Interference Testing for Atmospheric HOx Measurements by Laser-induced Fluorescence

Accurate OH and HO₂ (collectively called HO_x) measurements by laser-induced fluorescence (LIF) may be contaminated by spurious signals from interfering atmospheric chemicals or from the instrument itself. Interference tests must be conducted to ensure that observed OH signal originates solely from ambient OH and is not due to instrument artifacts. Several tests were performed on the Penn State LIF HO_x instrument, both in the laboratory and in the field. Theseincluded measurements of the instrument's zero signal by using either zero air or perfluoropropylene to remove OH, examination of spectral interferences from naphthalene, sulfur dioxide, and formaldehyde, and tests of interferences by addition of suspected interfering atmospheric chemicals, including ozone, hydrogen peroxide, nitrous acid, formaldehyde, nitric acid, acetone, and organic peroxy radicals (RO₂). All tests lacked evidence ofsignificant interferences for measurements in the atmosphere, including highly polluted urban environments.     

Intercomparison of Tropospheric OH Measurements by Different Laser Techniques during the POPCORN Campaign 1994

In-situ OH measurements by laser-induced fluorescence (LIF) spectroscopy and folded long-path differential optical absorption spectroscopy (DOAS) were carried out in a rural environment in North-East Germany as part of the field experiment POPCORN in August 1994. The large set of OH data obtained allowed an intercomparison of both techniques based on relative diurnal profiles and simultaneously measured absolute concentrations. Most of the time the two OH instruments encountered the same air and agreed well in the measured relative diurnal variations. Only on a few occasions the measurements significantly disagreed due to a perturbation of the DOAS measurements by a local OH source in the north-western wind sector. Excluding data from this wind direction, the statistical analysis of 137 data pairs yields a correlation coefficient of r = 0.90 and a weighted linear fit with a slope of 1.09 ± 0.12. The correlations are carefully analyzed. The comparison of both instruments is discussed in the light of newly published effective absorption cross-sections for H2O and O2 that affect the calibration of LIF.     

High resolution spectral features of a series of aromatic hydrocarbons and BrO: Potential interferences in atmospheric OH-measurements

Naphthalene (C₁₀H₈), several other hydrocarbons, mostly derivates of naphthalene, and bromine oxide (BrO) were analyzed for narrow band (0.01 nm) absorption lines in the wavelength range between 307.7 and 308.3 nm to study their potential impact on OH radical measurements by differential absorption spectroscopy.Only naphthalene showed narrow band absorption lines in this wavelength region. From nine naphthalene lines the differential absorption cross-section was determined.The strongest naphthalene line at 308.002 nm is close to the Q ₁(2) OH line, but about a factor of 200 weaker (=(65.2±15.3)×10^-20 cm²/molec). The corresponding detection limit for naphthalene is about 15 ppt. We re-evaluated some spectra of our OH measurement campaign in July 1987 with respect to naphthalene and obtained an upper limit of 30 ppt for its concentration.BrO was recorded in the larger wavelength interval between 307.7 and 308.7 nm. Structured absorptions were only observed at wavelengths above 308.2 nm and no significant structures were found in the vicinity of the Q ₁(2) and Q ₁(3) OH lines.     

Reaction of OH Radicals with Acetone: Determination of the Branching Ratio for the Abstraction Pathway at 298 K and 1 Torr

We have determined the 2-oxo-propyl CH₃C(O)CH₂ (sometimes called 1-methylvinoxy or acetonyl) radical yield for the reaction of acetone with OH radical relative to the 2-oxo-propyl yields for the reactions of F- and Cl atoms with acetone using the Discharge Flow technique. The 2-oxo-propyl radical has been monitored by Laser Induced Fluorescence LIF at short reaction times in the systems: OH + acetone (R1), F + acetone (R2), and Cl + acetone (R3). From these measurements we have deduced the branching ratio for the 2-oxo-propyl radical formation in the title reaction to be in the range 0.8 R 1.     

