K.J. Tiemann

Characterization of Cr(VI) binding and reduction to Cr(III) by the agricultural byproducts of Avena monida (oat) biomass.

Chromium contamination of the environment has become an important issue due to the potential health threat it poses. Conventional technologies to clean up heavy metal ions from contaminated waters have been utilized, but these technologies are not cost-effective. However, the use of agricultural waste byproducts for the removal of Cr(VI) from contaminated waters may be a new cost-effective alternative. Oat byproducts from the Juarez Valley in Mexico were studied for the ability to bind Cr(VI) under different temperature and time conditions. The metal binding ability of oat byproducts was calculated from experimental data collected at temperatures of 8, 26, and 54 degrees C, and time exposures of 1, 6, 24, 48, and 72 h at each temperature. These results showed that the binding of Cr(VI) to oat biomass increased as time and temperature increased. The bound chromium was recovered from the oat biomass by treatment with 0.2M HCl. Through the use of X-ray absorption spectroscopy, the reduction of Cr(VI) to Cr(III) was determined to occur by the oat byproducts. These results indicate that the use of agricultural waste byproducts could be a better alternative for the removal and subsequent reduction of Cr(VI) to Cr(III) from contaminated waters.

Phytofiltration of hazardous cadmium, chromium, lead and zinc ions by biomass of Medicago sativa (Alfalfa)

Abstract Previous laboratory batch experiments of Medicago sativa (Alfalfa) indicated that the African shoots population had an appreciable ability to bind copper(II) and nickel(II) ions from aqueous solution. Batch laboratory pH profile, time dependency and capacity experiments were performed to determine the binding ability of the African shoots for cadmium(II), chromium(III), chromium(VI), lead(II), and zinc(II). Batch pH profile experiments for the mentioned ions indicated that the optimum pH for metal binding is approximately 5.0. Time dependency experiments for all the metals studied showed that metal binding to the African alfalfa shoots occurred within 5 min. Binding capacity experiments revealed the following amounts of metal ions bound per gram of biomass: 7.1 mg Cd(II), 7.7 mg Cr(III), 43 mg Pb(II), and 4.9 mg Zn(II). However, no binding occurred for chromium(VI). Nearly all of the metals studied were recoverable by treatment with 0.1 M HCl. Column experiments were performed to study the binding of Cd(II), Cr(III), Cr(VI), Pb(II) and Zn(II) to silica-immobilized African alfalfa shoots under flow conditions. These experiments showed that the silica immobilized African alfalfa shoots were effective for removing metal ions from solution, and over 90% of the bound Pb(II), Cu(II), Ni(II), and Zn(II), and over 70%Cd(II), were recovered after treatment with 10 bed volumes of 0.1 M HCl. The results from these studies will be useful for a novel phytofiltration technology to remove and recover heavy metal ions from aqueous solution.

Effect of mixed cadmium, copper, nickel and zinc at different pHs upon alfalfa growth and heavy metal uptake

Alfalfa plants were grown in soil-pots contaminated with a mixture of Cd(II), Cu(II), Ni(II), and Zn(II), (at 50 mg/kg each) at pHs of 4.5, 5.8, and 7.1. The plants were fertilized using a nutrient solution, which was adjusted appropriately to the same pH. Plants in the control treatment were grown in the absence of the heavy metals mixture. The growth of the control plants was the same at the three pHs studied and the heavy metal stressed plants also showed similar behavior at each pHs. There were statistically significant differences (P<0.05) between the shoot length of the control treatment plants and the length of plants grown in the presence of the heavy metal mixture. Under the effects of the heavy metal mixture, nickel was the most accumulated element in the shoot tissue, with 437, 333, and 308 ppm at pH 7.1, 5.8, and 4.5, respectively. Cadmium was found to be second in accumulated concentrations with 202 ppm, 124 ppm, and 132 ppm at pH 7.1, 5.8, and 4.5, respectively, while zinc was third, followed by copper. The maximum relative uptakes (element in plant/element in soil-water-solution) were found to be 26 times for nickel, 23 times for cadmium, 12 times for zinc. and 6 times for copper. We considered these relations as indicative of the ability of alfalfa plants to take up elements from a soil matrix contaminated with a mixture of cadmium, copper, nickel, and zinc.

