Atmospheric Photolysis Rate Research Articles

Synthesis and Characterization of Atmospherically Relevant Hydroxy Hydroperoxides

Hydroxy hydroperoxides are formed upon OH oxidation of volatile organic compounds in the atmosphere and may contribute to secondary organic aerosol growth and aqueous phase chemistry after phase transfer to particles. Although the detection methods for oxidized volatile organic compounds improved much over the past decades, the limited availability of synthetic standards for atmospherically relevant hydroxy hydroperoxides prevented comprehensive investigations for the most part. Here, we present a straightforward improved synthetic access to isoprene-derived hydroxy hydroperoxides, i.e., 1,2-ISOPOOH and 4,3-ISOPOOH. Furthermore, we present the first successful synthesis of an α-pinene derived hydroxy hydroperoxide. All products were identified by 1H, 13C NMR spectroscopy for structure elucidation, additional 2D NMR experiments were performed. Furthermore, gas-phase FTIR- and UV/VIS spectra are presented for the first time. Using the measured absorption cross section, the atmospheric photolysis rate of up to 2.1 × 10−3 s−1 was calculated for 1,2-ISOPOOH. Moreover, we present the investigation of synthesized hydroxy hydroperoxides in an aerosol chamber study by online MS techniques, namely PTR-ToFMS and (NO3−)-CI-APi-ToFMS. Fragmentation patterns recorded during these investigations are presented as well. For the (NO3−)-CI-APi-ToFMS, a calibration factor for 1,2-ISOPOOH was calculated as 4.44 × 10−5 ncps·ppbv−1 and a LOD (3σ, 1 min average) = 0.70 ppbv.

Evaluation of local measurement-driven adjustments of modelled cloud-free atmospheric photolysis rate coefficients

Using time series of spectral radiometer measurements we reveal three sets of photolysis reactions that group together according to the adjustments required to their modelled j-values for local solar flux conditions.

Determination of the absorption cross sections of higher-order iodine oxides at 355 and 532 nm

Abstract. Iodine oxides (IxOy) play an important role in the atmospheric chemistry of iodine. They are initiators of new particle formation events in the coastal and polar boundary layers and act as iodine reservoirs in tropospheric ozone-depleting chemical cycles. Despite the importance of the aforementioned processes, the photochemistry of these molecules has not been studied in detail previously. Here, we report the first determination of the absorption cross sections of IxOy, x=2, 3, 5, y=1–12 at λ=355 nm by combining pulsed laser photolysis of I2∕O3 gas mixtures in air with time-resolved photo-ionization time-of-flight mass spectrometry, using NO2 actinometry for signal calibration. The oxides selected for absorption cross-section determinations are those presenting the strongest signals in the mass spectra, where signals containing four iodine atoms are absent. The method is validated by measuring the absorption cross section of IO at 355 nm, σ355nm,IO= (1.2±0.1) ×10-18 cm2, which is found to be in good agreement with the most recent literature. The results obtained are σ355nm,I2O3<5×10-19 cm2 molec.−1, σ355nm,I2O4= (3.9±1.2)×10-18 cm2 molec.−1, σ355nm,I3O6= (6.1±1.6)×10-18 cm2 molec.−1, σ355nm,I3O7= (5.3±1.4)×10-18 cm2 molec.−1, and σ355nm,I5O12= (9.8±1.0)×10-18 cm2 molec.−1. Photodepletion at λ=532 nm was only observed for OIO, which enabled determination of upper limits for the absorption cross sections of IxOy at 532 nm using OIO as an actinometer. These measurements are supplemented with ab initio calculations of electronic spectra in order to estimate atmospheric photolysis rates J(IxOy). Our results confirm a high J(IxOy) scenario where IxOy is efficiently removed during daytime, implying enhanced iodine-driven ozone depletion and hindering iodine particle formation. Possible I2O3 and I2O4 photolysis products are discussed, including IO3, which may be a precursor to iodic acid (HIO3) in the presence of HO2.

The photolysis of α-hydroperoxycarbonyls.

