OH Radical Concentration Research Articles

Measurement of OH radical CT for inactivating Cryptosporidium parvum using photo/ferrioxalate and photo/TiO2systems

This study investigates the inactivation of Cryptosporidium parvum using the OH radical and reports the OH radical CT (OH radical concentration x contact time) values for C. parvum inactivation. Although a wealth of information has demonstrated the efficacy of the microbial inactivation activity of the OH radical, no studies have performed a quantitative estimation of the OH radical for C. parvum inactivation. The CT value of the OH radical required for 2 log C. parvum inactivation was measured with two OH radical-generating systems, photo/ferrioxalate and photo/TiO2. The OH radical was approx. 10(4)-10(7)-fold more effective for microbial inactivation than other popular chemical disinfectants such as ozone, chlorine dioxide and free chlorine. The OH radical appears to be suitable for microbial inactivation with a calculated CT value required for 2 log C. parvum inactivation of 9.3 x 10(-5) mg min l(-1). This study is the first report of an investigation on the role of the OH radical in the photo/ferrioxalate and photo/TiO2 systems and on the OH radical CT required for C. parvum inactivation.

Photolysis of surface O3 and production potential of OH radicals in the atmosphere over the Tibetan Plateau

With an area of 2.5 million km2 and an average altitude of about 4000 m above sea level, the Tibetan Plateau is the largest and highest plateau in the mid‐latitudes of the Northern Hemisphere. The high altitude, low latitude, and large snow coverage create strong surface solar radiation on the plateau. It is therefore likely that the atmosphere over the plateau is very photochemically active, with a high production potential for OH radicals by ozone photolysis. We used the Tropospheric Ultraviolet‐Visible Radiation (TUV) model to calculate the photolysis rate of ozone in the Mt. Qomolangma (Everest) region under clear sky conditions. Field measurement data were used to calculate the production rate and concentration of OH radicals in the atmosphere. In the summer noon, over non‐snow‐covered area, surface ozone photolysis rates J(O1D) were 4–5 × 10−5 s−1, the OH radical production rate range was 1–4 × 106 s−1, and the OH concentrations range was 106 to 107 cm−3. Over areas covered with ice and snow, the J(O1D) and OH production rates could be as high as 1.3 × 10−4 s−1 and 5.5 × 106 cm−3 s−1, respectively, because of strong snow albedo. We also calculated the spatial distributions of J(O1D) and OH production over the whole Tibetan Plateau. Because of the large area covered with snow, the O3 photolysis rates in winter could be equal to or even higher than the rates in summer and might create as photochemically active an atmosphere as in summer.

Technical note: Measuring tropospheric OH and HO<sub>2</sub> by laser-induced fluorescence at low pressure. A comparison of calibration techniques

Abstract. The hydroxyl radical (OH) is one of the most important oxidants in the atmosphere, as it is involved in many reactions that affect regional air quality and global climate change. Because of its high reactivity, measurements of OH radical concentrations in the atmosphere are difficult, and often require careful calibrations that rely on the production of a known concentration of OH at atmospheric pressure. The Indiana University OH instrument, based on the Fluorescence Assay by Gas Expansion technique (FAGE), has been calibrated in the laboratory using two different approaches: the production of OH from the UV-photolysis of water-vapor, and the steady-state production of OH from the reaction of ozone with alkenes. The former technique relies on two different actinometric methods to measure the product of the lamp flux at 184.9 nm and the photolysis time. This quantity derived from N2O actinometry was found to be 1.5 times higher than that derived from O2 actinometry. The water photolysis and ozone-alkene techniques are shown to agree within their experimental uncertainties (respectively 17% and 44%), although the sensitivities derived from the ozone-alkene technique were systematically lower by 40% than those derived from the water-vapor UV- photolysis technique using O2 actinometry. The agreement between the two different methods improves the confidence of the water-vapor photolysis method as an accurate calibration technique for HOx instruments. Because several aspects of the mechanism of the gas phase ozonolysis of alkenes are still uncertain, this technique should be used with caution to calibrate OH instruments.

