Atmospheric chemistry of HFE-7000 (CF(3)CF (2)CF (2)OCH (3)) and 2,2,3,3,4,4,4-heptafluoro-1-butanol (CF (3)CF (2)CF (2)CH (2)OH): kinetic rate coefficients and temperature dependence of reactions with chlorine atoms

Background, aim, and scope  The adverse environmental impacts of chlorinated hydrocarbons on the Earth’s ozone layer have focused attention on the effort to replace these compounds by nonchlorinated substitutes with environmental acceptability. Hydrofluoroethers (HFEs) and fluorinated alcohols are currently being introduced in many applications for this purpose. Nevertheless, the presence of a great number of C–F bonds drives to atmospheric long-lived compounds with infrared absorption features. Thus, it is necessary to improve our knowledge about lifetimes and global warming potentials (GWP) for these compounds in order to get a complete evaluation of their environmental impact. Tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atoms reaction may also be important since rate constants are generally larger than those of OH. In the present work, we report the results obtained in the study of the reactions of Cl radicals with HFE-7000 (CF₃CF₂CF₂OCH₃) (1) and its isomer CF₃CF₂CF₂CH₂OH (2). Materials and methods  Kinetic rate coefficients with Cl atoms have been measured using the discharge flow tube–mass spectrometric technique at 1 Torr of total pressure. The reactions of these chlorofluorocarbons (CFCs) substitutes have been studied under pseudo-first-order kinetic conditions in excess of the fluorinated compounds over Cl atoms. The temperature ranges were 266–333 and 298–353 K for reactions of HFE-7000 and CF₃CF₂CF₂CH₂OH, respectively. Results  The measured room temperature rate constants were k(Cl+CF₃CF₂CF₂OCH₃) = (1.24 ± 0.28) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹and k(Cl+CF₃CF₂CF₂CH₂OH) = (8.35 ± 1.63) × 10⁻¹³ cm³ molecule⁻¹ s⁻¹ (errors are 2σ + 10% to cover systematic errors). The Arrhenius expression for reaction 1 was k ₁(266–333 K) = (6.1 ± 3.8) × 10⁻¹³exp[−(445 ± 186)/T] cm³ molecule⁻¹ s⁻¹ and k ₂(298–353 K) = (1.9 ± 0.7) × 10⁻¹²exp[−(244 ± 125)/T] cm³ molecule⁻¹ s⁻¹ (errors are 2σ). The reactions are reported to proceed through the abstraction of an H atom to form HCl and the corresponding halo-alkyl radical. At 298 K and 1 Torr, yields on HCl of 0.95 ± 0.38 and 0.97 ± 0.16 (errors are 2σ) were obtained for CF₃CF₂CF₂OCH₃ and CF₃CF₂CF₂CH₂OH, respectively. Discussion  The obtained kinetic rate constants are related to the previous data in the literature, showing a good agreement taking into account the error limits. Comparing the obtained results at room temperature, k ₁ and k ₂, HFE-7000 is significantly less reactive than its isomer C₃F₇CH₂OH. A similar behavior has been reported for the reactions of other fluorinated alcohols and their isomeric fluorinated ethers with Cl atoms. Literature data, together with the results reported in this work, show that, for both fluorinated ethers and alcohols, the kinetic rate constant may be considered as not dependent on the number of –CF₂– in the perfluorinated chain. This result may be useful since it is possible to obtain the required physicochemical properties for a given application by changing the number of –CF₂– without changes in the atmospheric reactivity. Furthermore, lifetimes estimations for these CFCs substitutes are calculated and discussed. The average estimated Cl lifetimes are 256 and 38 years for HFE-7000 and C₃H₇CH₂OH, respectively. Conclusions  The studied CFCs’ substitutes are relatively short-lived and OH reaction constitutes their main reactive sink. The average contribution of Cl reactions to global lifetime is about 2% in both cases. Nevertheless, under local conditions as in the marine boundary layer, τ _Cl values as low as 2.5 and 0.4 years for HFE-7000 and C₃H₇CH₂OH, respectively, are expected, showing that the contribution of Cl to the atmospheric degradation of these CFCs substitutes under such conditions may constitute a relevant sink. In the case of CF₃CF₂CF₂OCH₃, significant activation energy has been measured, thus the use of kinetic rate coefficient only at room temperature would result in underestimations of lifetimes and GWPs. Recommendations and perspectives  The results obtained in this work may be helpful within the database used in the modeling studies of coastal areas. The knowledge of the atmospheric behavior and the structure–reactivity relationship discussed in this work may also contribute to the development of new environmentally acceptable chemicals. New volatile materials susceptible of emission to the troposphere should be subject to the study of their reactions with OH and Cl in the range of temperature of the troposphere. The knowledge of the temperature dependence of the kinetic rate constants, as it is now reported for the case of reactions 1 and 2, will allow more accurate lifetimes and related magnitudes like GWPs. Nevertheless, a better knowledge of the vertical Cl tropospheric distribution is still required.     