In this work, we theoretically elucidated the mechanism and predicted the major products of the photolysis of α-hydroperoxycarbonyls, known to be products of the atmospheric oxidation of biogenic volatile organic compounds (BVOC) and components of secondary organic aerosol (SOA) in rural and remote areas. Using 2-hydroperoxypropanal OCHCH(OOH)CH3 as a model compound, we show that the likely major photolysis mechanism is a fast 1,5 H-shift in the initially excited singlet S1 state followed by spontaneous elimination of singlet oxygen to yield an enol HOCH[double bond, length as m-dash]CHCH3, while intersystem crossing (ISC) to the triplet T1 state and C-C scission into HC˙O + HOOC˙HCH3 followed by expulsion of a hydroxyl radical from the unstable HOOC˙HCH3 is another product channel. The direct S1 reaction was found to occur at such a high rate that the quantum yield in atmospheric conditions is expected to approach unity. In the atmosphere, the enol should generally react with OH radicals or tautomerize into the more stable carbonyl O[double bond, length as m-dash]CH-CH2CH3. Vinylalcohol is shown to be a major end product of the photolysis of hydroperoxyacetaldehyde, an isoprene oxidation product. Taking into account also the important enhancement of the absorption cross sections over those of the constituent monofunctional compounds as observed for the analogous β-ketohydroperoxides, (F. Jorand et al., J. Photochem. Photobiol. A: Chem., 2000, 134, 119-125) the atmospheric photolysis rate of α-hydroperoxycarbonyls was estimated to be in the range of (1 to 5) × 10-4 s-1, generally faster than the rate of their OH reactions.

Impacts of aerosol direct effects on tropospheric ozone through changes in atmospheric dynamics and photolysis rates.

Aerosol direct effects (ADEs), i.e., scattering and absorption of incoming solar radiation, reduce radiation reaching the ground and the resultant photolysis attenuation can decrease ozone (O3) formation in polluted areas. One the other hand, evidence also suggests that ADE-associated cooling suppresses atmospheric ventilation, thereby enhancing surface-level O3. Assessment of ADE impacts is thus important for understanding emission reduction strategies that seek co-benefits associated with reductions in both particuate matter and O3 levels. This study quantifies the impacts of ADEs on tropospheric ozone by using a two-way online coupled meteorology and atmospheric chemistry model, WRF- CMAQ, using a process analysis methodology. Two mani-festations of ADE impacts on O3 including changes in atmospheric dynamics (ᐃDynamics) and changes in photolysis rates (∆Photolysis) were assessed separately through multiple scenario simulations for January and July of 2013 over China. Results suggest that ADEs reduced surface daily maxima 1 h O3 (DM1O3) in China by up to 39μgm−3 through the combination of ∆Dynamics and ∆Photolysis in January but enhanced surface DM1O3 by up to 4μgm−3 in July. Increased O3 in July is largely attributed to ∆Dynamics, which causes a weaker O3 sink of dry deposition and a stronger O3 source of photochemistry due to the stabilization of the at-mosphere. Meanwhile, surface OH is also enhanced at noon in July, though its daytime average values are reduced in January. An increased OH chain length and a shift towards more volatile organic compound (VOC)-limited conditions are found due to ADEs in both January and July. This study suggests that reducing ADEs may have the potential risk of increasing O3 in winter, but it will benefit the reduction in maxima O3 in summer.

Solar Absorption by Aerosol-Bound Nitrophenols Compared to Aqueous and Gaseous Nitrophenols.

Nitrophenols are well-known absorbers of near-UV/blue radiation and are considered to be a component of solar-absorbing organic aerosol material commonly labeled brown carbon. Nitrophenols have been identified in a variety of phases in earth's atmosphere, including the gaseous, aqueous, and aerosol bound, and these different environments alter their UV-vis absorption spectra, most dramatically when deprotonated forming nitrophenolates. We quantify the impact of these different absorption profiles by calculating the solar power absorbed per molecule for several nitrophenols. For instance, aqueous 2,4-dinitrophenol absorption varies dramatically over the pH range of cloud droplets with pH = 5.5 solutions absorbing three times the solar power compared to pH = 3.5 solutions. We also measured the UV-vis spectra of 2-nitrophenol adsorbed on several aerosol substrates representative of mineral dust, inorganic salts, and organic aerosol and compare these spectra to gaseous and aqueous 2-nitrophenol. 2-Nitrophenol adsorbed on mineral and chloride aerosol substrates exhibits a red-shifted absorption band (∼450-650 nm) consistent with 2-nitrophenolate and absorbs twice the solar power per molecule compared to gaseous, aqueous, and organic aerosol-bound 2-nitrophenol. We also discuss how different nitrophenol absorption profiles alter important atmospheric photolysis rate constants [e.g., J(NO2) and J(O3)] by attenuating solar flux.

