Benzene in Auto Exhaust

The gas phase thermal decomposition rates of the C₁ and C₂-substituted peroxyacyl nitrates (RC(O)OONO₂), PAN (R = CH₃), PPN (R = C₂H₅) and vinyl-PAN (R = CH₂ = CH-) have been measured at ambient temperature (288 - 299 K) and 1 atm. of air. Our results for PAN (k = A exp (-E_a/RT), log₁₀ (A, s^-1) = 16.2 ± 1.6, E_a = 26.9 ± 2.1 kcal / mol, k₂₉₈ = 3.0 × 10^?4S^?1) are consistent with literature data. Thermal decomposition rates for PPN and vinyl-PAN are similar to that for PAN, with k₂₉₈ = 3.0 × 10^?4S^?1 for PAN, 3.4 × 10^?4S^?1 for PPN and 3.0 × 10^?4S^?1 for vinyl-PAN. Implications for the atmospheric persistence of PPN and vinyl-PAN as compared to that of PAN are briefly discussed.     

Influence of temperature on the chemical removal of 3-methylbutanal,trans-2-methyl-2-butenal,and 3-methyl-2-butenal by OH radicals in the troposphere

Absolute rate coefficients for the gas-phase reactions of OH radical with 3-methylbutanal (k₁), trans-2-methyl-2-butenal (k₂), and 3-methyl-2-butenal (k₃) have been obtained with the pulsed laser photolysis/laser-induced fluorescence technique. Gas-phase concentration of aldehydes was measured by UV absorption spectroscopy at 185 nm. Experiments were performed over the temperature range of 263–353 K at total pressures of helium between 46.2 and 100 Torr. No pressure dependence of all k_i (i = 1–3) was observed at all temperatures. In contrast, a negative temperature dependence of k_i (i.e., k_i increases when temperature decreases) was observed in that T range. The resulting Arrhenius expressions (±2σ) are: k₁(T) = (5.8 ± 1.7)×10^?12 exp{(499 ± 94)/T} cm³ molecule^?1 s^?1, k₂(T)=(6.9 ± 0.9)×10^?12 exp{(526 ± 42)/T} cm³ molecule^?1 s^?1, k₃(T)=(5.6 ± 1.2)×10^?12 exp{(666 ± 54)/T} cm³ molecule^?1 s^?1.The tropospheric lifetimes derived from the above OH-reactivity trend are estimated to be higher for 3-methylbutanal than those for the unsaturated aldehydes. A comparison of the tropospheric removal of these aldehydes by OH radicals with other homogeneous degradation routes leads to the conclusion that this reaction can be the main homogeneous removal pathway. However, photolysis of these aldehydes in the actinic region (λ > 290 nm) could play an important role along the troposphere, particularly for 3-methyl-2-butenal. This process could compete with the OH reaction for 3-methylbutanal or be negligible for trans-2-methyl-2-butenal in the troposphere.     

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.     

Rate Constants for the Reaction of OH with Halocarbons in the Presence of O2 + N2

Rates of CO₂ production in the reaction CO + OH and CO + OH + halocarbon have been used to determine rate constants for some OH + halocarbon reactions at 29.5°C relative to that of k(CO + OH) = 2.69 × 10^?13 cm³ molecule^?1 sec^?1. The following rate constants were obtained: k(OH + CH₃Cl) = 3.1 ± 0.8, k(OH + CH₂Cl₂) = 2.7 ± 1.0, k(OH + C₂H₅Cl) = 44.0 ± 25, k(OH + CICH₂CH₂CI) = 6.5, (<29) and k(OH + CH₃CCl₃) = 2.1 (<5.7) cm³ molecule^?1 sec^?1 × 10^?14. The k values, CH₂Cl₂ excepted, are in substantial agreement with determinations made in nonoxygen environments. The present results for CH₂Cl₂ are almost certainly in error due to difficulties with the competitive approach used.     

