Yu-Min Tzou

Cr(VI) Removal on Fungal Biomass of Neurospora crassa: the Importance of Dissolved Organic Carbons Derived from the Biomass to Cr(VI) Reduction

Interactions of toxic Cr(VI) with renewable biomaterials are considered an important pathway for Cr(VI) removal in ecosystems. Biomaterials are susceptible to dissolution, and their dissolved derivatives may provide an alternative to surface-involved pathway for scavenging of Cr(VI). In this study, dissolved organic carbon (DOC) derived from Neurospora crassa biomass was investigated. The proportion of Cr(VI) reduction by DOC to that on biomass was determined to evaluate the importance of DOC to Cr(VI) reduction. A rapid increase in DOC concentration from 145.6 to 193.7 mg L(-1) was observed when N. crassa-biomass was immersed in 0.01 M KCl solution at pH of 1-5, and polysaccharides, peptides, and glycoproteins with carboxyl, amide, and -NH functional groups, are the major compositions of DOC. On reaction of 96.2 microM Cr(VI) with N. crassa-biomass or DOC, it was estimated that DOC contributed approximately 53.8-59.5% of the total Cr(VI) reduction on biomass in the dark. Illumination enhanced Cr(VI) reduction via photo-oxidation of biomass/DOC under aeration conditions, which formed superoxide for Cr(VI) reduction. At pH 1, photoinduced Cr(VI) reduction by DOC proceeded more rapidly than reduction on the biomass surface. However, at pH >3, with a decrease in Cr(VI) reduction by DOC, photon-excited biomass may become an important electron source for Cr(VI) photoreduction.

Removal of hexavalent Cr by coconut coir and derived chars - The effect of surface functionality

The Cr(VI) removal by coconut coir (CC) and chars obtained at various pyrolysis temperatures were evaluated. Increasing the pyrolysis temperature resulted in an increased surface area of the chars, while the corresponding content of oxygen-containing functional groups of the chars decreased. The Cr(VI) removal by CC and CC-derived chars was primarily attributed to the reduction of Cr(VI) to Cr(III) by the materials and the extent and rate of the Cr(VI) reduction were determined by the oxygen-containing functional groups in the materials. The contribution of pure Cr(VI) adsorption to the overall Cr(VI) removal became relatively significant for the chars obtained at higher temperatures. Accordingly, to develop a cost-effective method for removing Cr(VI) from water, the original CC is more advantageous than the carbonaceous counterparts because no pyrolysis is required for the application and CC has a higher content of functional groups for reducing Cr(VI) to less toxic Cr(III).

Removal of hexavalent chromium from acidic aqueous solutions using rice straw-derived carbon

This study evaluates the removal of Cr(VI) from water by carbon derived from the burning of rice straw. Rice straw was burned in the air to obtain rice carbon (RC), and then the removal of Cr(VI) by RC was investigated under various pHs and ionic strengths. After the experiments, the oxidation state of Cr bound to RC was analyzed using X-ray photoelectron spectroscopy, which revealed that Cr bound to RC was predominately in the trivalent form. The results showed that upon reacting with RC, Cr(VI) was reduced to Cr(III), which was either adsorbed on RC or released back into solution. The extent and rate of Cr(VI) removal increased with decreasing solution pH because the Cr(VI) adsorption and the subsequent reduction of adsorbed Cr(VI) to Cr(III) both occur preferentially at low pH. The minimal effect of ionic strength on the rates of Cr(VI) removal and Cr(III) adsorption indicated specific interactions between Cr(VI)/Cr(III) and their surface binding sites on RC. These results suggest that rice straw-based carbon may be effectively used at low pH as a substitute for activated carbon for the treatment of Cr(VI) contaminated water.

Biosorption of Cr(VI) by coconut coir: spectroscopic investigation on the reaction mechanism of Cr(VI) with lignocellulosic material.