Detection of hydroxyl radical in plasma reaction on toluene removal

A new method was introduced to detect the concentration of OH radical in dielectric barrier discharge (DBD) reaction. A film, which was impregnated with salicylic acid, was used to detect OH radical in plasma reaction at room temperature and atmospheric pressure. Salicylic acid reacts with OH radical and produces 2,5-dihydroxybenzoic acid (2,5-DHBA). Then, a high performance liquid chromatography (HPLC) was carried out to detect the concentration of 2,5-DHBA. Therefore, OH radical in nonthermal plasma reaction could be calculated. In this plasma reaction, the applied voltage was controlled at 10 kV, the initial concentration of toluene was 400 mg/m3, and the gas flow rate was 300 ml/min. It was observed that when the film was placed away from the plasma area, 2,5-DHBA could not be detected by HPLC, although the sampling time lasted for 48 h. On the other hand, when the film was placed in the plasma area and the sampling time being too long (> 4 h), the concentration of 2,5-DHBA was also below detection limit, and it could not be detected by HPLC. However, when the film was placed in the plasma reaction field with the sampling time being 3 h, the concentration of OH radical was calculated to be 10.54 x 10(12) cm(-3). In addition, concentration of OH radical was investigated under different humidity, such as 0.2%, 0.4%, 0.6%, 0.8%, and 1.0%. The results showed that the amount of OH radical stayed at order of magnitude of 10(12) cm(-3) and increased with the increase of humidity.

Thermal Decomposition of CF3 and the Reaction of CF2 + OH → CF2O + H

The reflected shock tube technique with multipass absorption spectrometric detection (at a total path length of approximately 1.75 m) of OH-radicals at 308 nm has been used to study the dissociation of CF3-radicals [CF3 + Kr --> CF2 + F + Kr (a)] between 1,803 and 2,204 K at three pressures between approximately 230 and 680 Torr. The OH-radical concentration buildup resulted from the fast reaction F + H2O --> OH + HF (b). Hence, OH is a marker for F-atoms. To extract rate constants for reaction (a), the [OH] profiles were modeled with a chemical mechanism. The initial rise in [OH] was mostly sensitive to reactions (a) and (b), but the long time values were additionally affected by CF2 + OH --> CF2O + H (c). Over the experimental temperature range, rate constants for (a) and (c) were determined from the mechanistic fits to be kCF3+Kr = 4.61 x 10-9 exp(-30,020 K/T) and kCF2+OH = (1.6 +/- 0.6) x 10-10, both in units of cm3 molecule-1 s-1. Reaction (a), its reverse recombination reaction reaction (-a), and reaction (c) are also studied theoretically. Reactions (c) and (-a) are studied with direct CASPT2 variable reaction coordinate transition state theory. A master equation analysis for reaction (a) incorporating the ab initio determined reactive flux for reaction (-a) suggests that this reaction is close to but not quite in the low-pressure limit for the pressures studied experimentally. In contrast, reaction (c) is predicted to be in the high-pressure limit due to the high exothermicity of the products. A comparison with past and present experimental results demonstrates good agreement between the theoretical predictions and the present data for both (a) and (c).

Control of nanoparticle size and agglomeration through electric-field-enhanced flame synthesis

The isolated study of electrophoretic transport of nanoparticles (that are innately charged through thermionic emission), with no ionic wind, has been conducted under uniform electric fields. Titania nanoparticles are produced using a burner-supported low-pressure premixed flame in a stagnation-point geometry from corresponding organometallic vapor precursor. The material processing flow field is probed in-situ using laser-induced fluorescence (LIF) to map OH-radical concentrations and gas-phase temperatures. The experimental results of particle growth under different applied electric fields are compared with computations using monodisperse and sectional models. The results show that such electric field application can decrease aggregate particle size (e.g. from 40 to 18 nm), maintain metastable phases and particle crystallinity, and non-monotonically affect primary particle size (e.g. from 6 to 5 nm) and powder surface area. A specific surface area (SSA) for anatase titania nanopowder of 310 m2/g, when synthesized under an applied electric field of 125 V/cm, is reported. Results are also given for the synthesis of alumina nanoparticles.