Kinetic studies of O3 reactions with 3-bromopropene and 3-iodopropene in the temperature range 288–328 K

The kinetics of the reactions of O₃ with 3-bromopropene and 3-iodopropene has been studied over the temperature range of 288–328 K at atmospheric pressure. The results obtained for the room temperature rate constants are (1.88 ± 0.22) × 10^?18 and (3.52 ± 0.43) × 10^?18 cm³ molecule^?1 s^?1, and the proposed Arrhenius expressions are k = (3.47 ± 1.28) × 10^?15 exp[(?2233 ± 110)/T] and k = (8.17 ± 2.12) × 10^?14 exp[(?2991 ± 80)/T] cm³ molecule^?1 s^?1 for 3-bromopropene and 3-iodopropene, respectively. The atmospheric chemical lifetimes of these two compounds with O₃ were also estimated from these values.     

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.     

Photoassisted and photocatalytic degradation of sulfur mustard using TiO2 nanoparticles and polyoxometalates

The decomposition of highly toxic chemical warfare agent, sulfur mustard (bis(2-chloroethyl) sulfide or HD), has been studied by homogeneous photolysis and heterogeneous photocatalytic degradation on titania nanoparticles. Direct photolysis degradation of HD with irradiation system was investigated. The photocatalytic degradation of HD was investigated in the presence of TiO₂ nanoparticles and polyoxometalates embedded in titania nanoparticles in liquid phase at room temperature (33?±?2 °C). Degradation products during the treatment were identified by gas chromatography–mass spectrometry. Whereas apparent first-order kinetics of ultraviolet (UV) photolysis were slow (0.0091 min^?1), the highest degradation rate is obtained in the presence of TiO₂ nanoparticles as nanophotocatalyst. Simultaneous photolysis and photocatalysis under the full UV radiation leads to HD complete destruction in 3 h. No degradation products observed in the presence of nanophotocatalyst without irradiation in 3 h. It was found that up to 90 % of agent was decomposed under of UV irradiation without TiO₂, in 6 h. The decontamination mechanisms are often quite complex and multiple mechanisms can be operable such as hydrolysis, oxidation, and elimination. By simultaneously carrying out photolysis and photocatalysis in hexane, we have succeeded in achieving faster HD decontamination after 90 min with low catalyst loading. TiO₂ nanoparticles proved to be a superior photocatalyst under UV irradiation for HD decontamination.     

Heterogeneous reaction of NO2 with soot at different relative humidity

The influences of relative humidity (RH) on the heterogeneous reaction of NO₂ with soot were investigated by a coated wall flow tube reactor at ambient pressure. The initial uptake coefficient (γ _initial) of NO₂ showed a significant decrease with increasing RH from 7 to 70%. The γ _initial on “fuel-rich” and “fuel-lean” soot at RH = 7% was (2.59 ± 0.20) × 10^?5 and (5.92 ± 0.34) × 10^?6, respectively, and it decreased to (5.49 ± 0.83) × 10^?6 and (7.16 ± 0.73) × 10^?7 at RH = 70%, respectively. Nevertheless, the HONO yields were almost independent of RH, with average values of (72 ± 3)% for the fuel-rich soot and (60 ± 2)% for the fuel-lean soot. The Langmuir-Hinshelwood mechanism was used to demonstrate the negative role of RH in the heterogeneous uptake of NO₂ on soot. The species containing nitrogen formed on soot can undergo hydrolysis to produce carboxylic species or alcohols at high RH, accompanied by the release of little gas-phase HONO and NO.

     

Role of some organic inhibitors on the oxidation of dissolved sulfur dioxide by oxygen in rainwater medium

In August 2012, eight rainwater samples were collected and analyzed for pH and metal ions, viz., iron, copper, and manganese. The pH was within the range 6.84–7.65. The rate of oxidation of dissolved sulfur dioxide was determined using these rainwater samples as reaction medium. Kinetics was defined by the rate law: ?d[S(IV)]/dt = R _o = k _o[S(IV)]], where k _o is the first-order rate constant and R _o is the rate of the reaction. The effect of two volatile organic compounds—ethanol and 2-butanol—was examined and found to inhibit the oxidation as defined by the rate law: k _obs = k _o/(1 + B [Inh]), where k _obs is the first-order rate constant in the presence of the inhibitor, [Inh] is the concentration of the inhibitor, and B is the inhibitor parameter—an empirical constant. In the pH range of collected rainwater samples, the values of first-order rate constants ranged from 3.1?×?10^?5 to 1.5?×?10^?4 s^?1 at 25 °C. The values of inhibition parameter were found to be (5.99?±?3.91?×?10⁴) (ethanol) and (3.95?±?2.36)?×?10⁴ (2-butanol) at 25 °C.     

