Effect of oxide formation mechanisms on lead adsorption by biogenic manganese (hydr)oxides, iron (hydr)oxides, and their mixtures

The effects of iron and manganese (hydr)oxide formation processes on the trace metal adsorption properties of these metal (hydr)oxides and their mixtures was investigated by measuring lead adsorption by iron and manganese (hydr)oxides prepared by a variety of methods. Amorphous iron (hydr)oxide formed by fast precipitation at pH 7.5 exhibited greater Pb adsorption (gamma(max) = 50 mmol of Pb/mol of Fe at pH 6.0) than iron (hydr)oxide formed by slow, diffusion-controlled oxidation of Fe(II) at pH 4.5-7.0 or goethite. Biogenic manganese(III/IV) (hydr)oxide prepared by enzymatic oxidation of Mn(II) by the bacterium Leptothrix discophora SS-1 adsorbed five times more Pb (per mole of Mn) than an abiotic manganese (hydr)oxide prepared by oxidation of Mn(II) with permanganate, and 500-5000 times more Pb than pyrolusite oxides (betaMnO2). X-ray crystallography indicated that biogenic manganese (hydr)oxide and iron (hydr)oxide were predominantly amorphous or poorly crystalline and their X-ray diffraction patterns were not significantly affected by the presence of the other (hydr)oxide during formation. When iron and manganese (hydr)oxides were mixed after formation, or for Mn biologically oxidized with iron(III) (hydr)oxide present, observed Pb adsorption was similar to that expected for the mixture based on Langmuir parameters for the individual (hydr)oxides. These results indicate that interactions in iron/manganese (hydr)oxide mixtures related to the formation process and sequence of formation such as site masking, alterations in specific surface area, or changes in crystalline structure either did not occur or had a negligible effect on Pb adsorption by the mixtures.     

Reoxidation of reduced uranium with iron(III) (hydr)oxides under sulfate-reducing conditions

In cultures of Desulfovibrio desulfuricans 620 the effects of iron(III) (hydr)oxides (hematite, goethite, and ferrihydrite) on microbial reduction and reoxidation of uranium (U) were evaluated under lactate-limited sulfate-reducing conditions. With lactate present, G20 reduced U(VI) in both 1,4-piperazinediethanesulfonate (PIPES) and bicarbonate buffer. Once lactate was depleted, however, microbially reduced U served as an electron donor to reduce Fe(III) present in iron(III) (hydr)oxides. With the same initial amount of Fe(III) (10 mmol/L) for each iron(III) (hydr)oxide, reoxidation of U(IV) was greater with hematite than with goethite orferrihydrite. As the initial mass loading of hematite increased from 0 to 20 mmol of Fe(III)/L, the rate and extent of U(IV) reoxidation increased. Subsequent addition of hematite [15 mmol of Fe(III)/L] to stationary-phase cultures containing microbially reduced U(IV) also resulted in rapid reoxidation to U(VI). Analysis by U L3-edge X-ray absorption near-edge spectroscopy (XANES) of microbially reduced U particles yielded spectra similar to that of natural uraninite. Observations by high-resolution transmission electron microscopy, selected area electron diffraction, and energy-dispersive X-ray spectroscopic analysis confirmed that precipitated U associated with cells was uraninite with particle diameters of 3-5 nm. By the same techniques, iron sulfide precipitates were found to have a variable Fe and S stoichiometry and were not associated with cells.     

Atomistic simulations of uranium incorporation into iron (hydr)oxides

Atomistic simulations were carried out to characterize the coordination environments of U incorporated in three Fe-(hydr)oxide minerals: goethite, magnetite, and hematite. The simulations provided information on U-O and U-Fe distances, coordination numbers, and lattice distortion for U incorporated in different sites (e.g., unoccupied versus occupied sites, octahedral versus tetrahedral) as a function of the oxidation state of U and charge compensation mechanisms (i.e., deprotonation, vacancy formation, or reduction of Fe(III) to Fe(II)). For goethite, deprotonation of first shell hydroxyls enables substitution of U for Fe(III) with a minimal amount of lattice distortion, whereas substitution in unoccupied octahedral sites induced appreciable distortion to 7-fold coordination regardless of U oxidation states and charge compensation mechanisms. Importantly, U-Fe distances of ～3.6 ? were associated with structural incorporation of U and cannot be considered diagnostic of simple adsorption to goethite surfaces. For magnetite, the octahedral site accommodates U(V) or U(VI) with little lattice distortion. U substituted for Fe(III) in hematite maintained octahedral coordination in most cases. In general, comparison of the simulations with available experimental data provides further evidence for the structural incorporation of U in iron (hydr)oxide minerals.     

