Catalyzed oxidation of arsenic(III) by hydrogen peroxide on the surface of ferrihydrite: an in situ ATR FTIR study

Knowledge of arsenic redox kinetics is crucial for understanding the impact and fate of As in the environment and for optimizing As removal from drinking water. Rapid oxidation of As(III) adsorbed to ferrihydrite (FH) in the presence of hydrogen peroxide (H2O2) might be expected for two reasons. First, the adsorbed As(III) is assumed to be oxidized more readily than the undissociated species in solution. Second, catalyzed decomposition of H2O2 on the FH surface might also lead to As(III) oxidation. Attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy was used to monitor the oxidation of adsorbed As(III) on the FH surface in situ. No As(III) oxidation within minutes to hours was observed prior to H2O2 addition. Initial pseudo-first-order oxidation rate coefficients for adsorbed As(III), determined at H2O2 concentrations between 8.4 microM and 8.4 mM and pH values from 4 to 8, increased with the H2O2 concentration according to the equation log k(ox) (min(-1)) = 0.17 + 0.50 log [H2O] (mol/L), n = 21, r2 = 0.87. Only a weak pH dependence of log k(ox) was observed (approximately 0.04 logarithm unit increase per pH unit). ATR-FTIR experiments with As(III) adsorbed onto amorphous aluminum hydroxide showed that Fe was necessary to induce As(III) oxidation by catalytic H2O2 decomposition. Supplementary As(III) oxidation experiments in FH suspensions qualitatively confirmed the findings from the in situ ATR-FTIR experiments. Our results indicate that the catalyzed oxidation of As(III) by H2O2 on the surface of iron (hydr)oxides might be a relevant reaction pathway in environmental systems such as surface waters, as well as in engineered systems for As removal from water.     

Photocatalytic oxidation of arsenite in TiO2 suspension: kinetics and mechanisms

Arsenite [As(III)] and arsenate [As(V)] are highly toxic aquatic contaminants. Since arsenite is more mobile in natural waters and less efficiently removed in adsorption/coagulation processes than arsenate, the oxidation of arsenite to arsenate is desirable in water treatment. We performed the photocatalytic oxidation of arsenite in aqueous TiO2 suspension and investigated the effects of pH, dissolved oxygen, humic acid (HA), and ferric ions on the kinetics and mechanisms of arsenite oxidation. Arsenite oxidation in UV-illuminated TiO2 suspension was highly efficient in the presence of dissolved oxygen. Homogeneous photooxidation of arsenite in the absence of TiO2 was negligibly slow. Since the addition of excess tert-butyl alcohol (OH radical scavenger) did not reduce the rate of arsenite oxidation, the OH radicals should not be responsible for As(III) oxidation. The addition of HA increased both arsenite oxidation and H2O2 production at pH 3 under illumination, which could be ascribed to the enhanced superoxide generation through sensitization. We propose that the superoxide is the main oxidant of arsenite in the TiO2/UV process. The addition of ferric ions also significantly enhanced the arsenite photooxidation. In this case, the addition of tert-butyl alcohol reduced the arsenite oxidation rate, which implied thatthe OH radical-mediated oxidation path was operative in the presence of ferric ions. Since both Fe3+ and HA that were often found with the arsenic in groundwater were beneficial to the photocatalytic oxidation of arsenite, the TiO2/UV process could be a viable pretreatment method. This can be as simple as exposing the arsenic-polluted water in a TiO2-coated trough to sunlight.     

Photocatalytic oxidation of arsenic(III): evidence of hydroxyl radicals

Arsenic contamination has been found in the groundwater of several countries. Photocatalysis can rapidly oxidize arsenite (As(III)) to less labile and less toxic arsenate (As(V)), which then can be removed by adsorption onto photocatalyst surfaces. This study investigates the photocatalytic oxidation of As(III) to As(V) as a function of As(III) concentration, pH, catalyst loading, light intensity, dissolved oxygen concentration, type of TiO2 surfaces, and ferric ions to understand the kinetics and the mechanism of As(III) oxidation in the UV/TiO2 system. Photocatalytic oxidation of As(III) to As(V) takes place in minutes and follows zero-order kinetics. Benzoic acid (BA) was used as a hydroxyl radical (.OH) scavenger to provide evidence for the .OH as the main oxidant for oxidation of As(III). The .OH radical was independently generated by nitrate photolysis, and kinetics of As(III) oxidation by the .OH radical was determined. Formation of salicylic acid (SA) from the oxidation of BA by .OH also demonstrates the involvement of .OH in the mechanism of As(III) oxidation. The effect of Fe(III) on As(III) oxidation at different pH values with and without TiO2 under UV light was examined. The results suggest that .OH is the dominant oxidant for As(III) oxidation. Two commercially available TiO2 suspensions, Degussa P25 and Hombikat UV100, were tested for the removal of arsenic through oxidation of As(III) to As(V) followed by adsorption of As(V) onto TiO2 surfaces. Results showed that complete removal of arsenic below the World Health Organization drinking water limit of 10 microg/L could be achieved.     

