosystems, and phytoremediation. We studied uptake and translocation of Ti in plants when the main source of this metal was TiO2 nanoparticles. Two crops (Phaseolus vulgaris (bean) and Triticum aestivum (wheat)), a wetland species (Rumex crispus, curly dock), and the floating aquatic plant (Elodea canadensis, Canadian waterweed), were grown in nutrient solutions with TiO2 nanoparticles (0, 6, 18 mmol Ti L−1 for P. vulgaris, T. aestivum, and R. crispus; and 0 and 12 mmol Ti L−1 for E. canadensis). Also examined in E. canadensis was the influence of TiO2 nanoparticles upon the uptake of Fe, Mn, and Mg, and the influence of P on Ti uptake. For the rooted plants, exposure to TiO2 nanoparticles did not affect biomass production, but significantly increased root Ti sorption and uptake. R. crispus showed translocation of Ti into the shoots. E. canadensis also showed significant uptake of Ti, P in the nutrient solution significantly decreased Ti uptake, and the uptake patterns of Mn and Mg were altered. Ti from nano-Ti was bioavailable to plants, thus showing the potential for cycling in ecosystems and for phytoremediation, particularly where water is the main carrier.

Iron Nanoparticles Coated with Amphiphilic Polysiloxane Graft Copolymers: Dispersibility and Contaminant Treatability

Amphiphilic polysiloxane graft copolymers (APGCs) were used as a delivery vehicle for nanoscale zerovalent iron (NZVI). The APGCs were designed to enable adsorption onto NZVI surfaces via carboxylic acid anchoring groups and polyethylene glycol (PEG) grafts were used to provide dispersibility in water. Degradation studies were conducted with trichloroethylene (TCE) as the model contaminant. TCE degradation rate with APGC-coated NZVI (CNZVI) was determined to be higher as compared to bare NZVI. The surface normalized degradation rate constants, k(SA) (Lm(2-) h(-1)), for TCE removal by CNZVI and bare NZVI ranged from 0.008 to 0.0760 to 007-0.016, respectively. Shelf life studies conducted over 12 months to access colloidal stability and 6 months to access TCE degradation indicated that colloidal stability and chemical reactivity of CNZVI remained more or less unchanged. The sedimentation characteristics of CNZVI under different ionic strength conditions (0-10 mM) did not change significantly. The steric nature of particle stabilization is expected to improve aquifer injection efficiency of the coated NZVI for groundwater remediation.

Remediation of alachlor and atrazine contaminated water with zero-valent iron nanoparticles

Zero-valent iron nanoparticles (nZVI, diameter < 90 nm, specific surface area = 25 m2 g−1) have been used under anoxic conditions for the remediation of pesticides alachlor and atrazine in water. While alachlor (10, 20, 40 mg L−1) was reduced by 92–96% within 72 h, no degradation of atrazine was observed. The alachlor degradation reaction was found to obey first-order kinetics very closely. The reaction rate (35.5 × 10−3–43.0 × 10−3 h−1) increased with increasing alachlor concentration. The results are in conformity with other researchers who worked on these pesticides but mostly with micro ZVI and iron filings. This is for the first time that alachlor has been degraded under reductive environment using nZVI. The authors contend that nZVI may prove to be a simple method for on-site treatment of high concentration pesticide rinse water (100 mg L−1) and for use in flooring materials in pesticide filling and storage stations.

Rapid fractionation of natural organic matter in water using a novel solid-phase extraction technique.

This paper introduces a novel natural organic matter (NOM) fractionation technique using solid-phase extraction cartridges. The new technique requires only 6 hours of fractionation time, which is much faster than traditional fractionation techniques (24 hours). It uses three Bond Elute ENV cartridges (Varian, Inc., Lake Forest, California), one Strata X-C cartridge (Phenomenex, Torrance, California), and one Strata X-AW cartridge (Phenomenex) in series and was tested by using to fractionate NOM from Suwannee River, Georgia (SRNOM) and Red River, Minnesota (RRNOM). Hydrophobic acid was a major fraction and accounted for 66 to 70% and 36% of SRNOM and RRNOM, respectively. The NOM fractions obtained from the developed method were characterized using Fourier transformed infrared spectroscopy and 13C nuclear magnetic resonance. The acid fractions of SRNOM mainly consisted of carboxylic acids. An application of this new technique was demonstrated by using it to investigate the effectiveness of water treatment processes in removing different NOM fractions.

Nitrate removal by entrapped zero-valent iron nanoparticles in calcium alginate.

Zero-valent iron nanoparticles (nZVI) were successfully entrapped in calcium alginate beads. The potential use of this technique in environmental remediation using nitrate as a model contaminant was investigated. Kinetics of nitrate degradation using bare nZVI (approximately 35 nm dia) and entrapped nZVI were compared. Calcium alginate beads show promise as the entrapment medium for nZVI for possible use in permeable reactive barriers for groundwater remediation. Based on scanning electron microscopy images it can be inferred that the alginate gel cluster acts as a bridge that binds the nZVI particles together. Kinetic experiments with 100, 60, and 20 mg NO3--N L(-1) indicate that 50-73% nitrate-N removal was achieved with entrapped nZVI as compared to 55-73% with bare nZVI over a 2 h period. The controls ran simultaneously show little or no NO3--N removal. Statistical analysis indicates that there was no significant difference between the reaction rates of bare and entrapped nZVI. The authors have shown for the first time that nZVI can be effectively entrapped in Ca-alginate beads and no significant decrease in the reactivity of nZVI toward the model contaminant (nitrate here) was observed after the entrapment.