Gold nanoparticles obtained by bio-precipitation from gold(III) solutions

The use of metal nanoparticles has shown to be very important in recent industrial applications. Currently gold nanoparticles are being produced by physical methods such as evaporation. Biological processes may be an alternative to physical methods for the production of gold nanoparticles. Alfalfa biomass has shown to be effective at passively binding and reducing gold from solutions containing gold(III) ions and resulting in the formation of gold(0) nanoparticles. High resolution microscopy has shown that five different types of gold particles are present after reaction with gold(III) ions with alfalfa biomass. These particles include: fcc tetrahedral, hexagonal platelet, icosahedral multiple twinned, decahedral multiple twinned, and irregular shaped particles. Further analysis on the frequency of distribution has shown that icosahedral and irregular particles are more frequently formed. In addition, the larger particles observed may be formed through the coalescence of smaller particles. Through modification of the chemical parameters, more uniform particle size distribution may be obtained by the alfalfa bio-reduction of gold(III) from solution.

Use of X-ray absorption spectroscopy and esterification to investigate Cr(III) and Ni(II) ligands in alfalfa biomass

Previously performed studies have shown that alfalfa shoot biomass can bind an appreciable amount of nickel(II) and chromium(III) ions from aqueous solution. Direct and indirect approaches were applied to study the possible mechanis ms involved in metal binding by the alfalfa biomass. The direct approach involves investigations of the metal-bound alfal fa shoot biomass by X-ray absorption spectroscopic analysis (XANES and EXAFS). Results from these studies suggest that ni ckel(II) and chromium(III) binding mostly occurs through coordination with oxygen ligands. Indirect approaches consist of chemical modification of carboxylate groups that have been shown to play an important role in metal binding to the alfal fa biomass. An appreciable decrease in metal binding resulted after acidic methanol esterification of the biomass, indica ting that carboxyl groups are entailed in the metal binding by the alfalfa biomass. In addition, base hydrolysis of the a lfalfa biomass increased the binding of these metals, which further indicates that carboxyl groups play an important role in the binding of these metal ions from solution. Therefore, by combining two different techniques, our results indicate that carboxylate groups are the major ligands responsible for the binding of nickel(II) and chromium(III) by alfalfa bio mass.

Ability of silica-immobilized Medicago sativa (alfalfa) to remove copper ions from solution

Abstract Preliminary screening laboratory batch experiments to determine the binding ability of seven different populations of Medicago sativa (alfalfa) showed good copper binding characteristics of the biomasses studied. All seven populations examined had similar trends for binding copper as a function of pH. The copper binding by the different alfalfa populations occurred within 5 min. All the alfalfa biomasses showed high copper binding, but the capacities varied according to the alfalfa sample studied. The pH dependence of the copper ion binding to the alfalfa biomasses suggested that it might be possible to recycle the system much like an ion-exchange resin. However, the alfalfa cells cannot be packed into a column because the cells clump together and restrict the flow. We immobilized the cells of Malone alfalfa shoots in a silica matrix. Column experiments for copper binding by the silica immobilized alfalfa demonstrated that the alfalfa tissues were capable of removing considerable amounts of copper ions under flow conditions. After every copper binding cycle most of the copper was desorbed with a few bed volumes of 0.1 M HCl. Our work indicates that the Malone-silica preparations are highly durable. We subjected the biomaterial to as many as 10 cycles of binding and elution without observing any significant decrease in copper binding capacity.

An XAS study of the binding of copper(II), zinc(II), chromium(III) and chromium(VI) to hops biomass

Abstract Due to the increasing concentrations of heavy metals in potable water and industrial wastewater governmental agencies have created stricter regulations for the treatment of metal contaminated waste. However, current technologies are both expensive and time consuming to use for water and waste treatment. As an alternative to the current technologies, phytofiltration has been proposed, but to make phytofiltration effective the process must be further studied to better understand the metal–biomass chemical interactions. This current study on the use of hops biomass to remove heavy metal ions from aqueous solutions uses X-ray absorption spectroscopy (XAS) to investigate the binding mechanism of heavy metals to hops biomass. The XAS studies showed that copper(II), zinc(II) and chromium(III) remained in the same oxidation state as when they were reacted with the hops biomass. However, the reaction of chromium(VI) with the hops biomass resulted in the reduction of chromium(VI) to chromium(III). Analysis of the XAS spectra showed that copper(II) bound to the hops biomass with a molecular geometry of copper(II) acetate; zinc(II) bound to the hops biomass with a molecular geometry of zinc(II) gluconate; and chromium(VI) bound to the biomass with the geometry of chromium(III) acetate. In addition, the XAS studies showed that the nearest neighboring atom of all the bound metal ions was an oxygen atom.