Simultaneous conversion of CHClF(2) and CH(3)Br to CH(2)CF(2)

Gas phase reaction of CHClF(2) with CH(3)Br in an alumina tube reactor at 773-1123 K as a function of various input ratios of CH(3)Br to CHClF(2) is presented. The major products detected include C(2)F(4), CH(2)CF(2), and CH(4). Minor products include CH(3)Cl, CHF(3), C(2)H(4), C(2)H(2), CH(2)CF-CF(3), and C(2)H(3)F. The reaction produces a high yield of CH(2)CF(2) (53% based on CHClF(2) feed) at 1123 K and an input molar ratio of CH(3)Br to CHClF(2) of 1.8, suggesting that the reaction potentially can be developed as a process to convert two ozone depleting substances (CHClF(2) and CH(3)Br) to a highly valuable chemical, CH(2)CF(2). The reaction of CHClF(2) with CH(3)Cl and CH(3)I was also investigated under similar reaction conditions, to assist in understanding the reaction chemistry involved in the reaction of CHClF(2) with CH(3)Br.     

Comparative study on the removal efficiency of hydrogen sulfide (H2S) using three different packings

To improve the removal efficiency on hydrogen sulfide (H₂S), a biofilter was developed and was made of polyvinyl chloride (PVC) pipes. The effects of three different packings (i.e., packing A, packing B, and packing C), containing different proportions of activated carbon, sawdust, wormcast, perlite, and pig manure compost, based on different biofilter parameters on H₂S removal efficiency, were investigated. With the extension of running time, the H₂S removal rate of packing A reached up to 90.12%, that of packing B reached a peak at 92.96%, and that of packing C was highest at 87.21%. The contribution rate of each packing at the bottom of the device was significantly greater (p < 0.01) than that of other parts, and those of the top of the devices were all greater than those of the middle of the devices. The H₂S removal rate increased with greater filler layer height. The removal rate of group B increased first with humidity, and then declined, with the optimal humidity level for the removal of H₂S 50–65% in this study. With the prolongation of the run, the pH of packing A was reduced from 7.1 to 5.91, while the pH of packing B and C remained within the range of 6.53–7.10. An increase was found in the number of bacteria and fungi over time. The count of bacteria in packing B and C and following a decreasing order was bottom > middle > top, whereas that for fungi was the opposite. In conclusion, it is thought that packing B (comprising wormcast + sawdust + activated carbon) is more efficient in the removal of H₂S than the other packings and may thus be utilized in biofilters. These results hope to provide useful information for future related research on the removal efficiency of H₂S using packings.

Implications: Wormcasts use as biological filter packing to remove H₂S is limited and needs yet to be explored. A comparative study on the removal efficiency of H₂S using three packings showed the packings that included wormcast were more efficient than others, and showed the combined features of physical absorption and biological removal with long sustainability and good efficiency, although these were largely influenced by environmental factors and nutrient content for the microorganisms. In summary, wormcast could be utilized in biological filters in the future in related research beacuse of its good efficiency and low cost.     