花生分离蛋白氧化过程中的结构变化

利用2,2-盐酸脒基丙烷(AAPH)在有氧条件下热分解产生的烷过氧自由基(ROO·),对花生分离蛋白进行不同程度的氧化修饰,采用傅里叶红外变换光谱,结合去卷积和曲线拟合技术,研究花生分离蛋白氧化过程中的二级结构变化。结果表明,经去卷积后花生分离蛋白红外光谱酰胺I带共分出10个峰,表征聚集体形成的1 618,1 682 cm-1的吸收值在氧化过程中升高,表明在氧化过程中形成了蛋白聚集体。利用曲线拟合对酰胺I带进行定量分析,结果表明,当AAPH浓度小于3.00 mmol/L时,β-折叠和无规则卷曲含量升高,而β-转角和α-螺旋含量下降;在高氧化浓度(5.00,10.00 mmol/L)下,花生分离蛋白发生多肽链的断裂,进而影响其二级结构的变化。AAPH的浓度不同,花生分离蛋白之间的分子相互作用强度不同。在花生分离蛋白聚集体形成中,氢键和疏水相互作用发挥着重要作用。     

Photocatalytic oxidation of aqueous ammonia over microwave-induced titanate nanotubes

Characterizations of microwave-induced titanate nanotubes (NaxH(2-x)Ti3O7, TNTs) were conducted by the determinations of specific surface area (S(BET)), X-ray diffraction (XRD), X-ray photoelectron spectroscopic (XPS), ionic coupled plasma-atomic emission spectrometry(ICP-AES), scanning electron microscopy/ energy dispersive X-ray (SEM/EDX), and high-resolution transmission electron microscopy (HR-TEM). The applied level of microwave irradiation during the fabrication process is responsible for both the intercalation intensity of Na atoms into TNTs and the type of crystallization phase within TNTs, which dominate the efficiency of photocatalytic NH3/NH4+. A pure TNT phase presents no powerful ability toward photocatalytic NH3/ NH4+, while the photocatalytic efficiency can be enhanced with the presence of a rutile phase within TNTs. In addition, the mixture of anatase and rutile phase within P25 TiO2 prefers forming NO3-, whereas TNTs yield higher NO2- amount Regarding the effect of acid-washing treatment on TNTs, the acid-treated TNTs with enhanced ion exchangeability considerably improve the NH3/NH4+ degradation and NO2-/NO3- yields. This result is likely ascribed to the easy intercalation of NH3/ NH4+ into the structure of acid-washing TNTs so that the photocatalytic oxidation of intercalated NH3/NH4+ is not limited to the shielding effect resulting from the overload of TNTs.     

Photocatalytic oxidation and decomposition of acetic acid on titanium silicalite

Transient reaction of adsorbed monolayers of acetic acid was used to characterize the photocatalytic properties of titanium silicalite zeolites (TS-1). The TS-1 zeolites having Si/Ti ratios of 5, 12.5, and 50 are effective catalysts at room temperature for both photocatalytic oxidation (PCO) and decomposition (PCD) of acetic acid. The rates of PCO are higher than the rates of PCD for each catalyst. Acetic acid oxidized photocatalytically in 0.2% O2 to form gas-phase CO2 and CH4 and adsorbed H2O on the TS-1 catalysts, whereas no CH4 formed on Degussa P25 TiO2. Isotope labeling showed that, on both TiO2 and TS-1 catalysts, the alpha-carbon formed CO2 whereas the beta-carbon formed CH4 and CO2. The rates of oxidation of the two carbons have different dependencies on UV intensity. The catalysts with higher Si/Ti ratios adsorbed significantly more acetic acid, and the PCO rates per gram of titanium are highest on the TS-1 catalyst with the lowest Ti content, apparently because a larger fraction of the Ti atoms are surface atoms on this catalyst. During PCD in an inert atmosphere, CO2, CH4, and C2H6 formed on TiO2 and on the catalyst with a Si/Ti ratio of 5, but C2H6 was not detected on the other catalysts. The CO2/CH4 selectivity during PCD increased with increasing Si/Ti ratio. The first step in PCO and PCD on TS-1 catalysts appears to be similar and involves formation of a CH3 radical.     