POPCORN: A Field Study of Photochemistry in North-Eastern Germany

The intensive field study POPCORN (Photo-Oxidant Formation by Plant Emitted Compounds and OH Radicals in North-Eastern Germany) was carried out in a rural area of North-Eastern Germany during August 1994. An overview of the objectives, measurements and major results of this campaign is presented. Measurements of a set of relevant atmospheric trace compounds, including the hydroxyl radical, along with meteorological data were performed to increase the understanding of OH radical chemistry and photo-oxidant formation. Additionally, plant emissions and the exchange of trace gases between a maize field and the atmosphere were investigated. Budgets of selected trace gases were calculated to assess the relative importance of local sources, chemistry or transport. Intercomparisons between measurement techniques were a central issue of POPCORN and included measurements of OH, hydrocarbons, formaldehyde, photolysis frequencies and vertical fluxes. OH radical concentrations were measured simultaneously by LIF (Laser Induced Fluorescence) and DOAS (Differential Optical Absorption Spectroscopy). Both methods showed good agreement. Maximum OH concentrations were around 107 cm–3 and the diurnal cycles closely followed the rate of primary production via ozone photolysis. Generally, the trace gas composition during POPCORN was characterized by relatively low concentrations of most compounds, e.g. CO: 85–200 ppb, ethane: 0.6–2 ppb, and moderate NOx levels: 0.5–5 ppb (at noontime). Concentrations of individual biogenic volatile organic compounds (VOC) were mostly well below 100 ppt. However, formaldehyde and acetaldehyde which partly originate from biological sources were observed at mixing ratios of some ppb.     

Latitudinal variation of measured O3 photolysis frequencies J(O1D) and primary OH production rates over the Atlantic Ocean between 50° N and 30° S

The latitudinal variation of the photolysis frequency of ozone to O(¹D) atoms, J(O¹D), was measured using a filter radiometer during the cruise ANT VII/1 of the research vessel Polarstern in September/October 1988. The J(O¹D) noon values exhibited a maximum of 3.6×10^-5 s^-1 (2 sr) at the equator and decreased strongly towards higher latitudes. J(O¹D) reached highest values for clean marine background air with low aerosol load and almost cloudless sky. The J(O¹D) data, measured under these conditions and a temperature of 295 K, can be expressed by: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaamOsaiaacI% cacaqGpbWaaWbaaSqabeaaiiaacqWF8baFaaGccaqGebGaaeykaiaa% bccacqWF9aqpcaqGGaGaaeyzaiaabIhacaqGWbGaaeiiaiaabUhacq% GHsislcaaI4aGaaiOlaiaaicdacaaIYaGaeyOeI0IaaGioaiaac6ca% caaI4aGaaiiEaiaaigdacaaIWaWaaWbaaSqabeaacqGHsislcaaIZa% aaaOGaaeiiaiaabIhacaqGGaGaam4uaiabgUcaRiaaiodacaGGUaGa% aGinaiaacIhacaaIXaGaaGimamaaCaaaleqabaGaeyOeI0IaaGOnaa% aakiaadofadaahaaWcbeqaaiaaikdaaaGccaGG9bGaaeikaiaaboha% daahaaWcbeqaaiabgkHiTiaaigdaaaGccaGGPaaaaa!5EE9!\[J({\text{O}}^| {\text{D) }} = {\text{ exp \{ }} - 8.02 - 8.8x10^{ - 3} {\text{ x }}S + 3.4x10^{ - 6} S^2 \} {\text{(s}}^{ - 1} )\] where S represents the product of the overhead ozone column (DU) and the secant of the solar zenith angle. The meridional profile of the primary OH radical production rate P(OH) was calculated from the J(O¹D) measurements and simultaneously recorded O₃ and H₂O mixing ratios. While the latitudinal distribution of J(O¹D) and water vapour was nearly symmetric to the equator, high tropospheric ozone levels up to 40 ppb were observed in the Southern Hemisphere, SH, resulting in higher P(OH) in the SH.     