Environmental photochemical fate of pesticides ametryn and imidacloprid in surface water (Paranapanema River,São Paulo,Brazil)

In addition to direct photolysis studies, in this work the second-order reaction rate constants of pesticides imidacloprid (IMD) and ametryn (AMT) with hydroxyl radicals (HO^●), singlet oxygen (¹O₂), and triplet excited states of chromophoric dissolved organic matter (³CDOM^*) were determined by kinetic competition under sunlight. IMD and AMT exhibited low photolysis quantum yields: (1.23?±?0.07)?×?10^–2 and (7.99?±?1.61)?×?10^–3 mol Einstein^?1, respectively. In contrast, reactions with HO^● radicals and ³CDOM* dominate their degradation, with ¹O₂ exhibiting rates three to five orders of magnitude lower. The values of k_IMD,HO● and k_AMT,HO● were (3.51?±?0.06)?×?10⁹ and (4.97?±?0.37)?×?10⁹ L mol^?1 s^?1, respectively, while different rate constants were obtained using anthraquinone-2-sulfonate (AQ2S) or 4-carboxybenzophenone (CBBP) as CDOM proxies. For IMD this difference was significant, with k_IMD,3AQ2S*?=?(1.02?±?0.08)?×?10⁹ L mol^?1 s^?1 and k_IMD,3CBBP*?=?(3.17?±?0.14)?×?10⁸ L mol^?1 s^?1; on the contrary, the values found for AMT are close, k_AMT,3AQ2S*?=?(8.13?±?0.35)?×?10⁸ L mol^?1 s^?1 and k_AMT,3CBBP*?=?(7.75?±?0.80)?×?10⁸ L mol^?1 s^?1. Based on these results, mathematical simulations performed with the APEX model for typical levels of water constituents (NO₃^?, NO₂^?, CO₃^2?, TOC, pH) indicate that the half-lives of these pesticides should vary between 24.1 and 18.8 days in the waters of the Paranapanema River (São Paulo, Brazil), which can therefore be impacted by intensive agricultural activity in the region.

     

Corrosion and stability study of Bacillus thuringiensis var. kurstaki starch industry wastewater-derived biopesticide formulation

Biopesticides are usually sprayed on forests by using planes made up of aluminum alloy. Bioval derived from starch industry wastewater (SIW) in suspension form was developed as stable anticorrosive biopesticide formulation. In this context, various anticorrosion agents such as activated charcoal, glycerin, ethylene glycol, phytic acid, castor oil and potassium silicate were tested as anticorrosive agents. There was no corrosion found in Bioval formulation where potassium silicate (0.5% w/v) was added and compared with Foray 76 B, as an industrial standard, when stored over 6 months. In relation to other parameters, the anticorrosion formulation of Bioval+buffer+KSi reported excellent zeta potential (?33.19 ± 4 mV) and the viscosity (319.13 ± 32 mPa.s) proving it's stability over 6 months, compared to the standard biopesticide Foray 76 B (?36.62 ± 4 mV potential zeta, pH 4.14 ± 0.1 and 206 ± 21 mPa.s viscosity). Metal analysis of the different biopesticides showed that Bioval+buffer+KSi has no corrosion (5.11 ± 0.5 mg kg^?1 of Al and 13.53 ± 1.5 mg kg^?1 of Fe) on the aluminum alloy due to the contribution of sodium acetate buffer at pH 5. The bioassays reported excellent results for Bioval+Buffer+KSi (2.95 ± 0.3 × 10⁹ CFU mL^?1 spores and 26.6 ± 2.7 × 10⁹ IU L^?1 Tx) compared with initial Bioval (2.46 ± 0.3 × 10⁹ CFU mL^?1 spores and 23.09 ± 3 × 10⁹ IU L^?1 Tx) and Foray 76 B (2.3 ± 0.2 × 10⁹ CFU mL^?1 spores and 19.950 ± 2.1 UI L^?1 Tx) which was due to the break-up of the external chitinous membrane due to abrasive action of potassium silicate after ingestion by insects. The contribution of sodium acetate buffer and potassium silicate (0.5% and at pH = 5) as anticorrosion agent in the Bioval allowed production of an efficient biopesticide with a reduced viscosity and favorable pH as compared to Foray 76 B which enhanced the entomotoxic potential against spruce budworm (SB) larvae (Lepidoptera: Choristoneura fumiferana).     