Photocatalytic oxidation of gaseous 2-chloroethyl ethyl sulfide over TiO2

Photocatalytic oxidation of gaseous 2-chloroethyl ethyl sulfide (2-CEES, ClCH2CH2SCH2CH3) over TiO2 illuminated with UV light and maintained at 25 or 80 degrees C in air has been investigated. 2-CEES was found to suffer progressive oxidation to yield ethylene (CH2CH2), chloroethylene (ClCHCH2), ethanol (CH3CH2OH), acetaldehyde (CH3C(O)H), chloroacetaldehyde (ClCH2C(O)H), diethyl disulfide (CH3CH2S2CH2CH3), 2-chloroethyl ethyl disulfide (ClCH2CH2S2CH2CH3), and bis(2-chloroethyl) disulfide (ClCH2CH2S2CH2CH2Cl) as the main primary intermediates, and water (H2O), carbon dioxide (CO2), sulfur dioxide (SO2), surface sulfate ions (SO4(2-)), and hydrogen chloride (HCl) as the final products. Trace concentrations of gaseous 2-chloroethanol (ClCH2CH2OH), ethanesulfonyl chloride (CH3CH2SO2Cl), ethyl thioacetate (CH3CH2SC(O)CH3), and considerable amounts of acetic acid (CH3C(O)OH), crotonaldehyde (CH3CHCHC(O)H), methyl acetate (CH3C(O)OCH3), and methyl formate (CH3OC(O)H) were also detected in the gas phase during the photooxidation conducted at 80 degrees C. Increase in temperature from 25 to 80 degrees C accelerates formation of gaseous ethanol, acetaldehyde, chloroacetaldehyde, diethyl disulfide, 2-chloroethyl ethyl disulfide, and bis(2-chloroethyl) disulfide but suppresses ethylene and chloroethylene production at initial stages of the process. Some aspects of the possible reaction mechanism leading to this wide array of intermediates and final products are discussed.     

Photocatalytic oxidation of arsenite on TiO2: understanding the controversial oxidation mechanism involving superoxides and the effect of alternative electron acceptors

Previously we have reported that superoxide plays the primary role as oxidant of As(III) in the UV/TiO2 system, however, since then there has been a controversy over the true identity of the major As(III) oxidant. This study aims to establish a comprehensive understanding of the oxidative mechanism which satisfactorily explains all of the observed results during the photocatalytic oxidation (PCO) of As(III). The key step that has masked the true oxidative mechanism is related to the fact that the adsorbed As(III) on TiO2 serves as an external charge-recombination center where the reaction of As(III) with an OH radical (or hole) is immediately followed by an electron transfer to make a null cycle. This was confirmed by the observation that the photoanodic current obtained with a TiO2 electrode immediately decreased upon spiking with As(III), portraying the superoxide-mediated PCO as the dominant pathway. The degradation of competitive substrates (benzoic acid and formic acid) was delayed until As(III) was fully converted into As(V) since the normal PCO mechanism that is based on the action of adsorbed OH radicals (or holes) is not working as long as As(III) is present on the TiO2 surface. However, the As(III) PCO mechanism is entirely altered when alternative electron acceptors (Ag+, Cu2+, polyoxometalate) are present. When these alternative electron acceptors are more efficient than 02 they are able to intercept the CB electron, impeding the recombination pathway and enabling an anoxic oxidation mechanism in which OH radicals and holes play the role of main As(III) oxidant. In the presence of polyoxometalate or Cu2+, the above-mentioned photoanodic current immediately increases upon spiking As(III), indicating that the PCO mechanism has changed in the presence of more efficient electron acceptors. Comprehensive mechanisms of As(III) PCO and experimental factors that alter the mechanism are discussed.     