The UV and visible spectra of chlorine peroxide: Constraining the atmospheric photolysis rate

AbstractThe photolysis of chlorine peroxide (ClOOCl) is a key chemical step in the depletion of polar stratospheric ozone. As such, precise measurements of the absorption cross sections for ClOOCl are required. In this paper we provide two critical pieces of laboratory data with which to constrain the rate of ozone depletion. First, we provide an optically pure ClOOCl spectrum in the photolytically important UV wavelength region (200–350 nm). Second, we provide the first ever measurement of the ClOOCl spectrum in the visible region (509–536 nm) conclusively demonstrating the photolysis of ClOOCl to be negligible in this spectral region. The visible measurement is important because it can be used to anchor other previously recorded UV spectra and hence reduce the uncertainty in the ClOOCl photolysis rate. The calculated photolysis rate from this study indicates that the current models of stratospheric ozone depletion are correct.

NF3: UV absorption spectrum temperature dependence and the atmospheric and climate forcing implications

Nitrogen trifluoride (NF3) is an atmospherically persistent greenhouse gas that is primarily removed by UV photolysis and reaction with O(1D) atoms. In this work, the NF3 gas‐phase UV absorption spectrum, σ(λ,T), was measured at 16 wavelengths between 184.95 and 250 nm at temperatures between 212 and 296 K. A significant spectrum temperature dependence was observed in the wavelength region most relevant to atmospheric photolysis (200–220 nm) with a decrease in σ(210 nm,T) of ~45% between 296 and 212 K. Atmospheric photolysis rates and global annually averaged lifetimes of NF3 were calculated using the Goddard Space Flight Center 2‐D model and the σ(λ,T) parameterization developed in this work. Including the UV absorption spectrum temperature dependence increased the stratospheric photolysis lifetime from 610 to 762 years and the total global lifetime from 484 to 585 years; the NF3 global warming potentials on the 20‐, 100‐, and 500‐year time horizons increased <0.3, 1.1, and 6.5% to 13,300, 17,700, and 19,700, respectively.

Nitryl Chloride (ClNO2): UV/Vis Absorption Spectrum between 210 and 296 K and O(3P) Quantum Yield at 193 and 248 nm

Recent studies have shown that the UV/vis photolysis of nitryl chloride (ClNO2) can be a major source of reactive chlorine in the troposphere. The present work reports measurements of the ClNO2 absorption spectrum and its temperature dependence between 210 and 296 K over the wavelength range 200–475 nm using diode array spectroscopy. The room temperature spectrum obtained in this work was found to be in good agreement with the results from Ganske et al. (J. Geophys. Res. 1992, 97, 7651) over the wavelength range common to both studies (200–370 nm) but differs systematically from the currently recommended spectrum for use in atmospheric models. The present results lead to a decrease in the calculated atmospheric ClNO2 photolysis rate by 30%. Including the temperature dependence of the ClNO2 spectrum decreases the calculated atmospheric photolysis rate at lower temperatures (higher altitudes) even further. A parametrization of the wavelength and temperature dependence of the ClNO2 spectrum is presented. O(3P) quantum yields, Φ(ClNO2)(O), in the photolysis of ClNO2 at 193 and 248 nm were measured at 296 K using pulsed laser photolysis combined with atomic resonance fluorescence detection of O(3P) atoms. Φ(ClNO2)(O)(λ) was found to be 0.67 ± 0.12 and 0.15 ± 0.03 (2σ error limits, including estimated systematic errors) at 193 and 248 nm, respectively, indicating that multiple dissociation channels are active in the photolysis of ClNO2 at these wavelengths. The Φ(ClNO2)(O)(λ) values obtained in this work are discussed in light of previous ClNO2 photodissociation studies and the differences are discussed.

Measurement of the Fourth O−H Overtone Absorption Cross Section in Acetic Acid Using Cavity Ring-Down Spectroscopy

We report the absolute absorption cross sections of the fourth vibrational O-H (5ν(OH)) overtone in acetic acid using cavity ring-down spectroscopy. For compounds that undergo photodissociation via overtone excitation, such intensity information is required to calculate atmospheric photolysis rates. The fourth vibrational overtone of acetic acid is insufficiently energetic to effect dissociation, but measurement of its cross section provides a model for other overtone transitions that can affect atmospheric photochemistry. Though gas-phase acetic acid exists in equilibrium with its dimer, this work shows that only the monomeric species contributes to the acetic acid overtone spectrum. The absorption of acetic acid monomer peaks at ∼615 nm and has a peak cross section of 1.84 × 10(-24) cm(2)·molecule(-1). Between 612 and 620 nm, the integrated cross section for the acetic acid monomer is (5.23 ± 0.73) × 10(-24) cm(2)·nm·molecule(-1) or (1.38 ± 0.19) × 10(-22) cm(2)·molecule(-1)·cm(-1). This is commensurate with the integrated cross section values for the fourth O-H overtone of other species. Theoretical calculations show that there is sufficient energy for hydrogen to transition between the two oxygen atoms, which results in an overtone-induced conformational change.