Investigation of acute toxicity of cadmium sulfate (CdSO4 x H2O) and behavioral changes of grass carp (Ctenopharyngodon idellus Val., 1844)

This study attempts to determine the 96-h LC50 values of CdSO4 x H2O, a metal salt widely used in industry, for grass carp (Ctenopharyngodon idellus Val., 1844). The study was carried out in two stages with 120 grass carp individuals using statistic method of aquatic toxicity. In addition, the behavioral changes of grass carp at different CdSO4 x H2O concentrations were determined. The results were evaluated using probit analysis method and the LC50 value for grass carp species was calculated as 9.42 mg/l.     

Estimated photochemical ozone creation potentials (POCPs) of CF3CFCH2 (HFO-1234yf) and related hydrofluoroolefins (HFOs)

The photochemical ozone creation potentials (POCPs) for CF₃CFCH₂ and other commercially significant hydrofluoroolefins have been estimated for the first time. CF₃CFCH₂ (HFO-1234yf) has a POCP of 7.0 which is less than that for ethane (12.3) and greater than for methane (0.6). Methane and ethane have sufficiently low POCPs that they are usually considered unreactive with respect to ozone formation in urban areas and accordingly are exempt from volatile organic compound (VOC) emission regulations. Estimated POCPs for other hydrofluoroolefins are: CH₂CF₂, 18.0; CF₂CF₂, 12.5; CH₂CHCF₃, 10.7; CF₂CFCF₃, 5.4; Z-CHFCFCF₃, 5.6; E-CHFCFCF₃, 7.3; CH₂CHCF₂CF₃, 6.6; and t-CHFCHCF₃, 6.4.     

MnO2负载树脂的制备及对As(Ⅴ)的去除效果

制备了大孔和DH302 2种MnO2的负载树脂.并用SEM、EDS手段表征了负载树脂,实验了负载MnO2后树脂对As(Ⅴ)的去除效果.结果表明:负载树脂对As(Ⅴ)的去除效果比原树脂有很大提高;吸附As(Ⅴ)后的2种负载树脂,均能较好地解吸并可重新用于对As(Ⅴ)的吸附实验.     

Quantitative evaluation of electron injection efficiency in dye-sensitized TiO(2) films

The efficiency of electron injection (Φ(inj)) in dye-sensitized nanocrystalline films was studied through transient absorption (TA) and time-resolved microwave conductivity (TRMC) measurements. Here, I show the absolute value of Φ(inj) for several dye-sensitized nanocrystalline films and discuss the relationship between Φ(inj) and the free energy change (-ΔG (inj)) for the injection process. Some systems exhibited lower Φ(inj) values even when -ΔG (inj) was sufficiently large to promote electron injection. Recent experimental findings are used to propose possible explanations for this phenomenon. Quantitative evaluation of Φ(inj) using TA and TRMC will give us new insights for developing high-performance solar cell devices.     

Experimental and modeling study of the effect of CO and H2 on the urea DeNO(x) process in a 150kW laboratory reactor

An experimental and modeling investigation has been performed to study the effect of process additives, H2 and CO on NO(x) removal from flue gases by a selective non-catalytic reduction process using urea as a reducing agent. Experiments were performed with a flow reactor in which flue gas was generated by the combustion of propane in air at 3% excess oxygen and the desired levels of initial NO(x) (500ppm) were achieved by doping the flame with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 850 to 1200 degrees C for investigation of the effects of the process additives on the performance of aqueous urea DeNO(x). Subsequently, computational kinetic modeling with SENKIN code was performed to analyze the performance of urea providing a direct comparison of modeling prediction with experimental measurements. With CO addition, a downwards shift of 215 degrees C in the peak reduction temperature from 1125 to 910 degrees C was observed during the experimentation while the kinetic modeling suggests it to be 150 degrees C, i.e. from 1020 to 870 degrees C. The addition of H2 impairs the peak NO(x) reduction but suggests a low temperature application of the process. A downward shift of 250 degrees C in the peak reduction temperature, from 1020 to 770 degrees C, was observed during kinetic modeling studies. The kinetic modeling shows a good qualitative agreement with the experimental observations and reveals additional information about the process.     

