Chain photoreduction of CCl3F in TiO2 suspensions: enhancement induced by O2

Trichlorofluoromethane (CFC 11) was photoreduced in aqueous suspensions of TiO2 particles containing HCO2- ions and air. Dissolved O2 inhibited the reaction during an induction period that preceded the rapid formation of chloride ions. Reaction rates were higher in systems containing O2 as compared to analogous reactions that occurred in anaerobic suspensions. High photonic efficiencies of Cl- formation (> or =15) were achieved using suspensions with pH > or = 5. As was the case for studies with air-free suspensions, reactions are best described using a photoinitiated chain mechanism that produced CHCl2F and Cl- during the propagation steps. The enhanced yields obtained in the presence of air are attributed to the removal by O2 of electrons trapped in the oxide, which are converted first into H2O2 and then into reducing radicals that participate in the chain process. Enhanced yields of Freon photoreduction were also observed during illumination of air-free suspensions containing hydrogen peroxide, which were interpreted using a similar mechanism.     

H2 and Cl2 production in the radiolysis of calcium and magnesium chlorides and hydroxides

The production of H2 has been examined in the gamma-ray and 5 MeV He ion radiolysis of CaCl2.2H2O, CaCl2.6H2O, Ca(OH)2, MgCl2.2H2O, MgCl2.6H2O, and Mg(OH)2. The highest yield for the formation of H2 is observed in the gamma-radiolysis of MgCl2.2H2O (0.72 molecule/(100 eV), 75 nmol/J), but the yield decreases with dose due to the relative instability of the dihydrate. The H2 yields with the other compounds range from 0.04 to 0.2 molecule/(100 eV) (4.2-21 nmol/J), which is lower than that from pure water or 2 M chloride solutions. There appears to be no relationship between the results for H2 from waters of hydration with that from aqueous salt brines. No particular trend is observed in the radiation chemical yields of H2 with respect to the cation or the degree of hydration. The production of Cl2 is found only in the gamma-radiolysis of CaCl2 with a few weight percent of excess water. No Cl2 was found in the 5 MeV He ion radiolysis of identical systems. None of the other compounds examined here showed detectable amounts of Cl2 formation.     

Products of the triplet excited state produced in the radiolysis of liquid benzene

The radiation chemical yields of the products derived from the triplet excited state produced in the radiolysis of liquid benzene with gamma-rays, 10 MeV 4He ions, and 10 MeV 12C ions have been determined. Iodine scavenging techniques have been used to examine the formation and role of radicals, especially the H atom and phenyl radical. For all irradiation types examined here, the increase in hydrogen iodide yields with increasing iodine concentration matches the increase in iodobenzene yields. This agreement suggests that the benzene triplet excited state is the common precursor for the H atom and the phenyl radical. Pulse radiolysis studies in liquid benzene have determined the rate coefficients for the reactions of phenyl radicals with iodine and with the solvent benzene to be 9.3 x 10(9) M(-1) s(-1) and 3.1 x 10(5) M(-1) s(-1), respectively. Direct measurements of polymer formation, which refers to trimers (C18) and higher order compounds (>C18), in liquid benzene radiolysis using gamma-rays, 4He ions, and 12C ions at relatively high doses have been performed using gel permeation chromatography. The yields of trimers increase from gamma-rays to 12C ions due to the increased importance of intratrack radical-radical reactions that can be scavenged by the radical scavenging reactions of iodine. On the other hand, the >C18 product yields decrease from gamma-rays to 12C ions. The structure of the polymer consists of a partly saturated ring as determined by infrared and gas chromatography/mass spectrometry studies. A schematic representation for the radiolytic decomposition of the benzene triplet excited state is presented.     