Reduction of Tc(VII) by Fe(II) sorbed on Al (hydr)oxides

Under oxic conditions, Tc exists as the soluble, weakly sorbing pertechnetate [TcO4-] anion. The reduced form of technetium, Tc(IV), is stable in anoxic environments and is sparingly soluble as TcO2 x nH2O(s). Here we investigate the heterogeneous reduction of Tc(VII) by Fe(II) adsorbed on Al (hydr)oxides [diaspore (alpha-AlOOH) and corundum (alpha-Al2O3)]. Experiments were performed to study the kinetics of Tc(VII) reduction, examine changes in Fe surface speciation during Tc(VII) reduction (M?ssbauer spectroscopy), and identify the nature of Tc(IV)-containing reaction products (X-ray absorption spectroscopy). We found that Tc(VII) was completely reduced by adsorbed Fe(II) within 11 (diaspore suspension) and 4 days (corundum suspension). M?ssbauer measurements revealed thatthe Fe(II) signal became less intense with Tc(VII) reduction and was accompanied by an increase in the intensity of the Fe(III) doublet and magnetically ordered Fe(III) sextet signals. Tc-EXAFS spectroscopy revealed that the final heterogeneous redox product on corundum was similar to Tc(IV) oxyhydroxide, TcO2 x nH2O.     

Kinetics and mechanisms for reactions of Fe(II) with iron(III) oxides

Uptake of Fe(II) onto hematite (alpha-Fe2O3), corundum (alpha-Al2O3), amorphous ferric oxide (AFO), and a mixture of hematite and AFO was measured. Uptake was operationally divided into adsorption (extractable by 0.5 N HCl within 20 h) and fixation (extractable by 3.0 N HCl within 7 d). For 0.25 mM Fe(II) onto 25 mM iron(III) hematite at pH 6.8: (i) 10% of Fe(II) was adsorbed within 1 min; (ii) 20% of Fe(II) was adsorbed within 1 d; (iii) uptake slowly increased to 24% of Fe(II) during the next 24 d, almost all adsorbed; (iv) at 30 d, the uptake increased to 28% of Fe(II) with 6% of total Fe(II) fixed; and (v) uptake slowly increased to 30% of Fe(II) by 45 d with 10% of total Fe(II) fixed. Similar results were observed for 0.125 mM Fe(II) onto 25 mM iron(III) hematite, except that percent of adsorption and fixation were increased. There was adsorption but no fixation for 0.25 mM Fe(II) onto corundum [196.2 mM Al(III)] at pH 6.8, for 0.125 mM Fe(II) onto 25 mM iron(III) hematite at pH 4.5, and for 0.25 mM Zn(II) onto 25 mM iron(III) hematite at pH 6.8. A small addition of AFO to the hematite suspension increased Fe(II) fixation when 0.25 mM Fe(II) was reacted with 25 mM iron(III) hematite and 0.025 mM Fe(III) AFO at pH 6.8. Reaction of 0.125 mM Fe(II) with 2.5 mM Fe(III) AFO resulted in rapid adsorption of 30% of added Fe(II), followed by conversion of AFO to goethite and a decrease in adsorption without Fe(II) fixation. The fixation of Fe(II) by hematite at pH 6.8 is consistent with interfacial electron transfer and the formation of new mineral phases. We propose that electron transfer from adsorbed Fe(II) to structural Fe(III) in hematite results in oxidation of Fe(II) to AFO on the surface of hematite and that solid-phase contact among hematite, AFO, and structural Fe(II) produces magnetite (Fe3O4). The unique interactions of Fe(II) with iron(III) oxides would be environmentally important to understand the fate of redox-sensitive chemicals.     