Atmospheric chemistry of perfluorobutenes (CF3CFCFCF3 and CF3CF2CFCF2): Kinetics and mechanisms of reactions with OH radicals and chlorine atoms,IR spectra,global warming potentials,and oxidation to perfluorocarboxylic acids

Relative rate techniques were used to determine k(Cl + CF₃CFCFCF₃) = (7.27 ± 0.88) × 10^?12, k(Cl + CF₃CF₂CFCF₂) = (1.79 ± 0.41) × 10^?11, k(OH + CF₃CFCFCF₃) = (4.82 ± 1.15) × 10^?13, and k(OH + CF₃CF₂CFCF₂) = (1.94 ± 0.27) × 10^?12 cm³ molecule^?1 s^?1 in 700 Torr of air or N₂ diluent at 296 K. The chlorine atom- and OH radical-initiated oxidation of CF₃CFCFCF₃ in 700 Torr of air gives CF₃C(O)F in molar yields of 196 ± 11 and 218 ± 20%, respectively. Chlorine atom-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 97 ± 9% CF₃CF₂C(O)F and 97 ± 9% COF₂. OH radical-initiated oxidation of CF₃CF₂CFCF₂ gives molar yields of 110 ± 15% CF₃CF₂C(O)F and 99 ± 8% COF₂. The atmospheric fate of CF₃CF₂C(O)F and CF₃C(O)F is hydrolysis to give CF₃CF₂C(O)OH and CF₃C(O)OH. The atmospheric lifetimes of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ are determined by reaction with OH radicals and are approximately 24 and 6 days, respectively. The contribution of CF₃CFCFCF₃ and CF₃CF₂CFCF₂ to radiative forcing of climate change will be negligible.     

Photodegradation of hexabromocyclododecane (HBCD) by Fe(III) complexes/H2O2 under simulated sunlight

Hexabromocyclododecane (HBCD) is a globally produced brominated flame retardant used primarily as an additive flame retardant in polystyrene and textile products. Photodegradation of HBCD in the presence of Fe(III)-carboxylate complexes/H₂O₂ was investigated under simulated sunlight. The degradation of HBCD decreased with increasing pH in the Fe(III)-oxalate solutions. In contrast, the optimum pH was 5.0 for the Fe(III)-citrate-catalyzed photodegradation within the range of 3.0 to 7.0. For both Fe(III)-oxalate and Fe(III)-citrate complexes, the increase of carboxylate concentrations facilitated the photodegradation. The photochemical removal of HBCD was related to the photoreactivity and speciation distribution of Fe(III) complexes. The addition of H₂O₂ markedly accelerated the degradation of HBCD in the presence of Fe(III)-citrate complexes. The quenching experiments showed that ·OH was responsible for the photodegradation of HBCD in the Fe(III)-carboxylate complexes/H₂O₂ solutions. The results suggest that Fe(III) complexes/H₂O₂ catalysis is a potential method for the removal of HBCD in the aqueous solutions.     

High temperature dependence of 2,4-dichlorophenoxyacetic acid degradation by Fe3+/H(2)O(2) system