Radiolysis of aqueous solutions of 1,1- and 1,2-dichloroethane

The yields of chloride ion and molecular hydrogen were determined in the gamma, the fast electron, and the 5 MeV helium ion radiolysis of deaerated and aerated aqueous solutions of 1,1- and 1,2-dichloroethane. In deaerated solutions irradiated with gamma-rays or fast electrons, the yield of chloride ion increases while the yield of molecular hydrogen decreases with increasing dichloroethane concentration. These results are due to the quantitative reaction of both the hydrated electron and the hydrogen atom with the dichloroethane to produce chloride ions. The yield of chloride ions is significantly larger in aerobic than in anaerobic conditions and is dependent upon the dose rate. Formation of peroxyl radicals by the reaction of molecular oxygen with chlorinated hydrocarbon radicals and their subsequent chemistry are responsible for the observed increase in chloride ions. The yield of chloride ion with 5 MeV helium ions is smaller than with gamma irradiation, while the yield of molecular hydrogen is larger reflecting the higher density of reactive species and consequent increase in intratrack reactions in a helium ion track compared to a gamma-ray track.     

High-LET radiolysis of liquid water with 1H+, 4He2+, 12C6+, and 20Ne9+ ions: effects of multiple ionization

Monte Carlo simulations are used to investigate the effects of multiple ionization of water molecules on the yields of formation of free radical and molecular species, including molecular oxygen, in the radiolysis of pure, deaerated liquid water by using different types of radiation (1H+, 4He2+, 12C6+, and 20Ne9+ ions) up to approximately 900 keV/microm, at neutral pH and 25 degrees C. Taking into account the double, triple, and quadruple ionizations of water, the primary (or "escape") yields (at 10(-6) s) of the various radiolytic species (G(e(aq)-), G(H*), G(H2), G(*OH), G(HO2*/O2*-), and G(H2O2) are calculated as a function of the linear energy transfer (LET) of the radiation. Our results quantitatively reproduce the large increase observed in G(HO2*/O2*-) at high LET. Under the conditions of this study, the mechanisms of triple and quadruple ionizations contribute only weakly to the production of HO2*/O2*-. With the exception of protons, our calculations also simultaneously predict a maximum in G(H2O2) corresponding to the LET of approximately 4.5-MeV helium ions (approximately 100 keV/microm) and approximately 110-MeV carbon ions (approximately 180 keV/microm). This maximum occurs where G(HO2*/O2*-) begins to rise sharply, suggesting, in agreement with previous experimental data, that the yields of HO2*/O2*- and H2O2 are closely linked. Moreover, our results show a steep increase in the initial and primary yields of molecular oxygen with increasing LET, giving support to the "oxygen in heavy-ion tracks" hypothesis. By contrast, it is found that, in the whole LET range considered, the incorporation of multiple ionization in the simulations has only little effect on the variation of our computed G(e(aq)-), G(H*), G(H2), and G(*OH) values as a function of LET. As expected, G(e(aq)-) and G(*OH) decrease continuously with increasing LET. G(H*) at first increases and then decreases at high LET. Finally, G(H2) monotonically rises with increasing LET. Our calculated yield values compare generally very well with experiment.     

Gas production in the radiolysis of poly(vinyl chloride)

The yields of H2 and Cl- were determined in the radiolysis of deaerated, aerated, and water mixtures of poly(vinyl chloride) (PVC) powders with gamma-rays and 5 MeV He ions. H2 yields with gamma-rays are low at about 0.25 molecule/100 eV and they double with He ion radiolysis indicating a second order formation process. The production of H2 in the gamma-radiolysis of water-PVC mixtures is much greater than expected from the weight fraction of the components and is due to acidification of the aqueous phase by the evolution of HCl from the polymer. Cl- yields in the gamma-radiolysis of PVC with number average weights of 22,000, 47,000, and 99,000 Daltons are 19.6, 33.8, and 32.5 atoms/100 eV. Cl- continuously evolves from the polymer for days following radiolysis. The extremely large yields suggest that a chain process involving radicals stabilized on the polymeric chain are responsible. Reflectance UV/vis and infrared spectroscopy show subtle changes in the PVC with radiolysis while UV/vis absorption spectra clearly indicate the formation of polyenes with 1 to 11 units. Cl- formation is probably initiated by Cl radical production followed by an electron rearrangement mechanism along the PVC chain to produce more Cl- and polyenes.     

