Yael G. Mishael

Selenium removal from drinking water by adsorption to chitosan-clay composites and oxides: Batch and columns tests

Polymer-clay composites were designed to adsorb selenium from water. The highest adsorption efficiency was obtained for chitosan-montmorillonite composites. These composites were characterized by XRD, zeta potential, and FTIR measurements. Adsorption isotherms of selenate on the composite, on Al-oxide and on Fe-oxide were in good agreement with the Langmuir model, yielding a somewhat higher capacity for the composite, 18.4, 17.2 and 8.2 mg/g, respectively. In addition, adsorption by the composite was not pH dependent while its adsorption by the oxides decreased at high pH. Selenium removal from well water (closed due to high selenium concentrations, 0.1 mg/L) by the composite, brought levels to below the WHO limit (0.01 mg/L) and was selective for selenium even in the presence of sulfur (13 mg/L). Selenium adsorption by the composite was higher than by the Al-oxide due to high adsorption of sulfur by the later. Unlike employment in batch Al-oxide is more suitable for employment in filtration columns due to its high hydraulic conductivity. A semi-pilot columns experiment demonstrated selenium removal from the well water below the recommended limit (first 400 pore volumes) by Al-oxide columns. Regeneration of Al-oxide and of the composite was studied and readsorption of selenium was demonstrated.

Clay-based formulations of metolachlor with reduced leaching

The current research in herbicide application aims to develop formulations that reduce leaching of the herbicide to deep layers of the soil and to concentrate its biological activity at the top layers. Adsorption of metolachlor on clay minerals, their organic derivatives or pillared forms provides the best possibility to develop slow-release formulations. Metolachlor is a selective pre-emergence herbicide widely used in irrigated crops to control annual weeds. It is adsorbed by bentonites and montmorillonites, but the amount adsorbed strongly depends on the type of bentonite and possible pretreatment reactions. Wyoming bentonites adsorbed considerable amounts of metolachlor but other bentonites did not bind this herbicide. An acid-activated pillared montmorillonite was also an effective adsorbent of metolachlor. Modification of this sample by preadsorbing different amounts of benzyl trimethylammonium ions did not influence the level of herbicide adsorption. The biological efficiency of the formulations was tested with bioassay soil columns. Slow-release formulations could be prepared with raw bentonites and the acid-activated pillared montmorillonite. A formulation, prepared by adsorbing metolachlor from aqueous solution on the acid-activated pillared montmorillonite, showed high herbicide activity at the top 10 cm, and did not diffuse significantly to greater depths. This formulation should allow a better weed control than the commercial formulations.

Organo-clay formulations of pesticides: reduced leaching and photodegradation

Adsorption of organic cations on several clay minerals is reviewed with an emphasis on the effect of ionic strength and modeling. The clay exchanged with suitable organic cations forms a basis for ecologically acceptable formulations of herbicides with reduced leaching, ground water contamination and enhanced weed control efficacy. Incomplete neutralization of the clay surface charge by an organic cation may be advantageous in achieving maximal adsorption of hydrophobic herbicides. One conclusion from these studies is that optimization of clay-based herbicide formulations requires a selection of structurally compatible organic cations preadsorbed on the clay at optimal coverage. New experimental results are presented for alachlor formulations, which significantly reduce herbicide leaching under conditions of heavy irrigation. We were able to demonstrate that organo-clay formulations of alachlor and metolachlor can increase crop yields in a 1-year field experiment. The photostabilization of pesticides is reviewed and improved organo-clay formulations of the herbicides trifluralin and norflurazon are described. A pillared clay, nanocomposite micro- and/or meso porous material, was effective in reducing leaching and in conferring photostabilization, without added organic cations.

Atrazine removal from water by polycation–clay composites: Effect of dissolved organic matter and comparison to activated carbon