Incorporation of oxygen contribution by plant roots into classical dissolved oxygen deficit model for a subsurface flow treatment wetland

It has been long established that plants play major roles in a treatment wetland. However, the role of plants has not been incorporated into wetland models. This study tries to incorporate wetland plants into a biochemical oxygen demand (BOD) model so that the relative contributions of the aerobic and anaerobic processes to meeting BOD can be quantitatively determined. The classical dissolved oxygen (DO) deficit model has been modified to simulate the DO curve for a field subsurface flow constructed wetland (SFCW) treating municipal wastewater. Sensitivities of model parameters have been analyzed. Based on the model it is predicted that in the SFCW under study about 64% BOD are degraded through aerobic routes and 36% is degraded anaerobically. While not exhaustive, this preliminary work should serve as a pointer for further research in wetland model development and to determine the values of some of the parameters used in the modified DO deficit and associated BOD model. It should be noted that nitrogen cycle and effects of temperature have not been addressed in these models for simplicity of model formulation. This paper should be read with this caveat in mind.

Removal of aqueous cyanide with strongly basic ion-exchange resin

The removal of cyanide (CN−) from aqueous solutions using a strongly basic ion-exchange resin, Purolite A-250, was investigated. The effects of contact time, initial CN− concentration, pH, temperature, resin dosage, agitation speed, and particle size distribution on the removal of CN− were examined. The adsorption equilibrium data fitted the Langmuir isotherm very well. The maximum CN− adsorption capacity of Purolite A-250 was found to be 44 mg CN− g−1 resin. More than 90% CN− adsorption was achieved for most CN− solutions (50, 100, and 200 mg CN− L−1) with a resin dose of 2 g L−1. The equilibrium time was ∼20 min, optimum pH was 10.0–10.5, and optimum agitation speed was 150 rpm. An increase in adsorption of CN− with increasing resin dosage was observed. Adsorption of CN− by the resin was marginally affected (maximum 4% variation) within an environmentally relevant temperature range of 20–50 °C. Fixed-bed column (20.5 mm internal diameters) experiments were performed to investigate the effects of resin bed depth and influent flow rate on breakthrough behaviour. Breakthrough occurred in 5 min for 0.60 cm bed depth while it was 340 min for 5.40 cm bed depth. Adsorption capacity was 25.5 mg CN− g−1 for 5 mL min−1 flow rate and 3.9 mg CN− g−1 for 20 mL min−1 flow rate. The research has established that the resin can be effectively used for CN− removal from aqueous solutions.

Characterization of zinc oxide nanoparticle (nZnO) alginate beads in reducing gaseous emission from swine manure

ABSTRACT Hydrogen sulfide (H2S) and greenhouse gases’ emission from livestock production facilities are of concern to human welfare and the environment. Application of nanoparticles (NPs) has emerged as a potential option for minimizing these gaseous emissions. Application of bare NPs, however, could have an adverse effect on plants, soil, human health, and the environment. To minimize NPs’ exposure to the environment by recovering them, NPs were entrapped in polymeric beads for treating livestock manure. The objectives of the research were to understand the mechanism of gaseous reduction in swine manure treated for 33 days with zinc oxide nanoparticles (nZnO) or nZnO-entrapped alginate (alginate-nZnO) beads by different characterization techniques. Headspace gases from treated manure flasks were collected in 2–6-day intervals during the experimental period and were analyzed for methane (CH4), carbon dioxide (CO2), and H2S concentrations. The microbial analysis of manure was carried out using bacterial plate counts and Real-Time Polymerase Chain Reaction methods. Morphology and chemical composition of alginate-nZnO beads were analyzed by Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), and X-ray Photoelectron Spectroscopy (XPS). Alginate-nZnO beads or bare nZnO proved to be an effective NP in reducing H2S (up to 99%), CH4 (49–72%), and CO2 (46–62%) from manure stored under anaerobic conditions and these reductions are likely due to the microbial inhibitory effect from nZnO, as well as chemical conversion. Both SEM-EDS and XPS analysis confirmed the presence of zinc sulfide (ZnS) in the beads, which is likely formed by reacting nZnO with H2S.

Groundwater Arsenic Remediation using Amphiphilic Polysiloxane Graft Copolymer Coated Iron Nanoparticles

Arsenic (As) contamination has aroused attention in many parts of the world because of its toxic effects. The predominant forms of arsenic in groundwater and surface water are the inorganic species arsenite [As( III) ] and arsenate [As( V )]. Nanoscale zero-valent iron (NZVI) have been used successfully for the rapid removal of arsenic from water. The present research examined the kinetics of the As( V ) degradation with bare NZVI and a novel polymer coated NZVI (CNZVI). The 10 –90 nm diameter NZVI particles were synthesized by sodium borohydride reduction of ferrous iron. To be effective for groundwater remediation, the iron nanoparticles must be dispersible and transportable through the aquifer into the contaminant plume (in this case As plumes of industrial or agricultural origin). An amphiphilic polysiloxane graft copolymer (APGC) was synthesized as the surface modifier to enhance nanoparticle colloidal stability in aqueous environment. The polymer promotes colloidal stability of NZVI in aqueous suspension and makes more reactive surface available for contaminant degradation. The results of As degradation using CNZVI showed an increase in reaction rate as compared to bare NZVI.