This study demonstrates the importance of reaction temperature on the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D). In addition, we provide a mechanistic explanation for the temperature dependence of 2,4-D degradation. Thermal enhancement of 2,4-D degradation and H(2)O(2) decomposition was measured in the absence and in the presence of the z.rad;OH scavenger (t-butanol). The half-life for 2,4-D degradation was reduced by more than 70-fold in the absence of t-butanol, and by more than 700-fold, in the presence of t-butanol, when the reaction temperature was increased from 10 to 50 degrees C. In addition, similar temperature relationships were found for H(2)O(2) decomposition. The major reason for the high temperature dependence of the Fe(3+)/H(2)O(2) system in the case of 2,4-D degradation is due to the dependence of the initiation reaction of the Fe(3+)/H(2)O(2) system (i.e., Fe(3+)+H(2)O(2)-->Fe(2+)+HO(2)(z.rad;)+H(+) upon temperature), which is entirely consistent with the kinetics of the activation energy. In the presence of a z.rad;OH scavenger, the initiation reaction of the Fe(3+)/H(2)O(2) system became a determining factor of this temperature dependence, whereas in the absence of z.rad;OH scavenger, several other radical reactions played a role and this result in an apparent decrease in the activation energy for 2,4-D degradation. Moreover, the enhanced 2,4-D removal at higher temperatures did not alter H(2)O(2) utilization. The practical implications of the thermal enhancement of the Fe(3+)/H(2)O(2) system are discussed.     

Comparative study of H(2)O(2) and O3 effects on radiation treatment of TCE and PCE

The effects of H(2)O(2) and O(3) on the decomposition of trichloroethylene (TCE) and perchloroethylene (PCE) by gamma-rays (gamma-rays) were investigated in this work. The combined gamma-rays/O(3) process showed a synergistic effect and enhanced the removal of TCE and PCE compared with gamma-rays alone, but, the gamma-rays/H(2)O(2) process did not increase the removal. This interesting result was successfully identified by an electron paramagnetic resonance spectroscopy/spin-trapping method that can quantify hydroxyl radicals, which is directly related to the efficiency of TCE and PCE decomposition. For gamma-rays/H(2)O(2) system, there was no difference of hydroxyl radical production between gamma-rays alone and gamma-rays/H(2)O(2). This indicates gamma-rays cannot activate H(2)O(2) to produce hydroxyl radicals and this causes no increase of TCE and PCE removals. To the contrary, the production of hydroxyl radicals was obviously increased in the case of gamma-rays/O(3) process. This suggests additional hydroxyl radicals are produced from the reaction of O(3) with the irradiation products of water such as hydrated electrons, hydrogen atoms, etc. and this accelerates the removal of TCE and PCE.     

常见阴离子对TiO2/H2O2/O3体系氧化效能的影响

酸性条件下考察了常见阴离子对TiO2/H2O2/O3氧化效率的影响,目标化合物为羟基自由基的探针化合物乙酸。结果表明,硫酸根和硝酸根对体系氧化乙酸的效率几乎没有影响。加入磷酸盐可以减缓H2O2的分解速率,进而导致乙酸的降解效率下降,这可能与其在TiO2表面的吸附作用有关。在初始pH为3.0时,氯离子对子乙酸的降解速率具有明显的抑制作用,氯离子浓度越高,抑制作用越明显。当溶液初始pH大于4.4以上时,氯离子对乙酸的降解效率几乎没有影响。以上结果对推动TiO2/H2O2/O3体系处理酸性废水意义较为突出。     

微气泡曝气O3／H2O2处理RO浓水的效能及影响因素

采用O3／H2O2高级氧化工艺处理炼油厂反渗透（RO）浓水,用溶气泵加压溶气并产生微气泡强化传质,确定装置运行条件,考察气体中臭氧浓度、O3／H2O2初始摩尔比、pH和温度对O3／H2O2处理RO浓水效果的影响,并对RO浓水处理效能进行研究。结果表明,随着气体中臭氧浓度的增加,COD的去除率基本呈线性增加;加入适当量H,0,能提高臭氧氧化RO浓水的效果,O3／H2O2初始摩尔比在0～0．8范围内,COD的去除率先增加后下降,O3／H2O2初始摩尔比为O．5时COD去除率最大;pH从6．84增加到9．01,COD去除率逐渐增大,pH为10．03时COD去除率反而降低;在14～28℃范围内,温度低时,升高温度COD去除率增加较大,温度较高时,升高温度对COD去除率的影响较小。为考察该工艺的稳定性,在H：0：／0,初始摩尔比为O．5、溶液pH为8～9、臭氧浓度为80～100mg／L、温度为10-28℃条件下,对COD为90～140mg／L的RO浓水氧化处理4～10h,出水COD维持在39．9～49．9mg／L,达到《城镇污水处理厂污染物排放标准（GB18918—2002）》中的一级A标准;去除1gCOD消耗031．4～3．3g,消耗0,与H,02的总氧量为2．2～4．4g。     