Mechanistic aspects of pyrite oxidation in an oxidizing gaseous environment: an in situ HATR-IR isotope study

The reaction of FeS2 (pyrite) with gaseous H2O, O2, and H2O/O2 was investigated using horizontal attenuated total reflection Fourier transform infrared spectroscopy (HATR-FTIR). Spectra were interpreted with the aid of hybrid molecular orbital/density functional theory calculations of sulfate-iron hydroxide clusters. Reaction of pyrite in gaseous H2O led primarily to the formation of iron hydroxide on pyrite. Exposure of the pyrite to gaseous O2 after exposure to H2O vapor led to the formation of sulfur oxyanions that included SO42-. Isotopic labeling experiments showed that after this exposure sequence the oxygen in the sulfate product was primarily derived from the H2O reactant. If, however, pyrite was exposed to gaseous O2 prior to pure H2O vapor, both SO42- and iron oxyhydroxide became significant products. Isotopic rabeling experiments using the O2-then-H2O sequence showed that the oxygen in the SO42- product was derived from both H2O and O2. The results indicate that H2O and O2 exhibit a competitive adsorption on pyrite, with H2O blocking surface sites for O2 adsorption. The extent of oxygen incorporation from either the H2O or the O2 component into the surface-bound sulfur oxyanion product appears to be a strong function of the relative concentration ratio of the reactant H2O and O2.     

Recovery of phenanthrene-degrading bacteria after simulated in situ persulfate oxidation in contaminated soil

A continuous-flow column study was conducted to investigate the long-term effects of persulfate oxidation on the abundance and activity of the indigenous microbial community and phenanthrene-degrading bacteria in contaminated soil from a former manufactured gas plant (MGP) site. Approximately six pore volumes of a 20 g/L persulfate solution were introduced into the column, followed by simulated groundwater for 500 days. Soil samples were collected from the surface of the soil bed and along the column length immediately before and after persulfate injection and up to 500 days following injection. Exposure to persulfate led to a 2- to 3-log reduction in total bacterial 16S rRNA genes, severe inhibition of (14)C-acetate mineralization (as a measure of general microbial activity), and a decrease in community diversity. However, relatively rapid recovery of both bacterial gene abundance and activity was observed within 30 days after persulfate exposure. Mineralization of (14)C-phenanthrene was also inhibited but did not recover until 100 days postoxidation. Known phenanthrene-degrading bacterial groups decreased to below detection limits throughout the column, with recovery times from 100 to 500 days after persulfate injection. These findings suggest that coupling biological processes with persulfate oxidation is possible, although recovery of specific contaminant degraders may occur much later than the general microbial community recovers. Furthermore, the use of total bacterial quantity or nonspecific measures of activity as a surrogate for the recovery of contaminant degraders may be inappropriate for evaluating the compatibility of chemical treatment with subsequent bioremediation.     

FTIR kinetic, product, and modeling study of the OH-initiated oxidation of 1-butanol in air

A kinetic and product study was performed on the reaction of OH radicals with 1-butanol in a 480 L indoor photoreactor and also in the EUPHORE outdoor smog chamber in Valencia, Spain. Long path in situ FTIR spectroscopy and gas chromatography with photoionization detection were used to analyze reactants and products. Using a kinetic relative rate technique, a rate coefficient of k(OH + 1-butanol) = (8.28 +/- 0.85) x 10(-12) cm3 s(-1) was measured in 740 Torr synthetic air at 298 +/- 2 K. The reaction products observed and their fractional molar yields were (in percent) butanal (51.8 +/- 7.1), propanal (23.4 +/- 3.5), ethanal (12.7 +/- 2.2), and formaldehyde (43.4 +/- 2.4). In addition, the results support the probable formation of 4-hydroxy-2-butanone. Propanal, ethanal, and formaldehyde could also be formed in secondary reactions of some of the primary aldehydic products. However, under the conditions employed in the experiments, the contribution from secondary reactions is very minor. On the basis of the product studies, a detailed atmospheric degradation mechanism was constructed and tested against experimental data by chemical box model calculations. Measured and simulated concentration-time profiles for selected reactants were in excellent agreement.     

Photocatalytic oxidation using a new catalyst--TiO2 microsphere--for water and wastewater treatment