Temperature-responsive graphene oxide/N-isopropylacrylamide/2-allylphenol nanocomposite for the removal of phenol and 2,4-dichlorophenol from aqueous solution

In this study, a novel thermo-responsive polymer was synthesized with efficient grafting of N-isopropylacrylamide as a thermosensitive polymer onto the graphene oxide surface for the efficient removal of phenol and 2,4-dichlorophenol from aqueous solutions. The synthesized polymer was conjugated with 2-allylphenol. Phenol and 2,4-dichlorophenol were monitored by ultra-performance liquid chromatography system equipped with a photodiode array detector. The nanoadsorbent was characterized by different techniques. The nanoadsorbent revealed high adsorption capacity where the removal percentages of 91 and 99% were found under optimal conditions for phenol and 2,4-dichlorophenol, respectively (for phenol; adsorbent dosage = 0.005 g, pH = 8, temperature= 25 °C, contact time = 60 min; for 2,4-dichlorophenol; adsorbent dosage = 0.005 g, pH = 5, temperature = 25 °C, contact time = 10 min). Adsorption of phenol and 2,4-dichlorophenol onto nanoadsorbent followed pseudo-second-order kinetic and Langmuir isotherm models, respectively. The values of ΔG (average value = ? 11.39 kJ mol^?1 for phenol and 13.42 kJ mol^?1 for 2,4-dichlorophenol), ΔH (? 431.72 J mol^?1 for phenol and ? 15,721.8 J mol^?1 for 2,4-dichlorophenol), and ΔS (35.39 J mol^?1 K^?1 for phenol and ? 7.40 J mol^?1 K^?1 for 2,4-dichlorophenol) confirmed spontaneous and exothermic adsorption. The reusability study indicated that the adsorbent can be reused in the wastewater treatment application. Thermosensitive nanoadsorbent could be used as a low-cost and efficient sorbent for phenol and 2,4-dichlorophenol removal from wastewater samples.

     

Determination of Room Temperature OH Rate Constants for Acetylene,Ethylene Dichloride,Ethylene Dibromide,p-Dichlorobenzene and Carbon Disulfide

A relative rate procedure was used to measure hydroxyl rate constants at room temperature in the presence of oxygen. The photolysis of methyl nitrite in the presence of nitric oxide was used to generate OH radicals. The rate of loss of the test compounds was measured relative to that of ethane (k_OH = 2.74 × 10^-13 cm³ molec^-1 s^-1). The rates obtained at 297 ± 2 K are: acetylene = (7.8 ± 1.6) × 10^-13 cm³ molec^-1 s^-1,1,2-dichloroethane (2.8 ± Q.6) × 10^-13 cm³ molec^-1 s^-1, 1,2-dibromoethane (2.4 ± 0.5) × 10^-13 cm³ molec^-1 s^-1, p-dichlorobenzene (4.3 ± 0.9) × 10^-13 cm³ molec^-1 s^-1 and carbon disulfide (29 ± 6) × 10^-13 cm³ molec^-1 s^-1. Under a proposed EPA rule, this OH rate determination procedure could be used to determine if a given volatile organic will be subject to control for reduction of photochemical ozone.     

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.     