Urban photochemistry in central Tokyo: 1. Observed and modeled OH and HO2 radical concentrations during the winter and summer of 2004

We used laser‐induced fluorescence to measure the concentrations of OH and HO2 radicals in central Tokyo during two intensive campaigns (IMPACT IV and IMPACT L) in January–February and July–August 2004. The estimated detection limit for the 10‐min data was 1.3 × 105 cm−3 for the nighttime and 5.2 × 105 cm−3 for the daytime. The median values of the daytime peak concentrations of HO2 were 1.1 and 5.7 pptv for the winter and summer periods, respectively, while the values for OH were 1.5 × 106 and 6.3 × 106 cm−3. High HO2 mixing ratios (>50 pptv) were observed on a day in summer when O3 mixing ratios exceeded 100 ppbv. The average nighttime concentrations of HO2 were 0.7 and 2.6 pptv for the winter and summer periods, respectively, while the values for OH were 1.8 × 105 and 3.7 × 105 cm−3. A photochemical box model constrained by ancillary observations was able to reproduce daytime OH concentrations reasonably well for both periods, although daytime HO2 concentrations were underestimated in winter and overestimated in summer. Increasing the wintertime hydrocarbon concentrations in the model led to an increase in daytime HO2 concentrations, thereby showing better agreement with observations; however, the model continued to underestimate HO2 concentrations at high NO mixing ratios. This underestimate was most pronounced in the mornings of both periods and during the daytime in winter. We studied processes that are capable of explaining this discrepancy, including unknown reactions of HNO4 or an unidentified HOx source that is linearly scalable to the NO mixing ratio. The important processes in terms of producing radicals were the olefin + O3 reactions in the nighttime of both periods and during the daytime in winter, the photolysis of carbonyls in the daytime for both periods, and the photolysis of HONO during the daytime in winter (using measured HONO concentrations) and during mornings in summer (using estimated HONO concentrations).

Diurnal Cycle of PAHs, Nitro-PAHs, and oxy-PAHs in a High Oxidation Capacity Marine Background Atmosphere

To improve our understanding of the formation and fate of nitro-PAHs, which contribute to the toxicity of ambient particles, the diurnal variation of their ambient concentration was studied concurrently with the corresponding PAH, OH radical, ozone, and oxy-PAH concentration, during an intensive field campaign at an eastern Mediterranean marine background location (Finokalia, Island of Crete) in August, 2001. The gas-phase PAH and OH radical concentrations maximized at noon. Gas-phase PAH concentrations were correlated (p < 0.001) with ambient temperatures. The gas-phase OH-radical-initiated PAH reaction was identified as the major process contributing to the ambient burden of nitro-PAHs. 2-Nitrofluoranthene and 2-nitropyrene were the most abundant particle-associated nitro-PAHs. A well-defined diurnal pattern was identified for both compounds exhibiting a maximum during midday followed by a rapid decrease. 9,10-Anthracenodione and 9-fluorenone, the most abundant oxy-PAHs, did not present a diurnal variation of concentration.

Spatiotemporal measurement using L-band ESR-CT system for water sonolysis in the presence of 1-Hydroxy-2,2,5,5-tetramethyl-3-imidazoline-3-oxide

When using ESR to measure the radicals generated by ultrasound, it is necessary to extract a solution and place it in the ESR system. To avoid this process, we incorporated an ultrasonic reaction cell in an L-band ESR-CT system, producing a system that allows the detection of the concentration of radicals during ultrasonic irradiation. This system was used to measure the time and space dependences of OH radicals generated by ultrasonic irradiation. When a 10ml aqueous solution of 1-hydroxy-2,2,5,5-tetramethyl-3-imidazoline-3-oxide (HTIO) was irradiated with ultrasound, it was found that the generation of radicals was clearly shown in a CT image after a period of 10min. It was also found that continued irradiation resulted in an increased concentration of radicals. In addition to this system, an X-band ESR system was also used to measure the concentration of OH radicals generated, and the results of both systems were then compared. Both results are very similar, showing that the proposed system, which was realized by incorporating an ultrasonic irradiation cell in the L-band ESR-CT system, operated properly. Because this system allows the measurement of sonochemical reactions in an opaque cell or an opaque solution such as blood and industrial wastewater, it is a very useful measurement system for achieving the applying of sonochemistry to the medical engineering field.

