K. Dokken

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.

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.

Chemical Modification and X-Ray Absorption Studies for Lead(II)Binding by Medicago sativa (Alfalfa) Biomass

Traditional methods currently employed to remediate heavy metal contaminated waters prove to be cost prohibitive. Therefore, more cost-effective methods of remediating heavy metals from contaminated waters need to be developed. The use of plant materials as metal adsorbents may be a possible solution. Previously performed experiments have shown that alfalfa shoot biomass can bind an appreciable amount of heavy metal ions, even from multi-contaminate containing solutions. Although the alfalfa biomass has shown to be very effective at removing heavy metal ions from aqueous solution, more research is needed to understand the metal binding mechanism. Carboxyl groups were chemically modified in order to determine their contribution to the metal binding process. Batch experiments were performed with the modified biomass and suggest that carboxyl groups play a significant role in the binding of lead(II). In addition, X-ray absorption spectroscopic analysis (XANES and EXAFS) corroborate these results. These studies are important for determining the ligands that may be involved in the binding of lead ions to alfalfa biomass, thus aiding in our understanding of the mechanisms involved in the removal and recovery of metal ions from contaminated waters through phytofiltration.

Effects of chemical competition for multi-metal binding by Medicago sativa (alfalfa)

Alfalfa shoot biomass has demonstrated the ability to bind an appreciable amount of cadmium(II), chromium(III), copper(II), lead(II), nickel(II), and zinc(II) separately from aqueous solutions. Since most heavy metal contaminated waters contain more than one heavy metal ion, it was necessary to determine the binding abilities of the alfalfa biomass with multi-metal solutions. Batch laboratory experiments were performed with a solution containing 0.1 mM of each of the following metal ions: cadmium(II), chromium(III), copper(II), lead(II), nickel(II), and zinc(II). We determined the pH profile, time dependency, and binding capacity by the alfalfa biomass of each metal ion under multi-elemental conditions. For all the metal ions studied, the alfalfa biomass showed to have a high affinity for metal binding around pH 5.0 within a time period of approximately 5 min. The binding capacity experiments showed that there was a preferential binding of the metal ions from the multi-elemental solution with the following amounts of metal ion bound per gram of biomass: 368.5 micromol/g for copper(II), 215.4 micromol/g for chromium(III), 168.0 micromol/g for lead(II), 56.9 micromol/g for zinc(II), 49.2 micromol/g for nickel(II), and 40.3 micromol/g for cadmium(II). Reacting the biomass from the capacity experiments with 0.1 M HCl resulted in 90% or greater recovery of bound cadmium, copper, lead, nickel, and zinc. However, only 44% of the bound chromium was recovered. These experiments show the ability of Medicago sativa (alfalfa) to bind several metal ions under multi-contaminant conditions. Similar results were obtained when the experiments were performed under flow conditions using silica-immobilized alfalfa biomass. Chromium bound on the silica-immobilized biomass was also difficult to be desorbed with 0. 1 M HCl. The information obtained will be useful for the future development of an innovative technology to remove heavy metal contaminants from polluted ground waters.

X-ray Absorption Near Edge Structure and Extended X-ray Absorption Fine Structure Analysis of Standards and Biological Samples Containing Mixed Oxidation States of Chromium(III) and Chromium(VI)

For the first time a method has been developed for the extended X-ray absorption fine structure (EXAFS) data analyses of biological samples containing multiple oxidation states of chromium. In this study, the first shell coordination and interatomic distances based on the data analysis of known standards of potassium chromate (Cr(VI)) and chromium nitrate hexahydrate (Cr(III)) were investigated. The standards examined were mixtures of the following molar ratios of Cr(VI): Cr(III), 0:1, 0.25:0.75, 0.5:0.5, 0.75:0.25, and 1:0. It was determined from the calibration data that the fitting error associated with linear combination X-ray absorption near edge structure (LC-XANES) fittings was approximately ±10% of the total fitting. The peak height of the Cr(VI) pre-edge feature after normalization of the X-ray absorption (XAS) spectra was used to prepare a calibration curve. The EXAFS fittings of the standards were also investigated and fittings to lechuguilla biomass samples laden with different ratios of Cr(III) and Cr(VI) were performed as well. An excellent agreement between the XANES data and the data presented in the EXAFS spectra was observed. The EXFAS data also presented mean coordination numbers directly related to the ratios of the different chromium oxidation states in the sample. The chromium oxygen interactions had two different bond lengths at approximately 1.68 and 1.98 Å for the Cr(VI) and Cr(III) in the sample, respectively.

Localization and speciation of arsenic in soil and desert plant Parkinsonia florida using μXRF and μXANES.

Parkinsonia florida is a plant species native to the semidesert regions of North America. The cultivation characteristics of this shrub/tree suggest that it could be used for phytoremediation purposes in semiarid regions. This work describes, through the use of synchrotron μXRF and μXANES techniques and ICP-OES, the arsenic (As) accumulation and distribution in P. florida plants grown in two soils spiked with As at 20 mg kg(-1). Plants grown in a sandy soil accumulated at least twice more As in the roots compared to plants grown in a loamy soil. The lower As accumulation in plants grown in the loamy soil corresponded to a lower concentration of As in the water-soluble fraction (WSF) of this soil. LC-ICP-MS speciation analysis showed only As(V) in the WSF from all treatments. In contrast, linear combination XANES speciation analysis from the root tissues showed As mainly present in the reduced As(III) form. Moreover, a fraction of the reduced As was found coordinating to S in a form consistent with As-Cys(3). The percentage of As coordinated to sulfur was smaller for plants grown in the loamy soil when compared to the sandy soil.

Accumulation, speciation, and coordination of arsenic in an inbred line and a wild type cultivar of the desert plant species Chilopsis linearis (Desert willow)

This study investigated the absorption of arsenic (As), sulfur (S), and phosphorus (P) in the desert plant Chilopsis linearis (Desert willow). A comparison between an inbred line (red flowered) and wild type (white flowered) plants was performed to look for differential responses to As treatment. One month old seedlings were treated for 7 days with arsenate (As(2)O(5), As(V)) at 0, 20, and 40 mg As(V)L(-1). Results from the ICP-OES analysis showed that at 20mg As(V)L(-1), red flowered plants had 280+/-11 and 98+/-7 mg As kg(-1) dry wt in roots and stems, respectively, while white flowered plants had 196+/-30 and 103+/-13 mg As kg(-1) dry wt for roots and stems. At this treatment level, the concentration of As in leaves was below detection limits for both plants. In red flowered plants treated with 40 mg As(V)L(-1), As was at 290+/-77 and 151+/-60 mg As kg(-1) in roots and stems, respectively, and not detected in leaves, whereas white flowered plants had 406+/-36, 213+/-12, and 177+/-40 mg As kg(-1) in roots, stems, and leaves. The concentration of S increased in all As treated plants, while the concentration of P decreased in roots and stems of both types of plants and in leaves of red flowered plants. X-ray absorption spectroscopy analyses demonstrated partial reduction of arsenate to arsenite in the form of As-(SX)(3) species in both types of plants.