Computer estimation of the Atmospheric gas-phase reaction rate of organic compounds with hydroxyl radicals and ozone

The Atmospheric Oxidation Program (AOP) is a computer program that estimates the rate constant for the atmospheric, gas-phase reaction between photochemically produced hydroxyl radicals (OH) and organic chemicals. It also estimates the rate constant for the gas-phase reaction between ozone and olefinic/acetylenic compounds. AOP, which uses estimation methods developed by Atkinson and co-workers, estimates more accurate rate constants than the PCFAP (Fate of Atmospheric Pollutants) program that was part of the U.S. EPA's Graphical Exposure Modeling System (GEMS). Due to its superior predictive ability, the EPA is currently using AOP to evaluate the atmospheric fate of compounds defined under Sections 4, 5 and 6 of the Toxic Substances Control Act (TSCA).     

Relative kinetic measurements of rate coefficients for the gas-phase reactions of Cl atoms and OH radicals with a series of methyl alkyl esters

Relative kinetic studies have been performed on the reactions of Cl atoms with a series of methyl alkyl esters in a 405-liter borosilicate glass chamber at (298 ± 3) K and one atmosphere of synthetic air using in situ FTIR spectroscopy to monitor the reactants. Rate coefficients (in units of cm³ molecule^?1 s^?1) were determined for the following compounds: methyl acetate (2.48 ± 0.58) × 10^?12; methyl propanoate (1.68 ± 0.36) × 10^?11; methyl butanoate (4.77 ± 0.87) × 10^?11; methyl pentanoate (7.84 ± 1.15) × 10^?11; methyl hexanoate (1.09 ± 0.31) × 10^?10; methyl heptanoate (1.56 ± 0.37) × 10^?10; methyl cyclohexane carboxylate (3.32 ± 0.76) × 10^?10; methyl-2-methyl butanoate (9.41 ± 1.39) × 10^?11.In addition rate coefficients (in units of 10^?11 cm³ molecule^?1 s^?1) have been obtained for the reactions of OH radicals with the following compounds: methyl butanoate (3.55 ± 0.71), methyl pentanoate (5.41 ± 1.08), and methyl-2-methyl butanoate (4.08 ± 0.82).Using the kinetic rate data tropospheric lifetimes for the methyl alkyl esters with respect to their reactions with OH, and Cl have been estimated for typical ambient air concentrations of these oxidants.     

Stable chlorine intramolecular kinetic isotope effects from the abiotic dehydrochlorination of DDT

INTENTION, GOAL, SCOPE, BACKGROUND: Identifying different sources and following reaction pathways of chlorinated organic contaminants in the environment can be challenging, especially when only their concentrations are available. Compound-specific stable chlorine measurements of some contaminants have recently been shown to provide additional information and an increased understanding of their biogeochemistry. These studies, however, have been generally limited to volatile molecules. OBJECTIVE: Here, the stable chlorine isotope ratios of the semi-volatile pesticide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane (DDT) were investigated. Specifically, the intramolecular stable chlorine isotopic compositions of DDT and the kinetic isotope effect (KIE) for the abiotic dehydrochlorination of DDT to 2,2-bis(p-chlorophenyl)-1,1-dichloroethene (DDE) were determined. METHODS: Selective chemical oxidation of DDT to dichlorobenzophenone (DCBP) and analysis of each compound was used to calculate the stable chlorine isotope ratios of the alkyl and aromatic chlorines in DDT. To determine the KIE for dehydrochlorination, DDT was reacted in a basic solution to yield DDE at 52 degrees C, 60 degrees C, and 72 degrees C for 3, 5, and 5 days, respectively. RESULTS AND DISCUSSION: Significant intramolecular stable chlorine isotopic differences were observed in one sample of DDT where the alkyl and aromatic delta 37Cl values were -5.76 +/- 0.45 and -2.21 +/- 0.24%@1000, respectively. Dehydrochlorination of DDT to DDE in basic solutions at 52, 60, and 70 degrees C resulted in a substantial intramolecular KIE where the alkyl chlorines of DDE shifted by approximately 3%@1000 relative to the alkyl chlorines in DDT. However, no temperature dependence was observed. The KIE, calculated by an iterative program, was 1.009. CONCLUSIONS: Intramolecular differences in the stable chlorine isotope ratios were observed in DDT and this is the first such finding. Dehydrochlorination of DDT yields a measurable and distinct intramolecular stable chlorine KIE. RECOMMENDATION AND OUTLOOK: The results of this study demonstrate the existence of significant intramolecular differences in chlorinated organic compounds. Many other chlorinated semi-volatile and volatile organic contaminants are synthesized from multiple sources of chlorine, and we recommend that similar studies be performed on many such molecules in order to attain a clear understanding of their intramolecular chlorine isotopic differences. The existence of a measurable KIE for the dehydrochlorination of DDT to DDE shows the potential strength of using isotopic measurements to investigate the biogeochemistry of these important compounds. For example, the isotopically depleted aqueous chloride produced by dehydrochlorination of DDT to DDE may be a useful tracer of these reactions in freshwater environments.     