Observations of OH and HO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; radicals in coastal Antarctica

Abstract. OH and HO2 radical concentrations have been measured in the boundary layer of coastal Antarctica for a six-week period during the austral summer of 2005. The measurements were performed at the British Antarctic Survey's Halley Research Station (75° 35' S, 26° 19' W), using the technique of on-resonance laser-induced fluorescence to detect OH, with HO2 measured following chemical conversion through addition of NO. The mean radical levels were 3.9×105 molecule cm−3 for OH, and 0.76 ppt for HO2 (ppt denotes parts per trillion, by volume). Typical maximum (local noontime) levels were 7.9×105 molecule cm−3 and 1.50 ppt for OH and HO2 respectively. The main sources of HOx were photolysis of O3 and HCHO, with potentially important but uncertain contributions from HONO and higher aldehydes. Of the measured OH sinks, reaction with CO and CH4 dominated, however comparison of the observed OH concentrations with those calculated via the steady state approximation indicated that additional co-reactants were likely to have been present. Elevated levels of NOx resulting from snowpack photochemistry contributed to HOx cycling and enhanced levels of OH, however the halogen oxides IO and BrO dominated the CH3O2 – HO2 – OH conversion in this environment, with associated ozone destruction.

Isoprene and monoterpene fluxes from Central Amazonian rainforest inferred from tower-based and airborne measurements, and implications on the atmospheric chemistry and the local carbon budget

Abstract. We estimated the isoprene and monoterpene source strengths of a pristine tropical forest north of Manaus in the central Amazon Basin using three different micrometeorological flux measurement approaches. During the early dry season campaign of the Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001), a tower-based surface layer gradient (SLG) technique was applied simultaneously with a relaxed eddy accumulation (REA) system. Airborne measurements of vertical profiles within and above the convective boundary layer (CBL) were used to estimate fluxes on a landscape scale by application of the mixed layer gradient (MLG) technique. The mean daytime fluxes of organic carbon measured by REA were 2.1 mg C m−2 h−1 for isoprene, 0.20 mg C m−2 h−1 for α-pinene, and 0.39 mg C m−2 h−1 for the sum of monoterpenes. These values are in reasonable agreement with fluxes determined with the SLG approach, which exhibited a higher scatter, as expected for the complex terrain investigated. The observed VOC fluxes are in good agreement with simulations using a single-column chemistry and climate model (SCM). In contrast, the model-derived mixing ratios of VOCs were by far higher than observed, indicating that chemical processes may not be adequately represented in the model. The observed vertical gradients of isoprene and its primary degradation products methyl vinyl ketone (MVK) and methacrolein (MACR) suggest that the oxidation capacity in the tropical CBL is much higher than previously assumed. A simple chemical kinetics model was used to infer OH radical concentrations from the vertical gradients of (MVK+MACR)/isoprene. The estimated range of OH concentrations during the daytime was 3–8×106 molecules cm−3, i.e., an order of magnitude higher than is estimated for the tropical CBL by current state-of-the-art atmospheric chemistry and transport models. The remarkably high OH concentrations were also supported by results of a simple budget analysis, based on the flux-to-lifetime relationship of isoprene within the CBL. Furthermore, VOC fluxes determined with the airborne MLG approach were only in reasonable agreement with those of the tower-based REA and SLG approaches after correction for chemical decay by OH radicals, applying a best estimate OH concentration of 5.5×106 molecules cm−3. The SCM model calculations support relatively high OH concentration estimates after specifically being constrained by the mixing ratios of chemical constituents observed during the campaign. The relevance of the VOC fluxes for the local carbon budget of the tropical rainforest site during the measurements campaign was assessed by comparison with the concurrent CO2 fluxes, estimated by three different methods (eddy correlation, Lagrangian dispersion, and mass budget approach). Depending on the CO2 flux estimate, 1–6% or more of the carbon gained by net ecosystem productivity appeared to be re-emitted through VOC emissions.