Infrared and X-Ray absorption spectroscopic studies on the mechanism of chromium(III) binding to alfalfa biomass

Previous studies have shown that alfalfa biomass possesses the potential to be a biosorbent for chromium(III) removal from contaminated and industrial wastewaters. However, the mechanism through which chromium(III) binds to alfalfa biomass has not been identified. Therefore, studies were conducted to determine how modification of chemical groups present on the alfalfa biomass affect the chromium(III) binding. Batch pH profile studies were performed on esterified, hydrolyzed and unmodified alfalfa biomasses. A comparison study with ion exchange resins containing carboxyl, thiol, amino, sulfonic, and phosphate groups were also performed. These studies showed that chromium(III) binds predominantly to the alfalfa biomass through carboxyl ligands and follows a binding trend similar to that of the carboxyl resin. In addition, Fourier transform infrared spectroscopy (FTIR) studies were conducted in order to better understand how the chemical modification affects the alfalfa biomass and the mechanism(s) by which chromium(III) binds to alfalfa. From these experiments, it was determined that chromium(III) may be coordinating with carboxyl ligands present on the surface of the alfalfa biomass through a bridging bidentate complex. X-Ray absorption spectroscopy (XAS) studies were also performed, which corroborate with batch modification and ion exchange resin comparison studies, further indicating carboxyl involvement in chromium(III) binding by inactivated alfalfa biomass.

Use of hop (Humulus lupulus) agricultural by-products for the reduction of aqueous lead(II) environmental health hazards

The agricultural by-products of the hop plant (Humulus lupulus L.) were investigated to determine their potential for use in the removal of heavy lead(II) ions from contaminated aqueous solutions. Separate batch laboratory experiments were performed to establish the optimal binding pH, time exposures, and capacity of the metal adsorption for lead(II) ions by dried and ground hop leaves and stems biomass. Results from these studies have shown a pH dependent binding trend from pH 2-6, with optimum binding occurring around pH 5.0. Time dependency experiments showed a rapid adsorption of lead(II) ions within the first 5 min of contact. Binding capacity experiments demonstrated that 74.2mg of lead(II) were bound per gram of leaf biomass. Similarly overall capacity was seen for the leaves and stems. Desorption of 99% of the bound lead(II) ions was achieved by exposing the metal laden biomass to 0.5M sodium citrate. Further experiments were performed with silica-immobilized hop tissues to determine the lead(II) binding ability under flow conditions. Comparison studies were performed with ion-exchange resins to evaluate the binding ability and to gain further insight into the metal binding mechanism. X-ray absorption spectroscopy experiments were also utilized to gain further insight into the possible lead(II) binding mechanism by the hop plant tissue. Results from these studies indicate that carboxyl ligands are involved in the binding of lead(II) from aqueous solution. These findings show that the use of hop agricultural waste products may be a viable alternative, for the removal and recovery of aqueous lead(II) ions from contaminated waters.

REMOVAL OF NICKEL IONS FROM AQUEOUS SOLUTION BY BIOMASS AND SILICA-IMMOBILIZED BIOMASS OF MEDICAGO SATIVA (ALFALFA)

The characteristics of the roots and shoots from seven different populations of Medicago sativa (alfalfa) were examined for their ability to bind nickel ions from aqueous solution. Batch laboratory experiments were performed to determine the optimal pH for nickel binding to the alfalfa plant tissues which was between pH 5 and 6. From these experiments, pH profiles were performed to gain information about the chemical functional groups in the alfalfa plant tissues responsible for the nickel binding. Binding time dependency studies determined that approximately 80% of the nickel ions bound to the alfalfa plant tissues in less than 5 min. Binding capacity experiments showed that nickel binding was as much as 4.1 mg of nickel per gram of alfalfa biomass. Nickel recovery experiments showed that more than 90% of the bound nickel was removed from the alfalfa biomass. Column experiments were conducted to examine the binding of nickel to silica immobilized alfalfa plant tissues under flow conditions. Results from these experiments showed that more than 90% of the retained nickel was recovered after four bed volumes of 0.1 M HC1 solution were passed through the column. After 12 cycles on the same column, the efficiency for nickel removal and recovery from solution was stable.