Radiation-induced decomposition of cyclotrimethylenetrinitramine in aqueous solutions

Radiation-induced decomposition of cyclotrimethylenetrinitramine, a representative of heterocyclic nitramines, in dilute aqueous solutions saturated with argon, air, and N₂O has been investigated. Dose dependence curves have been obtained, and the initial yields of formation of nitrite ions and hydrogen peroxide have been measured, making up 0.122 and 0.049 in deaerated solutions, 0.050 and 0.065 in aerated solutions, and 0 and 0.074 μmol/J in N₂O-saturated solutions, respectively. The main radiolysis initial steps involve the reaction of dissociative electron capture with nitro-group elimination in the form of nitrite ion and the reaction of hydrogen atom abstraction from the methylene group by hydroxyl radicals and atomic hydrogen.     

Temperature dependence of the Fricke dosimeter and spur expansion time in the low-LET high-temperature radiolysis of water up to 350 °C: a Monte-Carlo simulation study

Monte-Carlo simulations of the radiolysis of the ferrous sulfate (Fricke) dosimeter with low-linear energy transfer (LET) radiation (such as (60)Co γ-rays or fast electrons) have been performed as a function of temperature from 25 to 350 °C. The predicted yields of Fe(2+) oxidation are found to increase with increasing temperature up to ～100-150 °C, and then tend to remain essentially constant at higher temperatures, in very good agreement with experiment. By using a simple method based on the direct application of the stoichiometric relationship that exists between the ferric ion yields so obtained G(Fe(3+)) and the sum {3 [g(e(-)(aq) + H˙) + g(HO(2)˙)] + g(˙OH) + 2 g(H(2)O(2))}, where g(e(-)(aq) + H˙), g(HO(2)˙), g(˙OH), and g(H(2)O(2)) are the primary radical and molecular yields of the radiolysis of deaerated 0.4 M H(2)SO(4) aqueous solutions, the lifetime (τ(s)) of the spur and its temperature dependence have been determined. In the spirit of the spur model, τ(s) is an important indicator for overlapping spurs, giving the time required for the changeover from nonhomogeneous spur kinetics to homogeneous kinetics in the bulk solution. The calculations show that τ(s) decreases by about an order of magnitude over the 25-350 °C temperature range, going from ～4.2 × 10(-7) s at 25 °C to ～5.7 × 10(-8) s at 350 °C. This decrease in τ(s) with increasing temperature mainly originates from the quicker diffusion of the individual species involved. Moreover, the observed dependence of G(Fe(3+)) on temperature largely reflects the influence of temperature upon the primary free-radical product yields of the radiolysis, especially the yield of H˙ atoms. Above ～200-250 °C, the more and more pronounced intervention of the reaction of H˙ atoms with water also contributes to the variation of G(Fe(3+)), which may decrease or increase slightly, depending on the choice made for the rate constant of this reaction. All calculations reported herein use the radiolysis database of Elliot (Atomic Energy of Canada Limited) and Bartels (University of Notre Dame) that contains all the best currently available information on the rate constants, reaction mechanisms, and g-values in the range 20 to 350 °C.     

Heavy ion radiolysis of liquid pyridine

The radiation chemical yields of the main products produced in liquid pyridine radiolysis (molecular hydrogen and dipyridyl) have been examined as a function of particle linear energy transfer (LET) with protons, helium ions, and carbon ions of a few to 30 MeV and compared to gamma-radiolysis published in a previous work (J. Phys. Chem. A 2005, 109, 461). Anthracene and biphenyl scavenging techniques have been used to clarify the role of the triplet excited state. An increase in triplet scavenger concentration leads to a decrease in pyridine triplet excited state with a concurrent decrease in dipyridyl, but formation of the latter does not primarily involve pyridyl radicals expected to be produced in the decomposition of the triplet excited state. A decrease in the yield of dipyridyl and an increase in molecular hydrogen are observed with increasing track average LET. The dipyridyl yield with 10 MeV carbon ions is 0.20 molecules/100 eV, which is only 16% of that of observed with gamma-rays. The low yield of dipyridyl with carbon ions is attributed to intratrack triplet-triplet (T-T) annihilation processes due to the increase in local triplet excited-state concentrations with increasing LET. An increasing yield of molecular hydrogen with increasing LET is probably due to an increase in the formation and subsequent decay of singlet excited states produced by the T-T annihilation. A complete mechanism for the radiolysis of liquid pyridine is presented.     