Observations of total peroxy nitrates and aldehydes: measurement interpretation and inference of OH radical concentrations

Abstract. We describe measurements of total peroxy nitrates (ΣPNs), NO2, O3 and several aldehydes at Granite Bay, California, during the Chemistry and Transport of the Sacramento Urban Plume-2001 (CATSUP 2001) campaign, from 19 July–16 September 2001. We observed a strong photochemically driven variation of ΣPNs during the day with the median of 1.2 ppb at noon. Acetaldehyde, pentanal, hexanal and methacrolein had median abundances in the daytime of 1.2 ppb, 0.093 ppb, 0.14 ppb, and 0.27 ppb, respectively. We compare steady state and time dependent calculations of the dependence of ΣPNs on aldehydes, OH, NO and NO2 showing that the steady state calculations are accurate to ±30% between 10:00 and 18:00 h. We use the steady state calculation to investigate the composition of ΣPNs and the concentration of OH at Granite Bay. We find that PN molecules that have never been observed before make up an unreasonably large fraction of the ΣPNs unless we assume that there exists a PAN source that is much larger than the acetaldehyde source. We calculate that OH at the site varied between 2 and 7×106 molecule cm−3 at noon during the 8 weeks of the experiment.

Emission spectroscopy of atmospheric pressure plasmas for bio-medical and environmental applications

The paper demonstrates several ways of use of the UV–vis optical emission spectroscopy of medium resolution for the diagnostics of atmospheric pressure air and nitrogen plasmas relevant to bio-medical and environmental applications. Plasmas generated by DC discharges (streamer corona, transient spark, and glow discharge), AC microdischarges in porous ceramics, and microwave plasma were investigated. Molecular (OH, NO, CN) and atomic (H, O, N) radicals, and other active species, e.g. N 2 (C, B, A), N 2 + (B), were identified. The composition of the emission spectra gives insight in the ongoing plasma chemistry. Rotational, i.e. gas, and vibrational temperatures were evaluated by fitting experimental with simulated spectra. Streamer corona, transient spark and microdischarges generate cold, strongly non-equilibrium plasmas (300–550 K), glow discharge plasma is hotter, yet non-equilibrium (1900 K), and microwave plasma is very hot and thermal (∼3000–4000 K). Electronic excitation temperature and OH radical concentration were estimated in the glow discharge assuming the chemical equilibrium and Boltzmann distribution (9800 K, 3 × 10 16 cm −3). Optical emission also provided the measurement of the active plasma size of the glow discharge, and enabled calculating its electron number density (10 12 cm −3).

Role of atomic hydrogen diffusion in a hydrogen flame

A numerical modeling study of the propagation of a laminar flat homogeneous gas flame has shown that in a hydrogen-air flame, a rapid increase in the concentration of OH radicals begins in the range of low temperatures and the concentration profile has two maxima. The first maximum in the low-temperature region of the front is related to the diffusion of H atoms, formation of HO2 radicals, and the quadratic branching reaction H + HO2 → OH + OH. The second maximum in the OH concentration profile is due to the classical high-temperature branching reactions H + O2 → OH + O and O + H2 → OH + H.

Experimental and theoretical rate constants for CH 4 + O 2 → CH 3 + HO 2

In this study, rate constants for the primary initiation process in low to moderate temperature CH 4 oxidation CH 4 + O 2 → CH 3 + HO 2 have been measured in a reflected shock tube apparatus between 1655 and 1822 K using multipass absorption spectrometric detection of OH radicals at 308 nm. After rapid dissociation of HO 2 yielding H atoms, which are instantaneously converted to OH by H + O 2 → OH + O, the temporal concentration of OH radicals was observed as the final product from the rate-controlling title reaction. The present work utilizes 18 optical passes corresponding to a total path length of 1.6 m. This configuration gives a signal to noise ratio of unity at ∼ 3 × 10 12 radicals cm −3. Hence, kinetics experiments could be performed at conditions of low [CH 4] 0 (60–70 ppm), thereby substantially reducing secondary chemistry. Possible implications of CH 4 dissociation contributing to the OH formation rates were considered. The present experimental results agree with a priori variational transition state theoretical (VTST) calculations, k th = 3.37 × 10 −19 T 2.745 exp ( − 26 , 041 K / T ) cm 3 molecule −1 s −1 , clearly showing overlap of experiment and theory, within experimental error. The new rate constant values obtained in this study are 8–10 times higher than the values used in the popular mechanisms GRI-Mech 3.0 and Leeds Methane Mechanism, version 1.5.

