J.C. Liu

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.

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).

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.

Influence of chemical compositions and molecular weights of humic acids on Cr(VI) photo-reduction

Humic acids (HA) strongly affect the fate of trace metals in soils and aquatic environments. One of the remarkable properties of HA is its ability to reduce Cr(VI), an extremely toxic anion. However, it is unclear which HA components are involved in Cr(VI) reduction and possess the photo-induced properties. In this study, an ultrafiltration technique was used to fractionate HAs into four fractions of different nominal molecular weights (M(w)): >100, 50-100, 10-50 and <10 kDa. Each HA fraction was characterized by spectroscopic analyses followed by examining Cr(VI) removal on each fraction of HA at pH 1-5. Spectroscopic results indicated that low-M(w) HA was enriched with polar and aromatic domains. These polar, including polar C in aliphatic region, and aromatic groups were the major sites for Cr(VI) reduction because they disappeared rapidly upon interaction with Cr(VI). As a result, low M(w) of HA exhibited greater efficiency of Cr(VI) reduction. Light induced the rapid transfer of electrons between chromate-phenol/carboxyl ester, or the formation of peroxide radicals or H(2)O(2) through the ready decay of peroxy radicals associated with polar substituents, explained the rapid scavenging of Cr(VI) on polar and aromatic groups of HAs under illumination.

Enhanced chlorophenol sorption of soils by rice-straw-ash amendment.

Rice-straw burning is a common post-harvest practice on rice paddy land, which results in the accumulation of rice-straw ash (RSA) in paddy soil. Because the occurrence of RSA in soil may affect the fate and transport of contaminants, this study investigated the sorption of 3-chlorophenol (3-CP) on RSA and RSA amended soils to evaluate the sorptive properties of RSA in soils. The results showed that the sorption of 3-CP to RSA proceeds through a surface reaction rather than through partitioning and that the neutral form of 3-CP is preferentially sorbed to the surface when compared to the deprotonated anionic form of 3-CP. The addition of RSA to the soils enhanced the overall 3-CP sorption, indicating that RSA amendment may be applied to retard the movement of 3-CP in contaminated soils. As the RSA content in the soils was increased from 0% to 2%, the Langmuir sorption maximum of the soils increased from 18-80 to 256-274 mg kg(-1). Thus, RSA contributed more to the total sorption of the soils than other major components in the soils. Nonetheless, the 3-CP sorption of the soils containing RSA was less than the combination of pure RSA and the soils, thereby indicating that the 3-CP sorption of RSA was suppressed. This may be attributed to the competition of organic matter or other soil components for the surface binding sites of RSA.

Chromate removal as influenced by the structural changes of soil components upon carbonization at different temperatures.

Surface fire could induce heat transferring into the soil, creating a carbonized environment, which may alter the chemical compositions of soil organic matters (SOM). In the study, a surface soil was carbonized at up to 600 °C with limited air to simulate soils experiencing a surface fire, and Cr(VI) removal on the carbonized soils was investigated. NMR and FTIR analyses demonstrated a remarkable change of SOM structures at 300-400 °C. TGA-MS spectra indicated that (e.g. C(2)H(4), CH(3)OH and C(3)H(8)) were the major components in the evolved gases from the pyrolyzed soil. A maximum amount of Cr(VI) removal (ca. 4 mg g(-1) soil) occurred for the 200 °C-carbonized soils, attributed mainly to a significant increase of Cr(VI) reduction by 0.1 M KCl extractable organic carbon (EOC) with abundant carboxylic groups. Nonetheless, the formation of aromatic C upon carbonization of the soil at >400 °C may be responsible for Cr(VI) reduction.