Cyclooctane tropospheric degradation initiated by reaction with Cl atoms

Goal, Scope and Background Within the non-methane hydrocarbons, alkanes constitute the largest fraction of the anthropogenic emissions of volatile organic compounds. For the case of cyclic alkanes, tropospheric degradation is expected to be initiated mainly by OH reactions in the gas phase. Nevertheless, Cl atom reaction rate constants are generally one order of magnitude larger than those of OH. In the present work, the reaction of cyclooctane with Cl atoms has been studied within the temperature range of 279–333 K. Methods The kinetic study has been carried out using the fast flow tube technique coupled to mass spectrometry detection. The reaction has been studied under low pressure conditions, p=1 Torr, with helium as the carrier gas. Results The measured room temperature rate constant is very high, k=(2.63±0.54)×10⁻¹⁰ cm³molecule⁻¹s⁻¹, around 20 times larger than that for the corresponding OH reaction. We also report the results of the rate coefficients obtained at different temperatures: k = (3.5±1.2)×10⁻¹⁰ exp[(−79±110)/T] cm³ molecule⁻¹ s⁻¹ within the range of 279–333 K. This reaction shows an activation energy value close to zero. Discussion Quantitative formation of HCl has been observed, confirming the mechanism through H-atom abstraction. The reactivity of cyclic alkanes towards Cl atoms is clearly dependent on the number of CH₂ groups in the molecule, as is shown by the increase in the rate constant when the length of the organic chain increases. This increase is very high for the small cyclic alkanes and it seems that the reactions are approaching the collision-controlled limit for cyclohexane and cyclooctane. Conclusions These results show that gas-phase reaction with Cl in marine or coastal areas is an efficient sink (competing with the gas phase, OH initiated degradation) for the Earth’s emissions of cyclooctane, with a Cl-based lifetime ranging from 11 to 2000 hours, depending on the location and time of day. Recommendations and Perspectives Cl and OH fast reactions with cyclooctane are expected to define the lifetime of cyclooctane emissions to the atmosphere. The degradation of cyclooctane occurs in a short period of time and consequently (under conditions of low atmospheric mass transport), close to the emission sources enabling a significant contribution to local effects, like the formation of photochemical smog. ESS-Submission Editor: Prof. Dr. Gerhard Lammel (lammel@recetox.muni.cz)     

Kinetics of Sulfur-Oxide Formation in Flames: II. Low Pressure H2S Flames

The microstructure of 1/10 and 1/20 atmosphere, lean H₂S—O₂—N₂ flames is developed using the mass-spectrometric flame-sampling technique. The flame mechanism developed is in agreement with that determined from an earlier study on 1-atm H₂S flames. The formation of SO₂ appears to be primarily related to the production of SH and the ensuing oxidation steps SH + O₂ = SO + OH and SO + O₂ = SO₂ + O. While there is some question whether SO₂ formation occurs via an SO or an S₂O intermediate, the present study does not give direct support to the role of S₂O in the oxidation mechanism. However, the presence of significant quantities of free sulfur in the pre-flame zone may be indicative of S₂O formation via SO + S → S₂O, and, possibly, via the disproportionation of SO, 3SO → S₂O + SO₂. Kinetic analyses of some of the pre-flame reactions indicate an apparent activation energy of 17,300 calories/mole for the decomposition of H₂S. The actual initiation process in the flame mechanism requires further examination. The specific rate for the reaction step H₂S + O = OH + SH is given by k ₆ = 1.45 × 10₁₅ exp ( – 6600/RT) cm³ mole^–1 sec^–1, and the specific rate for the oxidation of SO, SO + O₂ = SO₂ + O, is given by k ₅ = 5.2 × 10₁₄ exp (—19,300/RT) cm³ mole^–1 sec^–1.     

Photooxidation of methylhydroperoxide and ethylhydroperoxide in the aqueous phase under simulated cloud droplet conditions

The photooxidation of methylhydroperoxide (MHP) and ethylhydroperoxide (EHP) was studied in the aqueous phase under simulated cloud droplet conditions. The kinetics and the reaction products of direct photolysis and OH-oxidation were studied for both compounds. The photolysis frequencies obtained were J_MHP=4.5 (±1.0)×10⁻⁵ s⁻¹ and J_EHP=3.8 (±1.0)×10⁻⁵ s⁻¹ for MHP and EHP respectively at 6 °C. The rate constants of OH-oxidation of MHP at 6 °C were 6.3 (±2.6)×10⁸ M⁻¹ s⁻¹ and 5.8 (±1.9)×10⁸ M⁻¹ s⁻¹ relative to ethanol and 2-propanol respectively, and the rate constant of OH-oxidation of EHP was 2.1 (±0.6)×10⁹ M⁻¹ s⁻¹ relative to 2-propanol at 6 °C. The reaction products obtained were not only the corresponding aldehydes, but also the corresponding acids, and hydroxyhydroperoxides as primary reaction products. The yields for these products were sensitive to the pH value. The carbon balance was higher than 85% for all experiments, showing that most reaction products were detected. A chemical mechanism was proposed for each reaction, and the atmospheric implications were discussed.     