Hydrogen addition to acetylene–air laminar diffusion flames: Studies on soot formation under different flow arrangements

Axisymmetric co-flowing acetylene/air laminar diffusion flames have been experimentally investigated to study the effect of hydrogen addition on soot formation and soot morphology. An acetylene–hydrogen jet burning in co-flowing air at atmospheric pressure has been studied under different flow arrangements, i.e., premixed and with separate addition of acetylene and hydrogen. Thermophoretic sampling and analysis by transmission electron microscopy are employed for soot diagnostics. Soot microstructure, primary particle size, soot volume fraction, and fractal geometry results are reported. The effect of hydrogen addition on the temperature field is moderate (maximum increase ∼ 100 K ), the effect being greater when hydrogen is premixed with acetylene. Soot volume fraction decreases with hydrogen addition. A shift was noted in the soot volume fraction peak with change in the Reynolds and Froude numbers at the burner exit. The primary soot particle diameter is in the range of 20–35 nm. Soot particles are larger in size close to the burner for the pure acetylene flame. A reverse trend is observed with hydrogen addition. The fractal dimension of the soot aggregates is about 1.7–1.8. It is unaffected by hydrogen addition and location in the flame. Soot aggregate size tends to decrease with hydrogen addition. The results of the present study on the effect of hydrogen addition on soot volume fraction and mean primary particle size are in good correlation with the results of other investigators for ethylene–, propane–, and butane–air flames, which have been described with regard to the HACA mechanism of soot nucleation and growth and enhanced soot oxidation in fuel-rich flames by increased OH radical concentration.

Investigation of a physical disinfection process based on pulsed underwater corona discharges

To overcome the side effects of commonly used water disinfection methods based on chemicals, advanced oxidation processes (AOP's) are presently considered as an alternative. These processes are based on the effect of highly reactive oxidants (like ozone, OH radicals, H 2 O 2 , et.) on microorganisms and toxic organic compounds. In this work the effects and products from pulsed underwater corona discharges have been investigated for their potential to remove contaminants from the water. Pulsed underwater corona discharges create oxidative and reductive species, UV radiation, shock waves and strong electric field at the tip of propagating streamers. It has been supposed that the combined appearance of these effects leads to an effective destruction of contaminants in the water. It was the aim of this work to quantify the production rates of oxidants and the intensity of other effects from underwater corona discharges, to demonstrate their effectiveness for the inactivation of microorganisms and to propose a suitable corona reactor that is scalable to large throughputs. For that purpose a coaxial corona reactor was designed with a central anode covered by a thin (200-300 μm) porous ceramic layer. The conductive porous ceramic and the anode cathode water gap form a parallel resistive-capacitive voltage divider. For times greater than the dielectric relaxation time of the water (τ=ee 0 /σ) resistive voltage division dominates and the electric field at the ceramic layer can be more enhanced than in the case of capacitive voltage division. Applying a pulsed voltage of 30-50 kV for a duration of 200-400 ns to the anode a large number of streamers is launched homogeneously from the ceramic surface extending up to 10 mm into the anode cathode water gap. An L-C chain Blumlein configuration has been selected to generate the pulses. By changing the number and the values of the LC elements the impedance of the generator and its pulse width could easily be adapted to the requirements of the experiment. Different ceramic layers were tried, but the best results were obtained with almandine which has a very low pH value at its isoelectric point. The number and the length of streamers increased linearly with the anode voltage. The reactor impedance was mainly determined by the water conductivity. Little influence from the appearance of streamers was observed. A large number of chemical probes have been selected to measure the oxidant production quantitatively. OH and H radicals created in core of a streamer channel are the most important primary products. As the channel cools down they recombine or form secondary products like H 2 O 2 and H 2 . H 2 O 2 accumulates in the bulk water and becomes a source of additional OH radicals due to the interaction with UV radiation and the liberation of Fenton reagents from the anode. Therefore, H 2 O 2 plays an important role in the disinfection process. Using DNTA as a chemical probe for OH radicals combined with an OH scavenger and measuring the H 2 O 2 yield simultaneously the initial OH radical concentration at the position of the cold streamer was found to be 30 mM. Different gases were percolated through the reactor to enhance the oxidant production. Saturating the water with N 2 O it was also possible to prove the existence of solvated electrons in the water after the formation of streamer discharges.