In-situ Measurements of Tropospheric Hydroxyl Radicals by Folded Long-Path Laser Absorption During the Field Campaign POPCORN

Absolutely calibrated in-situ measurements of tropospheric hydroxyl radicals, formaldehyde, sulfur dioxide, and naphthalene (C10H8) were performed by long-path laser absorption spectroscopy during the field campaign POPCORN. The absorption light path was folded into an open optical multiple reflection cell with a mirror separation of 38.5 m. Using a light path length of 1848 m and an integration time of 200 s, the average 1-detection limits of OH, HCHO, SO2 and C10H8 during POPCORN were 8.7 · 105 cm–3, 8.3 · 109 cm–3, 2.4 · 109 cm–3, 1.5 · 108 cm–3, respectively. In total, 392 identifications of OH in air spectra were made in a rural environment between August 5 and August 23, 1994. We present and discuss OH absorption spectra and diurnal OH concentration profiles of three days which are representative for measurements under different pollution conditions during POPCORN. The observed maximum and median OH radical concentrations are 1.3 · 107 OH/cm3 and 4.0 · 106 OH/cm3, respectively. The measured diurnal variation of the OH concentration shows a good correlation with the primary formation reaction of OH radicals which is the photolysis of ambient ozone. Deviations from this correlation in the morning and evening hours, when the OH concentration is higher than expected from the ozone photolysis, demonstrate the importance of other photochemical HOx production pathways during POPCORN.     

Impacts of Global Emissions of CO, NOx, and CH4 on China Tropospheric Hydroxyl Free Radicals

Using the global chemistry and transport model MOZART,the simulated distributions of tropospheric hydroxyl free radicals(OH) over China and its sensitivities to global emissions of carbon monoxide(CO),nitrogen oxide(NO x),and methane(CH 4) were investigated in this study.Due to various distributions of OH sources and sinks,the concentrations of tropospheric OH in east China are much greater than in west China.The contribution of NO + perhydroxyl radical(HO 2) reaction to OH production in east China is more pronounced than that in west China,and because of the higher reaction activity of non-methane volatile organic compounds(NMVOCs),the contributions to OH loss by NMVOCs exceed those of CO and take the dominant position in summer.The results of the sensitivity runs show a significant increase of tropospheric OH in east China from 1990 to 2000,and the trend continues.The positive effect of double emissions of NO x on OH is partly offset by the contrary effect of increased CO and CH 4 emissions:the double emissions of NO x will cause an increase of OH of 18.1%-30.1%,while the increases of CO and CH 4 will cause a decrease of OH of 12.2%-20.8% and 0.3%-3.0%,respectively.In turn,the lifetimes of CH 4,CO,and NO x will increase by 0.3%-3.1% with regard to double emissions of CH 4,13.9%-26.3% to double emissions of CO and decrease by 15.3%-23.2% to double emissions of NO x.     

Predicting plume meandering and averaging time effects on mean and fluctuating concentrations in atmospheric dispersion simulated in a water channel

Plume meandering and averaging time effects were measured directly using a high spatial resolution, high frequency, linescan laser-induced fluorescence (LIF) technique for measuring scalar concentrations in a plume dispersing in a water channel. Post-processing of the collected data removed time dependent background dye levels and corrected for attenuation across the laser beam to produce accurate measurements over long sample times in both a rough surface boundary-layer shear flow and shear free grid-generated turbulent flow. The data were used to verify the applicability of a meandering plume model for predicting the properties of mean and fluctuating concentrations. The centroid position of the crosswind concentration profile was found to have a Gaussian probability density function and the instantaneous plume spread about the centroid fluctuated log-normally. A modified travel-time power law model for averaging time adjustment was developed and compared to the widely used, but much less accurate, 0.2 power-law model.     

Free Radicals and Fast Photochemistry during BERLIOZ

The free radicals OH, HO₂, RO₂, and NO₃ are known to be the driving force for most chemical processes in the atmosphere. Since the low concentration of the above radicals makes measurements particularly difficult, only relatively few direct measurements of free radical concentrations have been reported to date.We present a comprehensive set of simultaneous radical measurements performed by Laser Induced Fluorescence (LIF), Matrix Isolation –Electron spin Resonance (MI-ESR), Peroxy Radical Chemical Amplification (PERCA), and Differential Optical Absorption Spectroscopy (DOAS) during the BERLIner OZonexperiment (BERLIOZ) during July and August of 1998 near Berlin, Germany. Most of the above radical species were measured by more than one technique and an intercomparison gave good agreement. This data set offered the possibility to study and quantify the role of each radical at a rural, semi-polluted site in the continental boundary layer and to investigate interconnections and dependencies among these free radicals.In general (box) modelled diurnal profiles of the different radicals reproduced the measurements quite well, however measured absolute levels are frequently lower than model predictions. These discrepancies point to disturbing deficiencies in our understanding of the chemical system in urban air masses.In addition considerable night-time peroxy radical production related to VOC reactions with NO₃ and O₃ could be quantified.     