Kinetic study of the OH reaction with some hydrochloroethers under simulated atmospheric conditions

Using the relative rate technique, rate constants for the gas-phase reactions of hydroxyl radicals with 2-chloroethyl methyl ether (k₁), 2-chloroethyl ethyl ether (k₂) and bis(2-chloroethyl) ether (k₃) have been measured. Experiments were carried out at (298 ± 2) K and atmospheric pressure using synthetic air as bath gas. Using n-pentane and n-heptane as reference compounds, the following rate constants were derived: k₁ = (5.2 ± 1.2) × 10^?12, k₂ = (8.3 ± 1.9) × 10^?12 and k₃ = (7.6 ± 1.9) × 10^?12, in units of cm³ molecule^?1 s^?1. This is the first experimental determination of k₂ and k₃ under atmospheric pressure. The rate constants obtained are compared with previous literature data and the observed trends in the relative rates of reaction of hydroxyl radicals with the ethers studied are discussed. The atmospheric implications of the results are considered in terms of lifetimes and fates of the hydrochloroethers studied.     

Gaseous and particulate water-soluble organic and inorganic nitrogen in rural air in southern Scotland

Simultaneous daily measurements of water-soluble organic nitrogen (WSON), ammonium and nitrate were made between July and November 2008 at a rural location in south-east Scotland, using a ‘Cofer’ nebulizing sampler for the gas phase and collection on an open-face PTFE membrane for the particle phase. Average concentrations of NH₃ were 82 ± 17 nmol N m^?3 (error is s.d. of triplicate samples), while oxidised N concentrations in the gas phase (from trapping NO₂ and HNO₃) were smaller, at 2.6 ± 2.2 nmol N m^?3, and gas-phase WSON concentrations were 18 ± 11 nmol N m^?3. The estimated collection efficiency of the nebulizing samplers for the gas phase was 88 (±8) % for NH₃, 37 (±16) % for NO₂ and 57 (±7) % for WSON; reported average concentrations have not been corrected for sampling efficiency. Concentrations in the particle phase were smaller, except for nitrate, at 21 ± 9, 10 ± 6 and 8 ± 9 nmol N m^?3, respectively. The absence of correlation in either phase between WSON and either (NH₃ + NH₄⁺) or NO₃^? concentrations suggests atmospheric WSON has diverse sources. During wet days, concentrations of gas and particle-phase inorganic N were lower than on dry days, whereas the converse was true for WSON. These data represent the first reports of simultaneous measurements of gas and particle phase water-soluble nitrogen compounds in rural air on a daily basis, and show that WSON occurs in both phases, contributing 20–25% of the total water-soluble nitrogen in air, in good agreement with earlier data on the contribution of WSON to total dissolved N in rainfall in the UK.     

Evaluation of the reaction artifacts in an annular denuder-based sampler resulting from the heterogeneous ozonolysis of naphthalene

The heterogeneous ozonolysis of naphthalene adsorbed on XAD-4 resin was studied using an annular denuder technique. The experiments involved depositing a known quantity of naphthalene on the XAD-4 resin and then measuring the quantity of the solid naphthalene that reacted away under a constant flow of gaseous ozone (0.064 to 4.9 ppm) for a defined amount of time. All experiments were performed at room temperature (26 to 30 °C) and atmospheric pressure. The kinetic rate coefficient for the ozonolysis reaction of naphthalene adsorbed on XAD-4 resin is reported to be (10.1?±?0.4)?×?10^?19 cm³ molecule^?1 s^?1 (error is 2σ, precision only). This value is five times greater than the currently recommended literature value for the homogeneous gas phase reaction of naphthalene with ozone. The obtained rate coefficient is used to evaluate reaction artifacts from field concentration measurements of naphthalene, acenaphthene, and phenanthrene. The observed uncertainties associated with field concentration measurements of naphthalene, acenaphthene, and phenanthrene are reported to be much higher than the uncertainties associated with the artifact reactions. Consequently, ozone reaction artifact appears to be negligible compared to the observed field measurement uncertainty results.