Atrazine removal from water by two polycations pre-adsorbed on montmorillonite was studied. Batch experiments demonstrated that the most suitable composite poly (4-vinylpyridine-co-styrene)-montmorillonite (PVP-co-S90%-mont.) removed 90-99% of atrazine (0.5-28 ppm) within 20-40 min at 0.367% w/w. Calculations employing Langmuirs equation could simulate and predict the kinetics and final extents of atrazine adsorption. Column filter experiments (columns 20x1.6 cm) which included 2g of the PVP-co-S90%-mont. composite mixed with excess sand removed 93-96% of atrazine (800 ppb) for the first 800 pore volumes, whereas the same amount of granular activated carbon (GAC) removed 83-75%. In the presence of dissolved organic matter (DOM; 3.7 ppm) the efficiency of the GAC filter to remove atrazine decreased significantly (68-52% removal), whereas the corresponding efficiency of the PVP-co-S90%-mont. filter was only slightly influenced by DOM. At lower atrazine concentration (7 ppb) the PVP-co-S90%-mont. filter reduced even after 3000 pore volumes the emerging atrazine concentration below 3 ppb (USEPA standard). In the case of the GAC filter the emerging atrazine concentration was between 2.4 and 5.3 microg/L even for the first 100 pore volumes. Thus, the PVP-co-S90%-mont. composite is a new efficient material for the removal of atrazine from water.

Applying zeta potential measurements to characterize the adsorption on montmorillonite of organic cations as monomers, micelles, or polymers.

A systematic study was carried out to characterize the adsorption of organic cations as monomers, micelles, or polymers on montmorillonite by monitoring zeta potential (ξ) as a function of cation loading on the clay. In general, the clays ξ became less negative as cation loading increased. A fairly good linear correlation between adsorption of organic cations on the clay, up to the cation exchange capacity (CEC) of the clay, and ξ potential of the composites was fitted. However, when the adsorption of the larger cation exceeded the CEC, a nonlinear increase in ξ was measured. The degree of this increase corresponds to the cation size and affinity to the clay (in the order surfactant<dye dimer<micelle). In contrast to the organic cations, ξ reached zero at polycation loadings that were significantly lower than the CEC. The zeta-adsorption plot of the polycations reached a well-defined plateau which correlates to the zeta potential of the polycations. The effect of electrolytes on ξ of the crude clay was monitored, and as expected, the extent of the effect increased with valency (Na(+)<Ca(2+)<Al(3+)) and with intrinsic cation radius (Na(+)<Cs(+)); however, an unexpected anion effect was observed.

Effect of Humic Acid on Pyrene Removal from Water by Polycation-Clay Mineral Composites and Activated Carbon

Pyrene removal by polycation-montmorillonite (MMT) composites and granulated activated carbon (GAC) in the presence of humic acid (HA) was examined. Pyrene, HA, and sorbent interactions were characterized by FTIR, fluorescence and zeta measurements, adsorption, and column filtration experiments. Pyrene binding coefficients to the macromolecules were in the order of PVPcoS (poly-4-vinylpiridine-co-styrene) > HA > PDADMAC (poly diallyl-dimethyl-ammonium-chloride), correlating to pyrene-macromolecules compatibility. Electrostatic interactions explained the high adsorption of HA to both composites (∼100%), whereas HA adsorption by GAC was low. Pyrene removal by the composites, unlike GAC, was enhanced in the presence of HA; removal by PDADMAC-MMT increased from ∼50 (k(d) = 2.2 × 10(3) kg/L) to ∼70% (k(d) = 2.4 × 10(3) kg/L) in the presence of HA. This improvement was attributed to the adsorption of pyrene-HA complexes. PVPcoS-MMT was most efficient in removing pyrene (k(d) = 1.1 × 10(4) kg/L, >95% removal) which was explained in terms of specific π donor-π acceptor interactions. Pyrene uptake by column filters of GAC reached ∼50% and decreased to ∼30% in the presence of HA. Pyrene removal by the PVPcoS-MMT filter was significantly higher (100-85% removal), exhibiting only a small decrease in the presence of HA. The utilization of HA as an enhancing agent in pollutant removal is novel and of major importance in water treatment.

Filtration of triazine herbicides by polymer-clay sorbents: coupling an experimental mechanistic approach with empirical modeling.

Triazine herbicides detected in surface and groundwater pose environmental and health risks. Removal of triazine herbicides (simazine, atrazine and terbuthylazine) by polymer-clay composites was studied and modeled. Their binding by a poly 4-vinyl pyridine co styrene-montmorillonite (HPVP-CoS-MMT) composite was especially high due to specific interactions between the herbicides and polymer, mainly hydrogen bonds and π-π stacking. The binding kinetics to the composite was in the order of simazine > atrazine > terbuthylazine, which was in accord with their equilibrium Langmuir binding coefficients; 44,000, 17,500 and 16,500 M(-1), respectively, which correlated with herbicide accessibility to form specific interaction with the polymer. Simazine binding kinetics to the composite was significantly faster than to granulated activated carbon (GAC), reaching 93% vs 38% of the maximal adsorption within 10 min, respectively. Herbicide filtration by composite columns was adequately fitted by a model which considers convection and employs Langmuir formalism for kinetics of adsorption/desorption. Filtration of simazine (10 μg L(-1)) by composite columns (40 cm long, which included 26 g composite mixed with sand 1:40 (weight ratio)), was well predicted by the model with nearly 120 L purified, i.e., effluent concentrations were below regulation limit (3 μg L(-1)). Effluent concentrations from GAC columns exceeded the limit after filtering 5 L. Experimental results and model predictions suggest that while GAC has a high capacity for simazine binding, the composite has higher affinity towards the herbicide and its adsorption is faster, which yields more efficient filtration by composite columns.