In this study, the removal mechanism of Cr(VI) from water by coconut coir (CC) was investigated using X-ray photoelectron spectroscopy (XPS), Cr K-edge X-ray absorption near edge structure (XANES) and FTIR spectroscopy. The results showed that, upon reaction with CC at pH 3, Cr(VI) was reduced to Cr(III), which was either bound to CC or released back into solution. As revealed by the FTIR spectra of CC before and after reacting with Cr(VI), the phenolic methoxyl and hydroxyl groups of lignin in CC are the dominant drivers of Cr(VI) reduction, giving rise to carbonyl and carboxyl groups on CC. These functional groups can subsequently provide binding sites for Cr(III) resulting from Cr(VI) reduction. In conjunction with forming complexes with carbonyl and carboxyl groups, the formation of Cr(III) hydroxide precipitate could also readily occur as revealed by the linear combination fitting of the Cr K-edge XANES spectrum using a set of reference compounds. The phenolic groups in lignin are responsible for initiating Cr(VI) reduction, so lignocellulosic materials containing a higher amount of phenolic groups are expected to be more effective scavengers for removal of Cr(VI) from the environment.

Catalytic and atmospheric effects on microwave pyrolysis of corn stover

Corn stover, which is one of the most abundant agricultural residues around the world, could be converted into valuable biofuels and bio based products by means of microwave pyrolysis. After the reaction at the microwave power level of 500W for the processing time of 30min, the reaction performance under N2 atmosphere was generally better than under CO2 atmosphere. This may be due to the better heat absorbability of CO2 molecules to reduce the heat for stover pyrolysis. Most of the metal-oxide catalysts effectively increased the maximum temperature and mass reduction ratio but lowered the calorific values of solid residues. The gas most produced was CO under N2 atmosphere but CO2 under CO2 atmosphere. Catalyst addition lowered the formation of PAHs and thus made liquid products less toxic. More liquid products and less gas products were generated when using the catalysts possibly due to the existence of the Fischer-Tropsch synthesis.

Chromate reduction by zero-valent Al metal as catalyzed by polyoxometalate.

In spite of a high reduction potential of zero-valent Al (ZVAl), its ability to reduce Cr(VI), a widespread pollutant, to less toxic Cr(III) remains to be uncovered. In the present study, Cr(VI) reduction by ZVAl was conducted to evaluate the potential application of Al as a reductant for Cr(VI). Polyoxometalate (POM, HNa(2)PW(12)O(40)), a catalyst, was used to accelerate Cr(VI) reduction by Al. The reaction of 0.192mM Cr(VI) on ZVAl was investigated in the presence of N(2) or O(2) at pH 1. A slight decrease in Cr(VI) concentration was observed on as-received (uncleaned) ZVAl due to the presence of oxide layer with a low surface area (ca. 3.4x10(-3)m(2)/g) of ZVAl. On addition of 0.1mM POM, Cr(VI) reduction on uncleaned ZVAl increased significantly. This is attributed to the unique properties of POM, which has a Brphinsted acidity higher than usual inorganic acids such as H(2)SO(4) and HCl. Thus, POM could remove rapidly the oxidize layer on ZVAl, followed by acting as a shuttle for electron transfer from ZVAl to Cr(VI). Under a N(2) atmosphere, one- or two-electron reduction of POM by ZVAl was responsible for Cr(VI) reduction in the early stage of the reaction. However, during reaction with ZVAl over 120min, three-electron reduction of POM predominated over Cr(VI) reduction. On interaction of O(2) with reduced POM, the formation of H(2)O(2) was responsible for subsequent Cr(VI) reduction. The results suggest that POM is an efficient catalyst for Cr(VI) reduction by Al due to the extremely rapid consumption of reduced POM or H(2)O(2) by Cr(VI).

Phosphate sorption by calcite, and iron-rich calcareous soils

Abstract P-sorption isotherms were determined for calcium carbonate (AR grade) and four soils, which contain various amounts of iron oxides and calcium carbonate. The results could be put into the Langmuir equation. The sorption maximum of calcite was 26 mg P kg−1. This result was used to calculate the surface coverage of calcite by sorbed P. The model indicated that only 1 4 to 1 8 of the unit cell surface was able to adsorb phosphate. High-gradient magnetic separation (HGMS) was used to fractionate soil clays into magnetic and tailing fractions. The amount of P-sorption was correlated with the free iron oxide (Fed) contents of the magnetic clay fractions (r = 0.82), but was not significantly correlated with the noncrystalline iron oxide (Feo) contents. Synthetic hematite and the Lin-Kuo alluvial reddish soils were treated at various pH values with 155 mg P g−1. The results of 57Fe Mossbauer spectra of the hematite treated at pH 3 possessed a FeP doublet, which indicated an FeP compound. It was not observed in the Lin-Kuo soils treated with phosphate. Phosphate treated soils were extracted sequentially with 1M NH4Cl (easily soluble P), NaOH/NaCl/citrate-bicarbonate (CB, FeAl-bound P), dithionite-citrate-bicarbonate (DCB, occluded P), and HCl (Ca-bound P). The P-treated soils were incubated with two cycles of wetting to field capacity water ( 1 3 bar) and drying for a 10 day period. The treatments resulted in higher portions FeAl-bound P in Lin-Kou and Tung-Wei soils. Calcareous Nan-Wan and Hou-Liao soils contained more Ca-bound P. Only a small proportion of the added-P was easily soluble and occluded-bound.