Effect of inorganic ligands and hydrogen peroxide on ThO2 dissolution. Behaviour of Th0.87Pu0.13O2 during leaching test

The dissolution of ThO2 powdered samples was examined in various conditions of pH and concentration of anions in the leachate. The first part of this paper describes the influence of pH on the dissolution of ThO2 in both nitric and hydrochloric media. The partial order relative to the proton concentration and the apparent normalized dissolution rate constants were determined. The second part of the paper describes the influence of other ligands such as perchlorate, chloride, sulfate, and hydrogen peroxide on the dissolution kinetics (at pH 1). An increase of RL was observed correlatively with the increase of complexing affinity of the ligand with Th. While nitric and hydrochloric media, which are weakly complexing, lead to RL values with the same order of magnitude as those for perchlorate media, the presence of sulfate or peroxide in the leachate significantly enhances the dissolution of ThO2. Consequently, the dissolution mechanism can be explained by the weakening of Th-O bonds through the formation of surface complexes at the solid/liquid interface, which enhance the detachment and thus accelerate the global dissolution. In addition, the dissolution of Th 0.87Pu 0.13O2 solid solution was also examined. The increase of the dissolution kinetics of Th 0.87Pu 0.13O 2, in comparison with that of ThO2, is considered to be caused by the presence of hydrogen peroxide formed by radiolysis of the leachate. Moreover, the redox properties of plutonium in acidic media, like disproportionation of Pu(IV) and Pu(V) and reduction of Pu(VI) and Pu(IV) in Pu(III) by H2O2, probably increase the dissolution of plutonium.     

Photoelectrochemical detection of oxidative DNA damage induced by Fenton reaction with low concentration and DNA-associated Fe2+

The metal ion dependent decomposition of hydrogen peroxide, the so-called Fenton Reaction, yields hydroxyl radicals that can cause oxidative DNA damage both in vitro and in vivo. We have previously reported a photoelectrochemical sensor for the detection of oxidative DNA damage induced by an Fe(2+)-mediated Fenton Reaction, using a DNA intercalator as a photoelectrochemical signal reporter (Liang, M.; Guo, L.-H. Environ. Sci. Technol. 2007, 41, 658). The intercalator binds less to the damaged DNA in the sensor film than the native form, resulting in a reduction in the measured photocurrent. In this report, some mechanistic aspects of the sensor were investigated. It was found that Fe(2+) alone (without the coexistence of H(2)O(2)) suppressed the photocurrent of the intercalator bound to the DNA film in a pH-dependent manner. Similar pH dependence was observed for the zeta potential of the tin oxide nanoparticle colloid used in the preparation of the semiconductor electrode, leading to the hypothesis that the metal ion binds to the surface oxide groups on the electrode and quenches the photoelectrochemical response. At pH 3, the quenching effect was reduced substantially to permit the detection of DNA damage by as low as 10 muM Fe(2+) and 40 microM H(2)O(2), a concentration that is within the physiologically relevant range. It was also found that Fe2+ ions associated with the DNA in the sensor film and participated in the DNA damage reaction, a mechanism that has been implicated in previous studies on metal carcinogenesis.     

Decomposition of solid amorphous hydrogen peroxide by ion irradiation

We present laboratory studies of the radiolysis of pure (97%) solid H2O2 films by 50 keV H+ at 17 K. Using UV-visible and infrared reflectance spectroscopies, a quartz-crystal microbalance, and a mass spectrometer, we measured the absolute concentrations of the H2O, O2, H2O2, and O3 products as a function of irradiation fluence. Ozone was identified by both UV and infrared spectroscopies and O2 from its forbidden transition in the infrared at 1550 cm(-1). From the measurements we derive radiation yields, which we find to be particularly high for the decomposition of hydrogen peroxide; this can be explained by the occurrence of a chemical chain reaction.     