Sorption of uranium(VI) onto ferric oxides in sulfate-rich acid waters

The mechanisms of the uranium(VI) sorption on schwertmannite and goethite in acid sulfate-rich solutions were studied by Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The samples were prepared under N2 atmosphere and initial uranium(VI) concentrations of 1 x 10(-5) (pH 6.5) to 5 x 10(-5) M (pH 4.2). The ionic strength was adjusted using 0.01 M Na2SO4 or 0.01 M NaClO4, respectively. The EXAFS structural parameters for uranium(VI) sorbed on goethite in sulfate-rich, acid and near-neutral solutions indicate that uranium(VI) forms an inner-sphere, mononuclear, bidentate surface complex. This complex is characterized by a uranium-ferric-iron distance of approximately 3.45 A. Uranium(VI) sorbed onto schwertmannite in acid and sulfate-rich solution is coordinated to one or two sulfate molecules with a uranium-sulfur distance of 3.67 A. The EXAFS results indicate formation of binuclear, bidentate surface complexes and partly of mononuclear, monodentate surface complexes coordinated to the structural sulfate of schwertmannite. The formation of ternary uranium(VI)-sulfate surface complexes could not be excluded because of the uncertainty in assigning the sulfate either to the bulk structure or to adsorption reactions. The uranium(VI) adsorption onto schwertmannite in perchlorate solution occurs predominantly as a mononuclear, bidentate complexation with ferric iron due to the release of sulfate from the substrate.     

Impacts of Shewanella putrefaciens strain CN-32 cells and extracellular polymeric substances on the sorption of As(V) and As(III) on Fe(III)-(hydr)oxides

We investigated the effects of Shewanella putrefaciens cells and extracellular polymeric substances on the sorption of As(III) and As(V) to goethite, ferrihydrite, and hematite at pH 7.0. Adsorption of As(III) and As(V) at solution concentrations between 0.001 and 20 μM decreased by 10 to 45% in the presence of 0.3 g L(-1) EPS, with As(III) being affected more strongly than As(V). Also, inactivated Shewanella cells induced desorption of As(V) from the Fe(III)-(hydr)oxide mineral surfaces. ATR-FTIR studies of ternary As(V)-Shewanella-hematite systems indicated As(V) desorption concurrent with attachment of bacterial cells at the hematite surface, and showed evidence of inner-sphere coordination of bacterial phosphate and carboxylate groups at hematite surface sites. Competition between As(V) and bacterial phosphate and carboxylate groups for Fe(III)-(oxyhydr)oxide surface sites is proposed as an important factor leading to increased solubility of As(V). The results from this study have implications for the solubility of As(V) in the soil rhizosphere and in geochemical systems undergoing microbially mediated reduction and indicate that the presence of sorbed oxyanions may affect Fe-reduction and biofilm development at mineral surfaces.     

Phosphonate- and carboxylate-based chelating agents that solubilize (hydr)oxide-bound MnIII

Recent field studies suggest that dissolved MnIII should be ubiquitous at oxic/anoxic interfaces in all natural waters and may play important roles in biogeochemical redox processes. Here, we uncovered environmentally relevant synthetic phosphonate-based chelators that solubilize (hydr)oxide-bound MnIII via ligand-promoted dissolution at circum-neutral pHs and that their ability to release aqueous MnIII can be predicted based on the chemical structure. For two (hydr)oxides (manganite and birnessite) reacting with excess concentrations of pyrophosphoric acid (PP), methylenediphosphonic acid (MDP), and phosphonoacetic acid (PAA), ligand-promoted dissolution is predominant from pH 6--8, initial dissolution rates and plateau concentrations for dissolved MnIII decrease in the order PP > MDP > PAA, and at pH 5, MDP reacts equally well (with birnessite) or more efficiently (with manganite) than PP, and PAA remains the least reactive chelator. For manganite reacting with an excess concentration of aminophosphonate/carboxylate-based chelators, the aminophosphonate-containing iminodimethylenephosphonic acid and glyphosate yield appreciable amounts of dissolved MnIII, but the aminocarboxylate-based methyliminodiacetic acid yields solely dissolved MnII via MnIII reduction.     