UV absorption cross sections of nitrous oxide (N<sub>2</sub>O) and carbon tetrachloride (CCl<sub>4</sub>) between 210 and 350 K and the atmospheric implications

Abstract. Absorption cross sections of nitrous oxide (N2O) and carbon tetrachloride (CCl4) are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm) at temperatures in the range 210–350 K. In addition, UV absorption spectra of CCl4 are reported between 200–235 nm as a function of temperature (225–350 K). The results from this work are critically compared with results from earlier studies. For N2O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N2O atmospheric photolysis rate. For CCl4, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5–7% increase in the modeled CCl4 photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl4 cross section parameterization for use in atmospheric model calculations is presented.

Photodissociation Cross Section of ClOOCl at 330 nm

The photolysis rate of ClOOCl is crucial in the catalytic destruction of polar stratospheric ozone. In this work, we determined the photodissociation cross section of ClOOCl at 330 nm with a molecular beam and with mass-resolved detection. The photodissociation cross section is the product of the absorption cross section and the dissociation quantum yield. We formed an effusive molecular beam of ClOOCl at a nozzle temperature of 200 or 250 K and determined its photodissociation probability by measuring the decrease of the ClOOCl intensity upon laser irradiation. By comparing with a reference molecule (Cl(2)), of which the absorption cross section and dissociation quantum yield are well-known, we determined the absolute photodissociation cross section of ClOOCl at 330 nm to be (2.31 +/- 0.11) x 10(-19) cm(2) at 200 K and (2.47 +/- 0.12) x 10(-19) cm(2) at 250 K. Impurity interference has been a well-recognized problem in conventional spectroscopic studies of ClOOCl; our mass-resolved measurement directly overcomes such a problem. This measurement of the ClOOCl photolysis cross section at 330 nm is particularly useful in constraining its atmospheric photolysis rate, which in the polar stratosphere peaks near this wavelength.

UV Absorption Spectrum of the ClO Dimer (Cl2O2) between 200 and 420 nm

The UV photolysis of Cl(2)O(2) (dichlorine peroxide) is a key step in the catalytic destruction of polar stratospheric ozone. In this study, the gas-phase UV absorption spectrum of Cl(2)O(2) was measured using diode array spectroscopy and absolute cross sections, sigma, are reported for the wavelength range 200-420 nm. Pulsed laser photolysis of Cl(2)O at 248 nm or Cl(2)/Cl(2)O mixtures at 351 nm at low temperature (200-228 K) and high pressure (approximately 700 Torr, He) was used to produce ClO radicals and subsequently Cl(2)O(2) via the termolecular ClO self-reaction. The Cl(2)O(2) spectrum was obtained from spectra recorded following the completion of the gas-phase ClO radical chemistry. The spectral analysis used observed isosbestic points at 271, 312.9, and 408.5 nm combined with reaction stoichiometry and chlorine mass balance to determine the Cl(2)O(2) spectrum. The Cl(2)O(2) UV absorption spectrum peaks at 244.5 nm with a cross section of 7.6(-0.5)(+0.8) x 10(-18) cm(2) molecule(-1) where the quoted error limits are 2sigma and include estimated systematic errors. The Cl(2)O(2) absorption cross sections obtained for wavelengths in the range 300-420 nm are in good agreement with the Cl(2)O(2) spectrum reported previously by Burkholder et al. (J. Phys. Chem. A 1990, 94, 687) and significantly higher than the values reported by Pope et al. (J. Phys. Chem. A 2007, 111, 4322). A possible explanation for the discrepancy in the Cl(2)O(2) cross section values with the Pope et al. study is discussed. Representative, atmospheric photolysis rate coefficients are calculated and a range of uncertainty estimated based on the determination of sigma(Cl(2)O(2))(lambda) in this work. Although improvements in our fundamental understanding of the photochemistry of Cl(2)O(2) are still desired, this work indicates that major revisions in current atmospheric chemical mechanisms are not required to simulate observed polar ozone depletion.