Radiolytic hydrogen yields in aqueous suspensions of gold particles

The effect of high concentrations of large gold particles, in the hundreds of nanometer size regime, on the yields of molecular hydrogen, G(H(2)), produced in the radiolysis of several aqueous solutions was determined. In particular we look for direct effect of radiation absorbed by the solid particles on the yield of water products. These particles, however, are catalytically active in the conversion of reducing radicals to molecular hydrogen as well. A very small increase in G(H(2)) observed in bromide solutions upon addition of 50 wt % of gold particles indicates that the radiolysis of the solid particles does not affect the yields in the aqueous phase. Very little exchange of charge carriers or energy between the two phases occurs in these large particle suspensions. On the other hand, efficient catalytic conversion of (CH(3))(2)C(*)OH radicals to H(2) is shown to occur. The efficiency of the presently studied suspensions in the redox-catalytic process is similar to that of suspensions of small particles of similar total surface area. In the presence of radicals from hydrogen atom abstraction from tert-butyl alcohol the yield decreases significantly, again similar to the behavior in suspensions of small particles. We conclude that the redox catalysis does not depend on the size of the particles when their size exceeds a few nanometers.     

On the mechanisms of oxidation of organic sulfides by H2O2 in aqueous solutions

The mechanism of oxidation of organic sulfides in aqueous solutions by hydrogen peroxide was investigated via ab initio calculations. Specifically, two reactions, hydrogen transfer of hydrogen peroxide to form water oxide and the oxidation of dimethyl sulfide (DMS) by hydrogen peroxide to form dimethyl sulfoxide, were studied as models of these processes in general. Solvent effects are included both via including explicitly water molecules and via the polarizable continuum model. The former was found to have a much more significant effect than the latter. When explicit water molecules are included, a mechanism different from those proposed in the literature was found. Specific interactions including hydrogen bonding with 2-3 water molecules can provide enough stabilization for the charge separation of the activation complex. The energy barrier of the oxidation of DMS by hydrogen peroxide was estimated to be 12.7 kcal/mol, within the experimental range of the oxidation of analogous compounds (10-20 kcal/mol). The major reaction coordinates of the reaction are the breaking of the O-O bond of H2O2 and the formation of the S-O bond, the transfer of hydrogen to the distal oxygen of hydrogen peroxide occurring after the system has passed the transition state. Reaction barriers of the hydrogen transfer of H2O2 are an average of 10 kcal/mol or higher than the reaction barriers of the oxidation of DMS. Therefore, a two-step oxidation mechanism in which, first, the transfer of a hydrogen atom occurs to form water oxide and, second, the transfer of oxygen to the substrate occurs is unlikely to be correct. Our proposed oxidation mechanism does not suggest a pH dependence of oxidation rate within a moderate range around neutral pH (i.e., under conditions in which hydronium and hydroxide ions do not participate directly in the reaction), and it agrees with experimental observations over moderate pH values. Also, without including a protonated solvent molecule, it has activation energies that correspond to measured activation energies.     

Long-term γ-radiolysis kinetics of NO3(-) and NO2(-) solutions

Radiolysis kinetics in NO(3)(-) and NO(2)(-) solutions during γ-irradiation were studied at an absorbed dose rate of 2.1 Gy·s(-1) at room temperature. Air- or argon-saturated nitrate or nitrite solutions at pH 6.0 and 10.6 were irradiated, and the aqueous concentrations of molecular water decomposition products, H(2) and H(2)O(2), and the variation in the concentrations of NO(3)(-) and NO(2)(-) were measured as a function of irradiation time. The experimental data were compared with computer simulations using a comprehensive radiolysis kinetic model to aid in interpretation of the experimental results. The effect of nitrate and nitrite, present at concentrations below 10(-3) M, on water radiolysis processes occurs through reactions with the radical species generated by water radiolysis, (?)e(aq)(-), (?)O(2)(-), and (?)OH. The changes in H(2) and H(2)O(2) concentrations observed in the presence of nitrate and nitrite under a variety of conditions can be explained by a reduction in the radical concentrations. The kinetic analysis shows that the main loss pathway for H(2) is the reaction with (?)OH and the main loss pathways for H(2)O(2) are reactions with (?)e(aq)(-) and (?)OH. Nitrate and nitrite compete for the radicals leading to an increase in the concentrations of H(2) and H(2)O(2). Post-irradiation measurements of H(2), H(2)O(2), NO(2)(-) and NO(3)(-) concentrations can be used to calculate the radical concentrations and provide information on the redox conditions of the irradiated aqueous solutions.     