Since the suspended TiO2 powder enjoys free contact with UV irradiation in a photoreactor system, it can generally achieve better efficiency than the immobilized TiO2 catalysts. However, the separation and reuse of this catalyst powder from treated water often limit its application in practice. In this study, a new type of TiO2 catalyst called TiO2 microsphere was prepared by a sol-spraying-calcination method, which can easily settle in its aqueous suspensions under gravity. The SEM image of the TiO2 microsphere samples demonstrated that they had an almost spherical shape with a particle size of 30-160 microm, while the XRD analysis indicated that these TiO2 microspheres still had a crystal size of 8.1 nm. Since these TiO2 microspheres had a porous structure with higher specific surface area and pore volume than normal TiO2 powders, they appeared to have strong adsorption ability in its aqueous suspensions. The photocatalytic activity of the TiO2 microspheres was evaluated in the photodegradations of salicylic acid (SA) and sulfosalicylic acid (SSA). The experimental results showed that the reaction rate using the TiO2 microspheres was similar to that using the TiO2 powders in the SA suspensions and even higher than that in the SSA suspensions. Chemical and physical properties of the TiO2 microspheres and powders that are attributed to photoactivity were discussed based on the Langmuir-Hinshelwood kinetic model. The prepared TiO2 microsphere samples were reused in the photooxidation reaction more than 50 times. It was found that there was no significant weakening in their photoactivity and no change in their particle shape. This TiO2 microsphere catalyst can be simply used to conduct an effective photooxidation in its suspension for water and wastewater treatment with ease of recovery from treated water.     

Removal of phenol from contaminated kaolin using electrokinetically enhanced in situ chemical oxidation

The application of electrokinetic treatment to phenol contaminated soil combined with the addition of a chemical oxidant (permanganate) to the catholyte has been evaluated. It was found that the counter-current flow of the phenol (by electrosmosis) and permanganate (by electromigration) leads to a rapid oxidation of the phenol in the soil. After 5 days of treatment over 90% of the phenol (initial concentration 1 g kg(-1) dry soil) in a 15 cm long container of kaolin was removed by electrokinetic treatment with a voltage gradient of 1 V cm(-1) and an initial concentration of KMnO4 of 9 g L(-1) in the catholyte. This level of treatment was achieved with an electrical energy consumption of less than 15 kWh per m3 of soil treated.     

FTIR investigation of adsorption and chemical decomposition of CCl4 by high surface-area aluminum oxide

Chlorinated hydrocarbons are among the most recalcitrant pollutants for control by sorption or catalytic destruction. High surface-area alumina holds promise as a catalytic media as well as a component of other binary catalyst systems. We have prepared an alumina catalyst using the aerogel technique that has a very high surface area of 550 m2/g. This catalyst destroys carbon tetrachloride with an efficiency >99% at 400 degrees C. Its reactivity toward carbon tetrachloride is remarkably higher than that of commercial alumina, which has a surface area of 155 m2/g. Carbon dioxide is the major product. Minor products include hydrogen chloride and tetrachloroethylene along with traces of phosgene. Some of the carbon tetrachloride reacts with the alumina to form aluminum chloride, which vaporizes to reveal a fresh catalytic surface. A mechanism for adsorption and destruction has been developed that involves chemisorption followed by surface to adsorbate oxygen transfer and adsorbate to surface chlorine transfer.     

纳米TiO2光催化氧化处理直接耐晒翠蓝染料溶液

采用纳米级TiO2悬浮法光催化氧化处理直接耐晒翠蓝染料溶液,讨论了pH4值、催化剂用量、染料浓度、脱色时间等因素对脱色与降解的影响。实验发现,纳米TiO2对染料的脱色效率高、降解彻底,是一种较有前途的印染废水的处理方法。     

Impact of in situ chemical oxidation on contaminant mass discharge: linking source-zone and plume-scale characterizations of remediation performance

A large-scale permanganate-based in situ chemical oxidation (ISCO) effort has been conducted over the past ten years at a federal Superfund site in Tucson, AZ, for which trichloroethene (TCE) is the primary contaminant of concern. Remediation performance was assessed by examining the impact of treatment on contaminant mass discharge, an approach that has been used for only a very few prior ISCO projects. Contaminant mass discharge tests were conducted before and after permanganate injection to measure the impact at the source-zone scale. The results indicate that ISCO caused a significant reduction in mass discharge (approximately 75%). The standard approach of characterizing discharge at the source-zone scale was supplemented with additional characterization at the plume scale, which was evaluated by examining the change in contaminant mass discharge associated with the pump-and-treat system. The integrated contaminant mass discharge decreased by approximately 70%, consistent with the source-zone-scale measurements. The integrated mass discharge rebounded from 0.1 to 0.2 kg/d within one year after cessation of permanganate injections, after which it has been stable for several years. Collection of the integrated contaminant mass discharge data throughout the ISCO treatment period provided a high-resolution, real-time analysis of the site-wide impact of ISCO, thereby linking source-zone remediation to impacts on overall risk. The results indicate that ISCO was successful in reducing contaminant mass discharge at this site, which comprises a highly heterogeneous subsurface environment. Analysis of TCE sediment concentration data for core material collected before and after ISCO supports the hypothesis that the remaining mass discharge is associated in part with poorly accessible contaminant mass residing within lower-permeability zones.     