Differential potentiometric titration: development of a methodology for determining the point of zero charge of metal (hydr)oxides by one titration curve

A new methodology is presented, called differential potentiometric titration (DPT), which allows the determination of the point of zero charge (pzc) of metal (hydr)oxides using only one potentiometric curve. By performing extensive simulations of potentiometric titrations for various model (hydr)oxides, we found that an inflection point in a H+(cons,surf) versus pH potentiometric curve (H+(cons,surf): hydrogen ions consumed on the surface of the (hydr)oxide) and a peak in the corresponding differential curve, dH+(cons,surf)/dpH versus pH, appear at a pH equal to the pzc assumed for a model (hydr)oxide. This distinguishable peak appears at the same position irrespective of the surface ionization and the interfacial model adopted as well as the assumed ionic strength. It was found that the aforementioned peak also appears in the high-resolution differential potentiometric curves experimentally determined for four oxides (SiO2, TiO2, gamma-Al2O3, and MgO) that are widely used in various environmental and other technological applications. The application of DPT to the above-mentioned oxides provided practically the same pzc values as the corresponding ones achieved by using four different techniques as well as the corresponding isoelectric point (iep) values determined by microelectrophoresis. Differences between the pzc and iep values determined using various techniques in the case of MgO were attributed to the increasing dissolution of this oxide as pH decreases and the adsorption of cations (Mg2+, Na+) on the MgO/electrolytic solution interface.     

Redox and complexation interactions of neptunium(V) with quinonoid-enriched humic derivatives

Actinides in their higher valence states (e.g., MO2+ and MO2(2+), where M can be Np, Pu, etc) possess a higher potential for migration and in turn pose a substantial environmental threat. To minimize this potential for migration, reducing them to lower oxidation states (e.g., their tetravalent state) can be an attractive and efficient remedial process. These lower oxidation states are often much less soluble in natural aqueous media and are, therefore, less mobile in the environment. The research presented here focuses on assessing the performance of quinonoid-enriched humic derivatives with regardsto complexing and/ or reducing Np(V) present in solution. These "designer" humics are essentially derived reducing agents that can serve as reactive components of a novel humic-based remediation technology. The derivatives are obtained by incorporating different quinonoid-moieties into leonardite humic acids. Five quinonoid-derivatives are tested in this work and all five prove more effective as reducing agents for selected actinides than the parent leonardite humic acid, and the hydroquinone derivatives are better than the catechol derivatives. The reduction kinetics and the Np(V) species formed with the different derivatives are studied via a batch mode using near-infrared (NIR)-spectroscopy. Np(V) reduction by the humic derivatives under anoxic conditions at 293 K and at pH 4.7 obeys first-order kinetics. Rate constants range from 1.70 x 10(-6) (parent humic acid) to 1.06 x 10(-5) sec(-1) (derivative with maximum hydroquinone content). Stability constants for Np(V)-humic complexes calculated from spectroscopic data produce corresponding Logbeta values of 2.3 for parent humic acid and values ranging from 2.5 to 3.2 at pH 4.7 and from 3.3 to 3.7 at pH 7.4 for humic derivatives. Maximum constants are observed for hydroquinone-enriched derivatives. It is concluded that among the humic derivatives tested, the hydroquinone-enriched ones are the most useful for addressing remedial needs of actinide-contaminated aquifers.     

Subsurface interactions of Fe(II) with humic acid or landfill leachate do not control subsequent iron(III) (hydr)oxide production at the surface

At least 93% of Fe(II) remained free, as defined by ferrozine assay under anoxic conditions in the presence of humic acid (HA) and two simulated landfill leachates of different maturities. However, tangential flow ultrafiltration showed a weaker but more extensive interaction of Fe with organic carbon (OC); 90% of Fe associated with the less mature leachate. Despite the existence of this weak interaction under anoxic conditions, there was no difference in iron(III) (hydr)oxide production whether HA was added prior to or coincident with the oxidation of Fe(II) on exposure to oxic conditions. Under oxic conditions ferrozine showed that more Fe(II) bound to OC, up to 50% to HA. However, this occurs via oxidation of Fe(II) to Fe(III), which is bound and then thermally reduced. This affinity for Fe(III) and the ability to carry out thermal reduction both increase with the maturity of the OC. The rate at which ferrozine-defined free Fe(II) was lost on exposure to dissolved oxygen was also enhanced by the more mature OC, while it was slowed by acetogenic leachate. The slowing must be a consequence of the filtration-defined Fe(II)/OC interaction.     