Experimental intercomparison of the absorption cross-sections of nitrous acid (HONO) in the ultraviolet and mid-infrared spectral regions

Nitrous acid, HONO, is an important trace gas in tropospheric photochemistry, because it is a source of OH radicals. In order to obtain HONO concentrations from spectroscopic measurements, the knowledge of accurate absorption cross-sections is essential. Furthermore, the ultraviolet absorption cross-sections of HONO determine its atmospheric photolysis rates, which are still being debated. In particular, in a recent field study focusing on the photolysis frequency of HONO, the absolute values of the ultraviolet absorption cross-sections have been proposed as a potential source for systematic errors. For these reasons, we have compared the absorption cross-sections for HONO in the infrared (IR) and ultraviolet (UV) by performing simultaneous measurements in both spectral regions. Assuming that the IR cross-sections (that show good agreement between different studies) are correct, our study shows a good agreement between the consistent infrared studies and some selected accurate UV spectra published previously (about 6%) while a rather large disagreement (about 22%) is observed when using other UV data sets.

Overtone Dissociation of Peroxynitric Acid (HO2NO2): Absorption Cross Sections and Photolysis Products

Band strengths for the second (3nuOH) and third (4nuOH) overtones of the OH stretch vibration of peroxynitric acid, HO2NO2 (PNA) in the gas-phase were measured using Cavity Ring-Down Spectroscopy (CRDS). Both OH overtone transitions show diffuse smoothly varying symmetrical absorption profiles without observable rotational structure. Integrated band strengths (base e) at 296 K were determined to be S(3nuOH) = (5.7 +/- 1.1) x 10(-20) and S(4nuOH) = (4.9 +/- 0.9) x 10(-21) cm(2) molecule(-1) cm(-1) with peak cross sections of (8.8 +/- 1.7) x 10(-22) and (7.0 +/- 1.3) x 10(-23) cm(2) molecule(-1) at 10086.0 +/- 0.2 cm(-1) and 13095.8 +/- 0.4 cm(-1), respectively, using PNA concentrations measured on line by Fourier-transform infrared and ultraviolet absorption spectroscopy. The quoted uncertainties are 2sigma (95% confidence level) and include estimated systematic errors in the measurements. OH overtone spectra measured at lower temperature, 231 K, showed a narrowing of the 3nuOH band along with an increase in its peak absorption cross section, but no change in S(3nuOH) to within the precision of the measurement (+/-9%). Measurement of a PNA action spectrum showed that HO2 is produced from second overtone photodissociation. The action spectrum agreed with the CRDS absorption spectra. The PNA cross sections determined in this work for 3nuOH and 4nuOH will increase calculated atmospheric photolysis rates of PNA slightly.

Electronic spectroscopy of bromopentafluorobenzene by high-resolution vacuum ultraviolet photoabsorption, electron impact, and photoelectron spectroscopies

The electronic transitions of bromopentafluorobenzene (C6F5Br) have been investigated by high-resolution photoabsorption spectroscopy in the energy range 4–10.8eV. In addition, the electron energy loss spectrum (EELS) was recorded in non-strictly electric dipolar interaction conditions (40eV incident energy, 10° scattering angle) over the range 4–13.0eV. The present spectra provide the first experimental data on the electronic states of bromopentafluorobenzene. The characteristics of the electronic excited states are discussed and the terrestrial atmospheric photolysis rates have been derived from the absolute photoabsorption cross-sections. The ionisation energies of the occupied molecular orbitals have been measured by high-resolution He(I) photoelectron spectroscopy, allowing a precise value of 9.679±0.002eV to be derived for the ionic ground state.

Atmospheric photolysis rate coefficients during the Polar Sunrise Experiment ALERT2000