Geochemical reactions resulting from in situ oxidation of PCE-DNAPL by KMnO4 in a sandy aquifer

Although the potential for KMnO4 to destroy chlorinated ethenes in situ was first recognized more than a decade ago, the geochemical processes that accompany the oxidation have not previously been examined. In this study, aqueous KMnO4 solutions (10-30 g/L) were injected into an unconfined sand aquifer contaminated by the dense non-aqueous-phase liquid (DNAPL) tetrachloroethylene (PCE). The effects of the injections were monitored using depth-specific, multilevel groundwater samplers, and continuous cores. Two distinct geochemical zones evolved within several days after injection. In one zone where DNAPL is present, reactions between KMnO4 and dissolved PCE resulted in the release of abundant chloride and hydrogen ions to the water. Calcite and dolomite dissolved, buffering the pH in the range of 5.8-6.5, releasing Ca, Mg, and CO2 to the pore water. In this zone, the aqueous Ca/Cl concentration ratio is close to 5:12, consistent with the following reaction for the oxidation of PCE in a carbonate-rich aquifer: 3C2Cl4 + 5CaCO3(s) + 4KMnO4 + 2H+ --> 11CO2 + 4MnO2(s) + H2O + 12Cl- + 5Ca2+ + 4K+. In addition to Mg from dolomite dissolution, increases in the concentration of Mg as well as Na may result from exchange with K at cation-exchange sites. In the second zone, where lesser amounts of PCE were present, KMnO4 persisted in the aquifer for more than 14 months, and the porewater pH increased graduallyto between 9 and 10 as a resultof reaction between KMnO4 and H2O. A small increase in SO4 concentrations in the zones invaded by KMnO4 suggests that KMnO4 injections caused oxidation of sulfide minerals. There are important benefits of carbonate mineral buffering during DNAPL remediation by in situ oxidation. In a carbonate-buffered system, Mn(VII) is reduced to Mn(IV) and is immobilized in the groundwater by precipitating as insoluble manganese oxide. Energy-dispersive X-ray spectroscopy analyses of the manganese oxide coatings on aquifer mineral grains have detected the impurities Al, Ca, Cl, Cu, Pb, P, K, Si, S, Ti, U, and Zn indicating that, similar to natural systems, precipitation of manganese oxide is accompanied by coprecipitation of other elements. In addition, the consumption of excess KMnO4 by reaction with reduced minerals such as magnetite will be minimized because the rates of these reactions increase with decreasing pH. Aquifer cores collected after the KMnO4 injections exhibit dark brown to black bands of manganese oxide reaction products in sand layers where DNAPL was originally present. Mineralogical investigations indicate that the manganese oxide coatings are uniformly distributed over the mineral grains. Observations of the coatings using transmission electron microscopy indicate that they are on the order of 1 microm thick, and consequently, the decrease in porosity through the formation of the coatings is negligible.     

Mechanistic studies of the photocatalytic oxidation of microcystin-LR: an investigation of byproducts of the decomposition process

Microcystins (cyclic heptapeptides) are produced by a number of freshwater cyanobacteria and cause concern in potable water supplies due to their acute and chronic toxicity. The present study reports the structural characterization of the degradation products of the photocatalytic oxidation of microcystin-LR, so aiding the mechanistic understanding of this process. TiO2 photocatalysis is a promising technology for removal of these toxins from drinking water. However, before it can be adopted in any practical application it is necessary to have a sufficient knowledge of degradation byproducts and their potential toxicity. Liquid chromatography-mass spectrometry analysis demonstrated that the major destruction pathway of microcystin appears to be initiated via three mechanisms: UV irradiation, hydroxyl radical attack, and oxidation. UV irradiation caused geometrical isomerization of microcystin converting the (4E), (6E) of the Adda configuration to (4E), 6(Z) or 4(Z), 6(E). Hydroxyl radical attack on the conjugated diene structure of Adda moiety produced dihyroxylated products. Further oxidation cleaved the hydroxylated 4-5 and/or 6-7 bond of Adda to form aldehyde or ketone peptide residues, which then were oxidized into the corresponding carboxylic acids. Photocatalysis also hydrolyzed the peptide bond on the ring structure of microcystin to form linear structures although this appeared to be a minor pathway.