A new detailed chemical model for indoor air pollution

A detailed chemical box model has been constructed based on a comprehensive chemical mechanism (the Master Chemical Mechanism) to investigate indoor air chemistry in a typical urban residence in the UK. Unlike previous modelling studies of indoor air chemistry, the mechanism adopted contains no simplifications such as lumping or the use of surrogate species, allowing more insight into indoor air chemistry than previously possible. The chemical mechanism, which has been modified to include the degradation reactions of key indoor air pollutants, contains around 15,400 reactions and 4700 species. The results show a predicted indoor OH radical concentration up to 4.0×10 5 molecule cm −3, only a factor of 10–20 less than typically observed outdoors and sufficient for significant chemical cycling to take place. Concentrations of PAN-type species and organic nitrates are found to be important indoors, reaching concentrations of a few ppb. Sensitivity tests highlight that the most crucial parameters for modelling the concentration of OH are the light-intensity levels and the air exchange rate. Outdoor concentrations of O 3 and NO X are also important in determining radical concentrations indoors. The reactions of ozone with alkenes and monoterpenes play a major role in producing new radicals, unlike outdoors where photolysis reactions are pivotal radical initiators. In terms of radical propagation, the reaction of HO 2 with NO has the most profound influence on OH concentrations indoors. Cycling between OH and RO 2 is dominated by reaction with the monoterpene species, whilst alcohols play a major role in converting OH to HO 2. Surprisingly, the absolute reaction rates are similar to those observed outdoors in a suburban environment in the UK during the summer. The results from this study highlight the importance of tailoring a model for its particular location and the need for future indoor air measurements of radical species, nitrated species such as PANs and organic nitrates, photolysis rates of key species over the range of wavelengths observed indoors and concurrent measurements of outdoor air pollutant concentrations.

Effect of CH3OOH on the atmospheric concentration of OH radicals

Abstract Methyl hydroperoxide (CH3OOH, MHP) is known to be a significant sink and reservoir of HOx and ROx radicals in the atmosphere. In order to investigate the impact of MHP on the concentration of atmospheric OH radicals, two key gas-phase reactions of MHP, i.e. the reactions with OH radicals and with UV photolysis, have been simulated at temperature of 293±2 K and total pressure of 1.01×105 Pa, using the long path Fourier transform infrared (LP-FTIR) spectometry. OH radicals are generated by the photolysis of O3 in the presence of water vapor. Combined with the relative rate method, the reaction rate constant of MHP with OH radicals is determined to be (3.99±0.15)×10-12 cm3 molecule-1 s-1, and thus the atmospheric lifetime of MHP is estimated at 2.9 days. Furthermore, from detailed analysis of the UV photolysis of MHP, the yield of OH radicals is obtained to be 0.91±0.04. Based on the MHP atmospheric lifetime and the yield of OH radicals, it is concluded that MHP plays an essential role in the distri...

CH 3OCF 2CHFCl and CHF 2OCF 2CHFCl: Reaction with Cl atoms, atmospheric lifetimes, ozone depletion and global warming potentials

The relative rate technique has been used to determine the rate constants of the reactions of Cl atoms with 2-chloro-1,1,2-trifluoroethyl-methyl-ether (CH 3OCF 2CHFCl) and 2-chloro-1,1,2-trifluoroethyl-difluoromethyl-ether (CHF 2OCF 2CHFCl). Experiments were carried out at 296±2 K and atmospheric pressure using nitrogen or synthetic air as bath gases. The decay rates of the organic species were measured relative to those of 1,2-dichloroethane, dichloromethane and 1,1,1,2-tretrafluoroethane. The following rate coefficients were derived for the reaction of Cl atoms (in units of cm 3 molecule −1 s −1) with CH 3OCF 2CHFCl, k=(3.24±0.49)×10 −13 and CHF 2OCF 2CHFCl, k=(3.20±0.32)×10 −15. The rate constants obtained are compared with previous literature data to establish reactivity trends and used to estimate the atmospheric lifetimes for the studied ethers. From the calculated lifetimes, using average global concentrations of Cl atoms and OH radicals, the atmospheric loss of CH 3OCF 2CHFCl and CHF 2OCF 2CHFCl is determined by the OH-initiated oxidation. The atmospheric implications of these reactions are discussed based on the calculated ozone depletion potential (ODP) and global warming potential (GWP) of the ethers.