FTIR gas-phase kinetic study on the reactions of some acrylate esters with OH radicals and Cl atoms

Acrylate esters are α,β-unsaturated esters that contain vinyl groups directly attached to the carbonyl carbon. These compounds are widely used in the production of plastics and resins. Atmospheric degradation processes of these compounds are currently not well understood. The kinetics of the gas phase reactions of OH radicals with methyl 3-methylacrylate and methyl 3,3-dimethylacrylate were determined using the relative rate technique in a 50 L Pyrex photoreactor using in situ FTIR spectroscopy at room temperature (298?±?2 K) and atmospheric pressure (708?±?8 Torr) with air as the bath gas. Rate coefficients obtained were (in units cm³ molecule^?1 s^?1): (3.27?±?0.33)?×?10^?11 and (4.43?±?0.42)?×?10^?11, for CH₃CH═CHC(O)OCH₃ and (CH₃)₂CH═CHC(O)OCH_3, respectively. The same technique was used to study the gas phase reactions of hexyl acrylate and ethyl hexyl acrylate with OH radicals and Cl atoms. In the experiments with Cl, N₂ and air were used as the bath gases. The following rate coefficients were obtained (in cm³ molecule^?1 s^?1): k₃ (CH₂═CHC(O)O(CH₂)₅CH₃?+?Cl)?=?(3.31?±?0.31)?×?10^?10, k₄(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?Cl)?=?(3.46?±?0.31)?×?10^?10, k₅(CH₂═CHC(O)O(CH₂)₅CH₃?+?OH)?=?(2.28?±?0.23)?×?10^?11, and k₆(CH₂═CHC(O)OCH₂CH(CH₂CH₃)(CH₂)₃CH₃?+?OH)?=?(2.74?±?0.26)?×?10^?11. The reactivity increased with the number of methyl substituents on the double bond and with the chain length of the alkyl group in –C(O)OR. Estimations of the atmospheric lifetimes clearly indicate that the dominant atmospheric loss process for these compounds is their daytime reaction with the hydroxyl radical. In coastal areas and in some polluted environments, Cl atom-initiated degradation of these compounds can be significant, if not dominant. Maximum Incremental Reactivity (MIR) index and global warming potential (GWP) were also calculated, and it was concluded that these compounds have significant MIR values, but they do not influence global warming.     

Kinetics of the gas-phase reactions of NO3 radicals with ethyl acrylate,n-butyl acrylate,methyl methacrylate and ethyl methacrylate

The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO₃ radicals with a series of acrylate esters: ethyl acrylate (k₁), n-butyl acrylate (k₂), methyl methacrylate (k₃) and ethyl methacrylate (k₄) at 298 ± 1 K and 760 Torr. The obtained rate constants are k₁ = (1.8 ± 0.25) × 10^?16 cm³ molecule^?1 s^?1, k₂ = (2.1 ± 0.33) × 10^?16 cm³ molecule^?1 s^?1, k₃ = (3.6 ± 1.2) × 10^?15 cm³ molecule^?1 s^?1, k₄ = (4.9 ± 1.7) × 10^?15 cm³ molecule^?1 s^?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO₃ radicals. In addition, the atmospheric lifetimes of the compound against NO₃ attack are estimated and the results show that NO₃ reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.     