Influence of various reaction parameters on 2,4-D removal in photo/ferrioxalate/H(2)O(2) process

The influence of various reaction parameters on herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) removal were examined in the photo/ferrioxalate/H(2)O(2) system, with regard to: (1) sulfate, phosphate, and z.rad;OH scavenger, as solution constituent; and (2) light intensity, ferrioxalate, H(2)O(2), and oxalate concentration, as operating parameter. In terms of 2,4-D removal, the photo/ferrioxalate/H(2)O(2) system has always been superior to the photo/Ferric ion/H(2)O(2) system, despite the high presence of anions (sulfate 100 mM, phosphate 1 mM) or z.rad;OH scavenger. Not only the rate of 2,4-D removal, but also the decomposition rate of H(2)O(2) and oxalate proportionally increase with light intensity. The ferrioxalate concentration determines the light absorption fraction, and thus, controls the rates of 2,4-D removal, and the decomposition of H(2)O(2) and oxalate, are predicted from kinetic formulations. The optimal concentration of H(2)O(2) and oxalate, according to the extent of the z.rad;OH scavenging reaction with these reagents, has been demonstrated for 2,4-D removal. It was found that an increasing oxalate concentration, which bears the burden of increased dissolved organic carbon (DOC), does not occur. This is because its decomposition, as a result of the photochemical reduction of the ferric oxalate complex, results in a decrease of the equivalent DOC. The importance of the key reaction factors to be considered, when applying this system to real wastewater treatment, is also discussed.     

Kinetics of oxidation of chlorobenzenes and phenyl-ureas by Fe(II)/H2O2 and Fe(III)/H2O2. Evidence of reduction and oxidation reactions of intermediates by Fe(II) or Fe(III)

The rates of degradation of 1,2,4-trichlorobenzene (TCB), 2,5-dichloronitrobenzene (DCNB), diuron and isoproturon by Fe(II)/H2O2 and Fe(III)/H2O2 have been investigated in dilute aqueous solution ([Organic compound]0 approximately 1 microM, at 25.0 +/- 0.2 degrees C and pH < or = 3). Using the relative rate method with atrazine as the reference compound, and the Fe(II)/H2O2 (with an excess of Fe(II)) and Fe(III)/H2O2 systems as sources of OH radicals, the rate constants for the reaction of OH* with TCB and DCNB were determined as (6.0 +/- 0.3)10(9) and (1.1 +/- 0.2)10(9) M(-1) s(-1). Relative rates of degradation of diuron and isoproturon by Fe(II)/H2O2 were about two times smaller in the absence of dissolved oxygen than in the presence of oxygen. These data indicate that radical intermediates are reduced back to the parent compound by Fe(II) in the absence of oxygen. Oxidation experiments with Fe(III)/H2O2 showed that the rate of decomposition of atrazine markedly increased in the presence of TCB and this increase has been attributed to a regeneration of Fe(II) by oxidation reactions of intermediates (radical species and dihydroxybenzenes) by Fe(III).     