Specifics of radiolytic degradation of oxalic acid in aerated aqueous solutions

The radiolysis of aqueous solutions of oxalic acid has been studied. Data on the radiation-chemical transformations of the radiolysis liquid-phase products hydrogen peroxide, formaldehyde, glyoxylic acid, and hydrogen ions are presented. The significant effect of oxygen on the mechanism of radiolysis of oxalic acid, which in particular determines the nonmonotonic buildup of radiolysis products in the absorbed dose range of 0.5 to 2 kGy, has been confirmed.     

A common carbanion intermediate in the recombination and proton-catalysed disproportionation of the carboxyl radical anion, CO2*-, in aqueous solution

The carboxyl radical anion, CO2*- was produced by the reactions of OH radicals with either CO or formic acid in aqueous solution. The pKa(*CO2H) was determined by pulse radiolysis with conductometric detection at pH approximately equals 2.3. The bimolecular decay rate constant of CO2*- (2k approximately equals 1.4 x 10(9) dm3mol(-1)s(-1)) was found to be independent of pH in the range 3-8 at constant ionic strength. The yields of the products of the bimolecular decay of the carboxyl radicals, CO2 and the oxalate anion were found to depend strongly on the pH of the solution with an inflection point at pH 3.8. This pH dependence is explained by assuming a head-to-tail recombination of the CO2*- radicals followed by either rearrangement to oxalate or a protonation of the adduct, which subsequently leads to the formation of CO2 and formate. The recombination of CO2*- to give oxalate directly is estimated to have a contribution of <25%.     

Intermediates of radiation-induced polymerisation of maleimides studied by ESR

Radicals produced by radiolysis and photolysis of maleimides (maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenyl-maleimide) in bulk have been identified by ESR spectroscopy. γ-Irradiation of maleimides yields up to five different radicals depending on the type of maleimide. Because of the great linewidth of powder ESR spectra, the hyperfine splittings are determined by means of computer simulation. For N-alkyl maleimides the starting species of polymerisation are formed by abstraction of a H-atom from the alkyl group in radiolysis as well as in photolysis. The structure of the propagating radical shows that polymerisation proceeds via the ethylenic double bond. The detection of maleimide ions makes participation of these ions in polymerisation conceivable. Radiolysis of maleimide and N-phenylmaleimide yields the same type of radicals whereas only ions could be detected after u.v.-irradiation.     

TOF-SIMS evidence of intercalated molecular gases and diffusion-limited reaction kinetics in an alpha particle-irradiated PTFE matrix

The chemical evolution of poly(tetrafluoroethylene) (PTFE) that is brought about by increasing levels of irradiation with alpha particles is accompanied by the emergence and proliferation of functionalized moieties. Families of reaction products specifically identified in the alpha-irradiated polymer matrix include hydride-, hydroxide-, and oxide-functionalized fluorocarbons. The data also indicate the emergence of hydrogen peroxide (H2O2) and hydrazine (N2H4), but no distinct evidence suggesting the formation of perfluorinated amines, amides, or cyanogens is found. In this article we substantiate the speciation of emergent species and reveal evidence of intercalated molecular gases with which alpha particle-generated radicals may react to form the observed products. Furthermore, we present evidence to suggest that the kinetics of alpha particle-induced reaction is limited by the diffusion of radicals within the polymer matrix. That is to say, chemical additives in the polymer matrix are shown to be scavengers of H*, O*, and F* radicals and limit the rates of reaction that produce functionalized fluorocarbon moieties. Above a threshold dose of alpha particles, the concentration of radicals exceeds that of the scavenger species, and free radical diffusion commences as evidenced by a sudden increase in the yield of reaction products. Samples of PTFE were irradiated to alpha doses in the range of 10(7) to 5 x 10(10) rad with 5.5 MeV 4He2+ ions from a tandem accelerator. Residual gas analysis (RGA) was utilized to monitor the liberation of molecular gases from PTFE during alpha particle irradiation of samples in vacuum. Static time-of-flight SIMS (TOF-SIMS), equipped with a 20 keV C60+ source, was employed to probe chemical changes as a function of alpha particle irradiation. Chemical images and high-resolution mass spectra were collected in both the positive and negative polarities.