Rates of production of hydroxyl radicals and singlet oxygen from irradiated compost

The use of organic matter from compost to promote the catalytic photodegradation of micropollutants by solar light appears to be environmentally promising. However, quantitative evaluation of the photodegradation potential of the compost is needed. Our goal was to measure the formation rate of hydroxyl radicals and singlet oxygen, two strongly oxidant species, from irradiated compost organic matter. These two reactive species were photogenerated in all of our extracts regardless of the origin of the compost or the extraction procedure; however, their formation rates increased with composting time. Two herbicides and a fungicide were successfully photodegraded when irradiated with simulated or natural solar light in the presence of the compost organic matter or compost suspensions. For reasons of simplification and ease, the use of the latter is recommended in practice.     

A model for prediction of product distributions for the reactions of phenol derivatives with hydroxyl radicals

In this study, with the intention of estimating the photocatalytic or photodegradation rates and finding certain predictors to be used for the determination of the most probable reaction path and the primary intermediate, the reactions of (*)OH radicals with 11 phenol derivatives including benzene were modeled. For 43 possible reaction routes, calculations of the geometric parameters, the electronic and thermodynamic properties of the reactants, the product radicals and the transition state complexes were performed with the semiempirical PM3 and DFT/B3LYP/6-31G(*) methods. The solvation effects were computed using COSMO as the solvation model. Based on the results of quantum mechanical calculations, the rate constants, the branching ratios and the product distributions of all the possible reaction paths were calculated by means of the transition state theory. Three predictors were determined for the prediction of the most probable transition state and the reaction path. The differences in the reaction rates were explained in terms of the presence of hydrogen bonds in the transition state complexes and the entropy effects. Finally the results obtained were compared with the available experimental data in order to assess the reliability of the proposed model.     

Gas-phase photolytic production of hydroxyl radicals in an ultraviolet purifier for air and surfaces

We have measured the concentration of hydroxyl radicals (OH) produced in the gas phase by a commercially available purifier for air and surfaces, using the time rate of decay of n-heptane added to an environmental chamber. The hydroxyl generator, an Odorox® BOSS? model, produces the OH through 185-nm photolysis of ambient water vapor. The steady-state concentration of OH produced in the 120 m³ chamber is, with 2σ error bars, (3.25 ± 0.80) × 10⁶ cm^?3. The properties of the hydroxyl generator, in particular the output of the ultraviolet lamps and the air throughput, together with an estimation of the water concentration, were used to predict the amount of OH produced by the device, with no fitted parameters. To relate this calculation to a steady-state concentration, we must estimate the OH loss rate within the chamber owing to reaction with the n-heptane and the 7 ppb of background hydrocarbons that are present. The result is a predicted steady-state concentration in excellent agreement with the measured value. This shows we understand well the processes occurring in the gas phase during operation of this hydroxyl radical purifier.

Implications: Hydroxyl radical air purifiers are used for cleaning both gaseous contaminants, such as volatile organic compounds (VOCs) or hazardous gases, and biological pathogens, both airborne and on surfaces. This is the first chemical kinetic study of such a purifier that creates gas-phase OH by ultraviolet light photolysis of H₂O. It shows that the amount of hydroxyls produced agrees well with nonparameterized calculations using the purifier lamp output and device airflow. These results can be used for designing appropriate remediation strategies.     

Temperature-dependent rate coefficients for the reactions of Cl atoms with methyl methacrylate,methyl acrylate and butyl methacrylate at atmospheric pressure