Herbicide solubilization in micelle-clay composites as a basis for controlled release sulfentrazone and metolachlor formulations.

Sulfentrazone and metolachlor have been detected in groundwater due to extensive leaching. To reduce herbicide leaching and increase weed control, we have developed, designed, and tested controlled release formulations (CRFs) for both herbicides based on their solubilizion in cationic micelles and adsorption of the mixed micelles (surfactant and herbicide) on a clay mineral, montmorillonite. A better understanding of solubilizing anionic (sulfentrazone) and nonionic (metolachlor) organic molecules in cationic micelles was reached. The percent of active ingredient in the formulations was much higher than previously designed CRFs due to the enhanced solubilization of the herbicides in the micelles and due to their adsorption on the clay. Both CRFs demonstrated controlled release (compared to the commercial formulations) when applied to a thin soil layer. A bioassay in soil columns determined that the new sulfentrazone and metolachlor CRFs significantly improve weed control and reduce leaching (for the latter) in comparison with the commercial formulations.

Effective harvesting of microalgae: Comparison of different polymeric flocculants

Microalgae harvesting is a major hurdle in the use of microalgae for oil production. Here we describe the use of a standard cationic polymer used for water treatment, Polydiallyldimethylammonium chloride (PDADMAC), for sedimentation of Chlorella vulgaris and comparison of its flocculation properties with two other polymers, chitosan and Superfloc®. We found PDADMAC to be the most effective flocculant with 90% of the algae flocculating at concentrations as low as 5mg/L within 60min, and good activity even at pH=10. Interestingly, with both PDADMAC and chitosan maximum flocculation was achieved much before zeroing of zeta potential. PDADMAC flocculation was also very effective in enhancing harvest by filtration and somewhat at flocculation and sedimentation of marine algae, Nannochloropsis salina.

Nitrate Reduction By Redox-Activated, Polydiallyldimethylammonium-Exchanged Ferruginous Smectite

Nitrate is linked to chronic human illness and to a variety of environmental problems, and continues to be a contaminant of concern in soils and natural waters. Improved methods for nitrate abatement, thus, are still needed. The purpose of this study was to assess the potential for redox-modified, iron-bearing clay minerals to act as nitrate decontamination agents in natural environments. The model clay mineral tested was ferruginous smectite (sample SWa-1) exchanged with either sodium (Na+) or polydiallyldimethylammonium chloride (poly-DADMAC). Structural iron (Fe) in SWa-1 was in either the oxidized or reduced state. Little nitrate uptake was observed in the Na+-SWa-1, which was attributed to coulombic repulsion between the basal surfaces of the smectite and the nitrate anion. The addition of the DADMAC to the SWa-1 reversed the electrostatic charge manifested at the smectite surface from negative to positive, as measured by the zeta (ζ) potential. The positively charged poly-DADMAC-SWa-1 yielded high nitrate uptake due to coulombic attraction in both the oxidized and reduced states of the Fe in the SWa-1. The presence of reduced structural Fe(II) in the positively charged poly-DADMAC-SWa-1 enabled a chemical reduction reaction with the nitrate to produce nitrite. The amounts of nitrite found in solution, however, failed to account for all of the Fe(II) oxidized, so other N reduction products may also have formed or perhaps nitrite was also present in the adsorbed phase. The effects of other complexities, such as polymer configuration at the surface, also need further investigation. The results do clearly establish abiotic nitrate reduction to nitrite and possibly other reduction products. The combination of bacterial activity in soils and sediments, which is known to reduce structural Fe in smectites, and the abundance of organic cations in soil organic matter creates an environment where reversed-charge smectite could exist in nature. This represents a potentially effective system for mitigating harmful effects of nitrate in soils, sediments, groundwater, and surface water.