Infrared monitoring of dinitrotoluenes in sunflower and maize roots.

Infrared microspectroscopy (IMS) is emerging as an important analytical tool for the structural analysis of biological tissue. This report describes the use of IMS coupled to a synchrotron source combined with principal components analysis (PCA) to monitor the fate and effect of dinitrotoluenes in the roots of maize and sunflower plants. Infrared imaging revealed that maize roots metabolized 2,4-dinitrotoluene (DNT) and 2,6-DNT. The DNTs and their derivative aromatic amines were predominantly associated with epidermis and xylem. Both isomers of DNT altered the structure and production of pectin and pectic polysaccharides in maize and sunflower plant roots. Infrared peaks diagnostic for aromatic amines were seen at the 5 mg L concentrations for both DNTs in maize and sunflower treated tissue. However, only infrared peaks for nitro groups, not aromatic amines, were present in the maize treated at 10 mg L For sunflower, the 10 mg L level was toxic and also produced very dark root systems making spectra difficult to obtain. Maize and sunflower seem unable to metabolize effectively at concentrations higher than about 5 mg L DNT in hydroponic solution. Based on the results of this study, IMS combined with PCA can be an effective means of determining the fate and metabolism of organic contaminants in plant tissue when isotopically labeled compounds are not available.

Use of X-ray absorption spectroscopy and biochemical techniques to characterize arsenic uptake and reduction in pea (Pisum sativum) plants.

Arsenite (As(III)) and arsenate (As(V)) uptake by peas was investigated using inductively coupled plasma/optical emission spectroscopy (ICP-OES) at pH below 4 and at pH 5.8. Additionally, total amylolitic activity and alpha-amylase (1,4-alpha-d-glucan glucanohydrolase; EC 3.2.1.1) activity was assayed in plants exposed to arsenic treatments. At pH below 4, the uptake for As(III) and As(V) in roots was 137 and 124 mg As kg(-1) dry weight (d wt), respectively. Translocation of arsenic to the aerial part was relatively low ( approximately 5mg As kg(-1) d wt). The uptake for As(III) and As(V) in roots at pH 5.8 was about 43 and 30 mg As kg(-1) d wt, respectively, and translocation of As to the aerial part was not detectable. None of the arsenic treatments affected the total amylolitic activity in roots; however, the shoots from all treatments showed an increase in the total amylolitic activity. Alpha-amylase activity in the pea leaves was not significantly affected by arsenic treatments. X-ray absorption spectroscopy (XAS) studies showed a reduction of As(V) to As(III) in the roots. From linear combination X-ray absorption near edge structure (LC-XANES) fittings, it was determined that arsenic was present as a mixture of As(III) oxide and sulfide in pea roots.

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 A for the Cr(VI) and Cr(III) in the sample, respectively.

Reduction and Accumulation of Gold(III) by Medicago sativa Alfalfa Biomass: X-ray Absorption Spectroscopy, pH, and Temperature Dependence.

We report herein the use of Medicago sativa alfalfa shoot biomass for the removal of gold from aqueous solutions. The accumulation process involves the reduction of Au(III) to colloidal Au(0) and is shown to increase at elevated temperatures and at lower pH. X-ray absorption spectroscopy (XAS) was used to determine that gold(III) was reduced to form gold(0) colloids, which varied in size depending on the pH of the initial solution. The gold cluster radius was 6.2 ± 1 Å at pH 5 and 9.0 ± 1 Å at pH 2. Our findings indicate that essentially another layer of gold atoms was deposited onto the colloid surface at pH 2. Possible mechanisms of bioreduction and accumulation are discussed.

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.

Use of X-ray Absorption Spectroscopy and Esterification to Investigate Cr(III) and Ni(II) Ligands in Alfalf a 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.