Rate coefficients for the gas-phase reactions of Cl atoms with a series of unsaturated esters CH₂C(CH₃)C(O)OCH₃ (MMA), CH₂CHC(O)OCH₃ (MAC) and CH₂C(CH₃)C(O)O(CH₂)₃CH₃ (BMA) have been measured as a function of temperature by the relative technique in an environmental chamber with in situ FTIR detection of reactants. The rate coefficients obtained at 298 K in one atmosphere of nitrogen or synthetic air using propene, isobutene and 1,3-butadiene as reference hydrocarbons were (in units of 10^?10 cm³ molecule^?1 s^?1) as follows: k_(Cl+MMA) = 2.82 ± 0.93, k_(Cl+MAC) = 2.04 ± 0.54 and k_(Cl+BMA) = 3.60 ± 0.87. The kinetic data obtained over the temperature range 287–313 K were used to derive the following Arrhenius expressions (in units of cm³ molecule^?1 s^?1): k_(Cl+MMA) = (13.9 ± 7.8) × 10^?15 exp[(2904 ± 420)/T], k_(Cl+MAC) = (0.4 ± 0.2) × 10^?15 exp[(3884 ± 879)/T], k_(Cl+BMA) = (0.98 ± 0.42) × 10^?15 exp[(3779 ± 850)/T]. All the rate coefficients display a slight negative temperature dependence which points to the importance of the reversibility of the addition mechanism for these reactions. This work constitutes the first kinetic and temperature dependence study of the reactions cited above.An analysis of the available rates of addition of Cl atoms and OH radicals to the double bond of alkenes and unsaturated and oxygenated volatile organic compounds (VOCs) at 298 K has shown that they can be related by the expression: log k_OH = 1.09 log k_Cl ? 0.10. In addition, a correlation between the reactivity of unsaturated VOCs toward OH radicals and Cl atoms and the HOMO of the unsaturated VOC is presented. Tropospheric implications of the results are also discussed.     

Application of the EPR spin-trapping technique for the investigation of the reactions of carbonate, bicarbonate, and phosphate anions with hydroxyl radicals generated by the photolysis of H2O2

The spin trapping technique with electron paramagnetic resonance (EPR) detection of spin adducts was applied for the investigation of the reaction of hydroxyl radicals, generated by the photolysis of hydrogen peroxide, with bicarbonate and carbonate anions. The results have been compared with those obtained for aqueous solutions of hydrogen peroxide as well as solutions containing phosphate buffers at pH values identical with those of the carbonate, and bicarbonate solutions. Both the carbonate, and bicarbonate anions quenched the hydroxyl radicals more efficiently than phosphate buffers. The effect depended on the anion concentrations, and it was most pronounced in the presence of carbonate. Rate constants for the reaction of OH with the investigated anions have been calculated. They are very close to values reported in the literature, obtained using optical detection of the carbonate and phosphate radicals.     

Use of carbon and nitrogen stable isotope ratios to assess the effects of environmental contaminants on aquatic food webs

In this study, the value of carbon (delta13C) and nitrogen (delta15N) stable isotope ratios were determined in nymphs of a top-predator, the common backswimmer (Notonecta glauca L.), collected in 18 m3 outdoor freshwater mesocosms used to assess the fate and ecotoxicological effects of a diphenyl ether herbicide, fomesafen, applied alone or in combination with Agral 90 (mixture of polyethoxylated derivatives of nonylphenol). Both treatments had a negative effect on delta13C values which may reflect changes in carbon fluxes across food webs in the treated ponds associated with a shift in phytoplankton structure. A decrease in delta15N values was observed in the nymphs collected in mixture-treated ponds, which was presumably due to an increase in the abundance of rotifers and Chironominae larvae in these ponds. These preliminary results indicate that stable isotope ratios may be used as shortcuts to detect qualitative or quantitative shifts in the structure of aquatic food webs caused by pollutants.     

Activated carbon from industrial solid waste as an adsorbent for the removal of Rhodamine-B from aqueous solution: kinetic and equilibrium studies

The activated carbon was prepared using industrial solid waste called sago waste and physico-chemical properties of carbon were carried out to explore adsorption process. The effectiveness of carbon prepared from sago waste in adsorbing Rhodamine-B from aqueous solution has been studied as a function of agitation time, adsorbent dosage, initial dye concentration, pH and desorption. Adsorption equilibrium studies were carried out in order to optimize the experimental conditions. The adsorption of Rhodamine-B onto carbon followed second order kinetic model. Adsorption data were modeled using both Langmuir and Freundlich classical adsorption isotherms. The adsorption capacity Q0 was 16.12 mg g(-1) at initial pH 5.7 for the particle size 125-250 microm. The equilibrium time was found to be 150 min for 10, 20 mg l(-1) and 210 min for 30, 40 mg l(-1) dye concentrations, respectively. A maximum removal of 91% was obtained at natural pH 5.7 for an adsorbent dose of 100mg/50 ml of 10 mg l(-1) dye concentration and 100% removal was obtained when the pH was increased to 7 for an adsorbent dose of 275 mg/50 ml of 20 mg l(-1) dye concentration. Desorption studies were carried out in water medium by varying the pH from 2 to 10. Desorption studies were performed with dilute HCl and show that ion exchange is predominant dye adsorption mechanism. This adsorbent was found to be both effective and economically viable.     