Electrogeneration of H(2) for Pd-catalytic hydrodechlorination of 2,4-dichlorophenol in groundwater

A novel electrolytic groundwater remediation process, which used the H₂ continuously generated at cathode to achieve in situ catalytic hydrodechlorination, was developed for the treatment of 2,4-dichlorophenol (2,4-DCP) in groundwater. Catalytic hydrodechlorination using Pd supported on bamboo charcoal and external H₂ showed that 2,4-DCP was completely dechlorinated to phenol within 30 min at pH ? 5.5. In a divided electrolytic system, the catalytic hydrodechlorination of 2,4-DCP in cathodic compartment by H₂ generated at the cathode under 20 and 50 mA reached 100% at 120 and 60 min, respectively. Two column experiments with influent pHs of 5.5 (unconditioned) and 2 were conducted to evaluate the feasibility of this process. The 2,4-DCP removal efficiencies were about 63% and nearly 100% at influent pHs of 5.5 and 2, respectively. Phenol was solely produced by 2,4-DCP hydrodechlorination, and was subsequently degraded at the anode. A low pH could enhance the hydrodechlorination, but was not necessarily required. This study provides the preliminary results of a novel effective electrolytic process for the remediation of groundwater contaminated by chlorinated aromatics.     

Degradation of rhodamine B by Fe(0)-based Fenton process with H2O2

Degradation of rhodamine B by Fe(0)-based Fenton process with H₂O₂ was investigated. The effects of H₂O₂ dose, Fe(0) dose, initial concentration of rhodamine B and initial pH value on the degradation of rhodamine B were examined. The results showed that the degradation and mineralization of rhodamine B occurred with low dose of H₂O₂ and Fe(0). The intermediates of rhodamine B were analyzed with UV-Vis spectrophotometry and ion chromatography and the mechanism of oxidative degradation of rhodamine B was also discussed. The reactive oxygen species (·OH) produced in Fe(0)-based Fenton process with H₂O₂ is the key to the degradation of rhodamine B by ways of N-de-ethylation, chromophore cleavage, ring-opening and mineralization.     

Hydroxyl (OH) radical production rates in snowpacks from photolysis of hydrogen peroxide (H2O2) and nitrate (NO3−)

Atmospheric chemistry directly above snowpacks is strongly influenced by ultraviolet (UV) radiation initiated emissions of chemicals from the snowpack. The emission of gases from the snowpack to the atmosphere is in part due to chemical reactions between hydroxyl radical, OH (produced from photolysis of hydrogen peroxide (H₂O₂) or nitrate (NO₃⁻)) and impurities in the snowpack. The work presented here is a radiative-transfer modelling study to calculate the depth-integrated production rates of hydroxyl radical from the photolysis of hydrogen peroxide and nitrate anion in snow for four different snowpacks and for solar zenith angles 30°–90°. This work also demonstrates the importance of hydrogen peroxide photolysis to produce hydroxyl radical relative to nitrate photolysis with (a) different snowpacks, (b) different ozone column depths, and (c) snowpack depths. The importance of hydrogen peroxide photolysis over nitrate photolysis for hydroxyl radical production increases with increasing depth in snowpack, column ozone depth, and solar zenith angle. With a solar zenith angle of 60° the production of hydroxyl radical from hydrogen peroxide photolysis accounts for 91–99% of all hydroxyl radical production from hydrogen peroxide and nitrate photolysis.     

Abiotic reduction of antimony(V) by green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O)

Green rust (Fe(4)(II)Fe(2)(III)(OH)(12)SO(4).3H(2)O) is an intermediate phase in the formation of iron (oxyhydr)oxides such as goethite, lepidocrocite, and magnetite. It is widely considered that green rust occurs in many soil and sediment systems. Green rust has been shown to reduce sorbed Se(VI), Cr(VI), and U(VI). In addition, it is also reported that green rust does not reduce As(V) to As(III). In this study, we have investigated for the first time the interaction between Sb(V) and green rust using XAFS and HPLC-ICP-MS. Most of the added Sb(V) was adsorbed on green rust, and Sb(III), a reduced form, was observed in both solid and liquid phases. Thus, it was shown that green rust has high affinity for Sb(V), and that Sb(V) was reduced to more toxic Sb(III) by green rust despite the high stability of the Sb(V) species even under reducing condition as reported in previous studies. Therefore, green rust can be one of the most important reducing agents for Sb(V), which can influence the Sb mobility in suboxic environments where green rust is formed.