We measured and modeled UV radiation by three methods to quantify molecular photolysis rate coefficients during the light intensive period of the Polar Sunrise Experiment ALERT2000. UV radiation was measured by either a 2 π filter radiometer or a spectral irradiance sensor, or modeled with the phodis package. The phodis program uses a discrete ordinate radiation transfer method (DISORT) to calculate the actinic radiation field for a model atmosphere. The irradiance measurements must be converted to actinic fluxes in order to calculate photolysis rate coefficients. The conversion between irradiance and actinic flux is non-trivial and requires an assumption about the angular distribution of the diffuse radiation. We contrast two model assumptions. The first model assumes that the diffuse radiation is isotropic; we call this model the isotropic diffuse model (IDM). The second model calculates the angular distribution with DISORT, which we call the anisotropic diffuse model (ADM). Having calculated the actinic flux, we calculate the photolysis rate coefficient of NO 2, J(NO 2). Comparing the IDM and ADM-derived J(NO 2) due to downwelling radiation, we find that the IDM assumption leads to clear-sky photolysis rate coefficients 15% less than the ADM assumption. We show that the IDM method clear-sky results are not consistent with IDM method overcast sky results; therefore, the ADM assumption is preferred. The 2 π filter radiometer directly measures the actinic flux and uses filters appropriate to quantify J(NO 2). The comparison of these three methods for the downwelling component of J(NO 2) demonstrates good agreement; all three methods lie within a 20% range. The 2 π sensor measures 10% higher photolysis rate coefficients than does the ADM method, and the phodis model predicts 10% lower photolysis rate coefficients than does the ADM model. While the correlations between the ADM method and the 2 π sensor are quite compact during homogeneous sky conditions, partially cloudy sky conditions are difficult to model, leading to increased error. The overall standard deviation between the two measurements for all sky conditions is ±10% of the mean (1− σ). Using this full ADM model, we calculate photolysis rate coefficients for many other molecules of atmospheric interest.

Upper limit for the UV absorption cross sections of H2SO4

An upper limit for the gas phase absorption cross sections for H2SO4 over the wavelength range 195 to 330 nm has been determined. Absorption measurements were made using a diode array spectrometer and a 100 cm long heated absorption cell. Gas phase H2SO4 was generated in a gas flow by titrating (equilibrating) known amounts of SO3 via the reaction at elevated temperatures, ∼ 500 K. Upper limits to the H2SO4 absorption cross sections were obtained, <1 × 10−21 cm² molecule−1, and provide an upper limit to the atmospheric photolysis rate of H2SO4. The implications of this cross section limit to stratospheric sulfur chemistry are discussed.

The UV-Visible Absorption Cross-Sections and Atmospheric Photolysis Rate of HOI

The UV-visible absorption cross-sections of HOI have been recorded over the wavelength range 278-494 nm and at 298 K following generation of HOI in the gas phase using laser flash photolysis. The gas phase reaction of OH with I2 was used to produce HOI, and the absorption spectrum of HOI was calibrated relative to the consumption of I2. The HOI spectrum recorded exhibits 2 broad absorption maxima of σ = 3.99 × 10-19 cm2 and σ = 2.85 × 10-19 cm2, centred at 338.4 nm and 404.8 nm respectively. The spectrum is adequately described by a parameterisation consisting of two semi-logarithmic Gaussian distribution functions. The HOI spectrum is more intense than that recorded in previous work of Jenkin, but is in good agreement with more recent work by Bauer et al. The parameterised HOI absorption spectrum recorded in this work was used in a radiative model to calculate the atmospheric photolysis rate (J-value) of HOI. These results indicate that, under most sunlit conditions, HOI has a lifetime with respect to solar photolysis of the order of minutes. Experiments attempting to generate HOI by the reaction of O atoms with C2H5I led to complex absorption spectra containing a negative contribution to the absorption from the photolytic removal of an unidentified species. In addition, evidence was found for adsorption and desorption of an iodine-containing species in the reaction vessel. This behaviour is rationalised in terms of the disproportionation of HOI to I2O, and an uncalibrated spectrum tentatively attributed to I2O has been recorded.

Gas-phase photolysis of phorate, a phosphorothioate insecticide

Novel methods are described for determining atmospheric photolysis rates for the moderately volatile pesticide, phorate. The gas-phase sunlight photolysis of this substance was determined in three test systems which include: (1) 3-L borosilicate flasks exposed to sunlight and laboratory solar simulation, (2) 100-L Tedlar sunlight exposed air sample bags, and (3) 12,800-L Tedlar sunlight exposed chamber studies using a photochemically stable tracer compound. The kinetic results from all systems indicate rapid gas-phase photolysis under midsummer sunlight conditions with observed half-lives being less than 30 minutes. A pronounced increase in transformation rates with increasing volume to surface area suggests photoreactions occur at more rapid rates in the gas-phase. 14C Radiolabeled phorate irradiations resulted in one conversion product, phorate sulfoxide, and this photoproduct accounted for essentially all of the phorate lost.