Interactive effects of ozone and elevated carbon dioxide on the growth and physiology of black cherry, green ash, and yellow-poplar seedlings

Potted seedlings of black cherry (Prunus serotina Ehrh.) (BC), green ash (Fraxinus pennsylvanica Marsh.) (GA), and yellow-poplar (Liriodendron tulipifera L.) (YP) were exposed to one of the four treatments: (1) charcoal-filtered air (CF) at ambient CO(2) (control); (2) twice ambient O(3) (2 x O(3)); (3) twice ambient CO(2) (650 microl l(-1)) plus CF air (2 x CO(2)); or (4) twice ambient CO(2) (650 microl l(-1)) plus twice ambient O(3) (2 x CO(2) + 2 x O(3)). The treatments were duplicated in eight continuously stirred tank reactors for 10 weeks. Gas exchange was measured during the last 3 weeks of treatment and all seedlings were destructively harvested after 10 weeks. Significant interactive effects of O(3) and CO(2) on the gas exchange of all three species were limited. The effects of elevated CO(2) and O(3), singly and combined, on light-saturated net photosynthesis (A(max)) and stomatal conductance (g(s)) were inconsistent across species. In all three species, elevated O(3) had no effect on g(s). Elevated CO(2) significantly increased A(max) in GA and YP foliage, and decreased g(s) in YP foliage. Maximum carbon exchange rates and quantum efficiencies derived from light-response curves increased, while compensation irradiance and dark respiration decreased in all three species when exposed to 2 x CO(2). Elevated O(3) affected few of these parameters but any change that was observed was opposite to that from exposure to 2 x CO(2)-air. Interactive effects of CO(2) and O(3) on light-response parameters were limited. Carboxylation efficiencies, derived from CO(2)-response curves (A/C(i) curves) decreased only in YP foliage exposed to 2 x CO(2)-air. In general, growth was significantly stimulated by 2 x CO(2) in all three species; though there were few significant growth responses following exposure to 2 x O(3) or the combination of 2 x CO(2) plus 2 x O(3). Results indicate that responses to interacting stressors such as O(3) and CO(2) are species specific.     

Sorption of carbendazim and linuron from aqueous solutions with activated carbon produced from spent coffee grounds: Equilibrium,kinetic and thermodynamic approach

Spent coffee grounds (SCG) have been used for the production of activated carbon (AC) by impregnation with different ratios of phosphoric acid at 600?°C, Xp (H₃PO₄/coffee): 3:1^30%, 4:1^30%, 3:1^50% and 4:1^50%. The obtained AC was characterized by BET, FTIR and SEM. BET surface area corresponds to 803.422 m² g^?1. The influences of the main parameters such as contact time, the pesticides initial concentration, adsorbent dose, pH and temperature on the efficiency of separation process were investigated during the batch operational mode. Results were modeled by adsorption isotherms: Langmuir, Freundlich and Temkin isotherms, which gave satisfactory correlation coefficients. The maximum adsorption capacities calculated from the Langmuir isotherms were 11.918?mg g^?1 for carbendazim and 5.834?mg g^?1 for linuron at room temperature. Adsorption kinetics of carbendazim and linuron have been studied by the pseudo-first-order, the pseudo-second-order and the intraparticle diffusion model. The results of adsorption kinetics have been fitted the best by pseudo-second-order model. The resulted data from FTIR characterization pointed to the presence of many functional groups on the AC surface. SCG adsorbent, as an eco-friendly and low-cost material, showed high potential for the removal of carbendazim and linuron from aqueous solutions.     

Improvement of oxygen-containing functional groups on olive stones activated carbon by ozone and nitric acid for heavy metals removal from aqueous phase

Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O₃) and in liquid phase using nitric acid (HNO₃). The activated carbon samples were characterized using N₂ adsorption–desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m²/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich–Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO₃), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.     

Woody residues of the grape production chain as an alternative precursor of high porous activated carbon with remarkable performance for naproxen uptake from water

Environmental Science and Pollution Research - Activated carbon prepared from grape branches was used as a remarkable adsorbent to uptake naproxen and treat a synthetic mixture from aqueous...