Influence of sediment components on the immobilization of Zn during microbial Fe-(hydr)oxide reduction

The fate of Zn and other sorbed heavy metals during microbial reduction of iron oxides is different when comparing synthetic Fe-(hydr)oxides and natural sediments undergoing a similar degree of iron reduction. Batch experiments with the iron-reducing organism Shewanella putrefaciens were conducted to examine the effects of an aqueous complexant (nitrilotriacetic acid or NTA), two solid-phase complexants (kaolinite and montmorillonite), an electron carrier (anthraquinone disulfonic acid or AQDS), and a humic acid on the speciation of Zn during microbial reduction of synthetic goethite. Compared to systems containing only goethite and Zn, microbial Fe(III) reduction in the presence of clay resulted in up to a 50% reduction in Zn immobilization (insoluble in a 2 h 0.5 M HCl extraction) without affecting Fe(II) production. NTA (3 mM) increased Fe(II) production 2-fold and resulted in recovery of nearly 75% of Zn in the aqueous fraction. AQDS (50 microM) resulted in a 12.5% decrease in Fe(II) production and a 44% reduction in Zn immobilization. Humic acid additions resulted in up to a 25% decrease in Fe(II) production and 51% decrease in Zn immobilization. The results suggest that all the components examined here as either complexing agents or electron shuttles reduce the degree of Zn immobilization by limiting the availability of Zn for incorporation into newly formed biogenic minerals. These results have implications for the remediation of heavy metals in a variety of natural sediments.     

Arsenic(III) and arsenic(V) reactions with zerovalent iron corrosion products

Zerovalent iron (Fe0) has tremendous potential as a remediation material for removal of arsenic from groundwater and drinking water. This study investigates the speciation of arsenate (As(V)) and arsenite (As(III)) after reaction with two Fe0 materials, their iron oxide corrosion products, and several model iron oxides. A variety of analytical techniques were used to study the reaction products including HPLC-hydride generation atomic absorption spectrometry, X-ray diffraction, scanning electron microscopy-energy-dispersive X-ray analysis, and X-ray absorption spectroscopy. The products of corrosion of Fe0 include lepidocrocite (gamma-FeOOH), magnetite (Fe3O4), and/or maghemite (gamma-Fe2O3), all of which indicate Fe(II) oxidation as an intermediate step in the Fe0 corrosion process. The in-situ Fe0 corrosion reaction caused a high As(III) and As(V) uptake with both Fe0 materials studied. Under aerobic conditions, the Fe0 corrosion reaction did not cause As(V) reduction to As(III) but did cause As(III) oxidation to As(V). Oxidation of As(III) was also caused by maghemite and hematite minerals indicating that the formation of certain iron oxides during Fe0 corrosion favors the As(V) species. Water reduction and the release of OH- to solution on the surface of corroding Fe0 may also promote As(III) oxidation. Analysis of As(III) and As(V) adsorption complexes in the Fe0 corrosion products and synthetic iron oxides by extended X-ray absorption fine structure spectroscopy (EXAFS) gave predominant As-Fe interatomic distances of 3.30-3.36 A. This was attributed to inner-sphere, bidentate As(III) and As(V) complexes. The results of this study suggest that Fe0 can be used as a versatile and economical sorbent for in-situ treatment of groundwater containing As(III) and As(V).     

Formation of lead(IV) oxides from lead(II) compounds

Lead(IV) oxide (PbO(2)) is a corrosion product that can develop on lead pipes used for drinking water supply, and its stability can control lead concentrations in tap water. A set of batch experiments were performed to determine the extent of PbO(2) formation as a function of time, pH, the presence of dissolved inorganic carbon (DIC), and free chlorine concentration. Experiments were conducted with four lead(II) compounds that are precursors of PbO(2) formation: dissolved lead(II) chloride, massicot (β-PbO), cerussite (PbCO(3)), and hydrocerussite (Pb(3)(OH)(2)(CO(3))(2)). While PbO(2) formed in the presence and absence of DIC, the presence of DIC accelerated PbO(2) formation and affected the identity of the PbO(2) (scrutinyite vs plattnerite) product. For some conditions, intermediate solids formed that affected the identity of the PbO(2) produced. When no intermediate solids formed, hydrocerussite led to the formation of pure scrutinyite, and lead(II) chloride and massicot led to mixtures of scrutinyite and plattnerite. Based on the experimental results, a conceptual model of lead(IV) oxide formation pathways was proposed.     