A mechanism study of light-induced Cr(VI) reduction in an acidic solution.

The mechanisms of photo-catalytic reduction of Cr(VI) were investigated in acidic solutions with and without Fe(III). In a system without Fe(III), no Cr(VI) reduction was observed in dark conditions; conversely, under light conditions, the reduction reaction rate increased to 0.011 and 0.020microM min(-1) at pH 2 and pH 1, respectively, indicating the occurrence of Cr(VI) photo-reduction. The Cr(VI) photo-reduction reaction was induced by the photolysis of water molecules, leading to O(2) production. Upon the addition of Fe(III), the photo-reduction rate of Cr(VI) was significantly enhanced due to the formation of Fe(II), which is the photolytic product of FeCl(2)(+) and the electron donor for Cr(VI) reduction. However, with the same concentration of FeCl complexes, a strong inhibition of Cr(VI) reduction at pH 2 was observed, compared with pH 1. A possible explanation is that FeOH(2+) becomes predominant with increasing pH and that its photolytic product, the OH free radical, is an oxidant for Fe(II) and Cr(III) and can compromise Cr(VI) reduction. The kinetic result of each photo-reduction reaction pathway shows zero-order kinetics, suggesting that the photolysis reaction of H(2)O or FeCl(2+) is the rate-determining step in each pathway. The results also show the potential of developing a homogeneous photo-catalytic method to treat Cr(VI)-containing water.

Chromate reduction on humic acid derived from a peat soil – Exploration of the activated sites on HAs for chromate removal

Humic substances are a major component of soil organic matter that influence the behavior and fate of heavy metals such as Cr(VI), a toxic and carcinogenic element. In the study, a repetitive extraction technique was used to fractionate humic acids (HAs) from a peat soil into three fractions (denoted as F1, F2, and F3), and the relative importance of O-containing aromatic and aliphatic domains in humic substances for scavenging Cr(VI) was addressed at pH 1. Spectroscopic analyses indicated that the concentrations of aromatic C and O-containing functional groups decreased with a progressive extraction as follows: F1>F2>F3. Cr(VI) removal by HA proceeded slowly, but it was enhanced when light was applied due to the production of efficient reductants, such as superoxide radical and H(2)O(2), for Cr(VI). Higher aromatic- and O-containing F1 fraction exhibited a greater efficiency for Cr(VI) reduction (with a removal rate of ca. 2.89 mmol g(-1) HA under illumination for 3 h). (13)C NMR and FTIR spectra further demonstrated that the carboxyl groups were primarily responsible for Cr(VI) reduction. This study implied the mobility and fate of Cr(VI) would be greatly inhibited in the environments containing such organic groups.

Effect of organic complexing ligands on Cr(III) oxidation by MNOx

Although Cr(III) is considered a Cr species with low mobility and toxicity, the potential oxidation of Cr(III) to Cr(VI) in soils containing Mn requires further scientific attention because of the acute toxicity of Cr(VI). This study evaluates the inhibition or enhancement of Cr(III) oxidation by Mn oxide in the presence of various organic ligands and concentrations. Batch experiments indicate that 200 μM of organic ligands inhibited 20 μM Cr(III) oxidation by Mn oxide at pH 4 because of the occurrence of reductive dissolution of Mn oxide. Although oxalate did not show strong inhibition of Cr(III) oxidation at pH 10, nevertheless, citrate and N-hydroxyethyl-ethylenediamine-triacetic acid (HEDTA) ligands did retard Cr(III) oxidation. It is possible that the co-precipitation of Cr(III) and organic ligand, which has a low dissociation constant, results in low release of Cr(III) and subsequent oxidation. The current results imply that the management of Cr(III)-containing waste is very important to prevent potential oxidation of Cr(III) by Mn oxides, particularly at low pH. However, the presence of organic ligands in the field may lead to low Cr(III) oxidation where Cr(III) waste is disposed.