Kinetics of haloacetic acid reactions with Fe(0)

Detailed kinetic studies of the reactions of haloacetic acids (HAAs) with Fe(0) were performed in longitudinally mixed batch reactors. The reactions of tribromoacetic acid (TBAA), bromodichloroacetic acid, and chlorodibromoacetic acid were mass transfer limited, with corrected mass transfer coefficients of 3.7-3.9 x 10(-4) m/s. The reactions of trichloroacetic acid (TCAA), dichloroacetic acid (DCAA), chloroacetic acid (CAA), and bromoacetic acid (BAA) were reaction limited. Bromochloroacetic acid (BCAA) and dibromoacetic acid (DBAA) were partially reaction limited. For the reaction limited species and partially reaction limited species, intra- and interspecies competition effects were observed. A Langmuir-Hinshelwood-Hougen-Watson kinetic model incorporating a mass transfer term was adopted to account for these effects. The lumped kinetic parameters for the HAAs ranged from 0.04 to 248 microM min(-1) for an iron loading of 0.3 g of Fe/125 mL and followed the trend DBAA > BCAA > TCAA > BAA > DCAA. The adsorption parameters ranged from 0.0007 to 0.0065 microM(-1). The effect of dissolved oxygen (DO) on the reaction of TBAA or BAA with Fe(0) was also investigated. No significant effect of DO on the reaction rate of TBAA, which is a mass transfer limited species, was observed. A lag phase, however, was observed for the reaction of BAA, which is a reaction limited species, until the DO was depleted. Simulations were performed to investigate the potential significance of the reactions of HAAs with Fe(0) in water distribution systems.     

Simultaneous microbial reduction of iron(III) and arsenic(V) in suspensions of hydrous ferric oxide

Bacterial reduction of arsenic(V) and iron(III) oxides influences the redox cycling and partitioning of arsenic (As) between solid and aqueous phases in sediment-porewater systems. Two types of anaerobic bacterial incubations were designed to probe the relative order of As(V) and Fe(III) oxide reduction and to measure the effect of adsorbed As species on the rate of iron reduction, using hydrous ferric oxide (HFO) as the iron substrate. In one set of experiments, HFO was pre-equilibrated with As(V) and inoculated with fresh sediment from Haiwee Reservoir (Olancha, CA), an As-impacted field site. The second set of incubations consisted of HFO (without As) and As(III)- and As(V)- equilibrated HFO incubated with Shewanella sp. ANA-3 wild-type (WT) and ANA-3deltaarrA, a mutant unable to produce the respiratory As(V) reductase. Of the two pathways for microbial As(V) reduction (respiration and detoxification), the respiratory pathway was dominant under these experimental conditions. In addition, As(III) adsorbed onto the surface of HFO enhanced the rate of microbial Fe(III) reduction. In the sediment and ANA-3 incubations, As(V) was reduced simultaneously or prior to Fe(III), consistent with thermodynamic calculations based on the chemical conditions of the ANA-3 WT incubations.     

Speciation of bioaccessible (heme,ferrous and ferric) iron from school menus

A spectrophotometric method using batho-phenantroline as reagent has been optimized for iron speciation [ionic Fe(II) and Fe(III)] in the mineral soluble (bioaccessible) fraction obtained from the in vitro digestion of food dishes. The effect of the precipitant and reducing reagents, and the amount of sodium nitrite added was studied. Heme-Fe was estimated by subtraction of ionic Fe from the total bioaccessible Fe (determined by atomic absorption spectrometry). The method was applied to 13 dishes included in school menus. Soluble Fe was mainly in ionic form (49–100%). With the exception of spinach and potato omelets, a significant linear correlation (r=0.92) was obtained between Fe(II) and bioaccessible Fe. The Fe(II)/Fe(III) ratio increased with increasing meat protein content in the dish. In the analyzed dishes, heme-Fe content depended on meat content and also on the processing procedure applied.     

Chemistry and reactions of reactive oxygen species in foods

Reactive oxygen species (ROS) are formed enzymatically, chemically, photochemically, and by irradiation of food. They are also formed by the decomposition and the inter-reactions of ROS. Hydroxy radical is the most reactive ROS, followed by singlet oxygen. Reactions of ROS with food components produce undesirable volatile compounds and carcinogens, destroy essential nutrients, and change the functionalities of proteins, lipids, and carbohydrates. Lipid oxidation by ROS produces low molecular volatile aldehydes, alcohols, and hydrocarbons. ROS causes crosslink or cleavage of proteins and produces low molecular carbonyls from carbohydrates. Vitamins are easily oxidized by ROS, especially singlet oxygen. The singlet oxygen reaction rate was the highest in ss-carotene, followed by tocopherol, riboflavin, vitamin D, and ascorbic acid.