Gas phase reactions of alkyl nitrates with hydroxyl radicals under tropospheric conditions in comparison with photolysis

Rate constants for the reaction of OH radicals with some branched alkyl nitrates have been measured applying a competitive technique. Methyl nitrite photolysis in synthetic air was used as OH radical source at 295±2 K and 1000 mbar total pressure. Using a rate constant of 2.53×10^-12 cm³ s^-1 for the reaction of OH radicals with n-butane as reference, the following rate constants were obtained (units: 10^-12 cm³ s^-1): isopropyl nitrate, 0.59±0.22; isobutyl nitrate, 1.63±0.20; 3-methyl-2-butyl nitrate, 1.95±0.15; 2-methyl-1-butyl nitrate, 2.50±0.15; 3-methyl-1-butyl nitrate, 2.55±0.35. These values have been combined with the literature data to recalculate the substituent factors F(X) for the different nitrate groups which can be used to predict OH rate constants for organic nitrates for which experimental data are not available.Preliminary measurements of the photolysis frequency of isopropyl nitrate have shown that for this nitrate as a model substance, OH reactions and direct photolysis are of equal importance under tropospheric conditions.     

Enhanced spectral UV irradiance: a 1 year preliminary study

The ultraviolet (UV) spectra on cloudy days were compared to those on cloud free days to determine which part of the UV spectrum has the greatest enhancement due to the cloud compared to both corresponding measured clear sky spectra as well as other enhanced spectra. In this preliminary study, cloud enhanced UV spectra selected for maximum UVA enhancement compared to a clear sky UV spectrum at similar solar zenith angle (SZA) and ozone values, showed that the ratio of the two sets of spectral irradiances was approximately wavelength independent (approximately 1.1) above the cut-off wavelength of approximately 306 nm. Similarly, above 306 nm the average ratio of the spectral irradiances of a maximum UVB enhanced UV spectrum compared to a clear sky spectrum was 1.2 with maximum values generally above this average between 316 and 344 nm and generally below 1.2 above the wavelength of 344 nm. The UVA and UVB enhanced spectra were separated into five SZA ranges and the irradiance at each wavelength averaged for each range and compared to clear sky spectra in each of the ranges. Above approximately 306 nm, the ratios are wavelength independent for all SZA. However, with the exception of the SZA range centred on 20°, there is an increasing dependency with shorter wavelengths below the 306 nm. Also there appears to be two distinct groupings of the average irradiance ratios, corresponding to the SZA range centred on 20°, 37° and 49° (ratio of 1.2) and 32° and 42° (ratio 1.0), the latter cases suggesting that on average there is no enhancement for these SZA, except for wavelengths less than 306 nm.     

Formulation and Evaluation of IMS, an Interactive Three-Dimensional Tropospheric Chemical Transport Model 3. Comparison of Modelled C2–C5 Hydrocarbons with Surface Measurements

In part 3 of this series of papers on a new 3-D global troposphericchemical transport model, using an Integrated Modelling System (IMS), anevaluation of the model performance in simulating global distributions andseasonal variations for volatile organic compounds (VOCs) in the atmosphere,is presented. Comparisons of model OH concentrations with previous modelstudies show consistent modelled OH levels from the subtropics tomidlatitudes, while more discrepancies occur over the tropical lowlatitudes, with IMS predicting the highest levels of OH. The close agreementbetween modelled OH concentrations over midlatitudes, where high surfaceNO_xand VOC concentrations are also found, is indicative of the strongphotochemical coupling between NO_x, VOCs and O₃ overthese latitudes. IMSOH concentrations in the Northern Hemisphere (NH) midlatitudes during summerare generally lower than available measurements, implying that models ingeneral are underestimating OH levels at this location and time of year.Substantial differences between model OH concentrations over low latitudesclearly highlight areas of uncertainty between models. IMS OH concentrationsare the highest in general of the models compared, one possible reason isthat biogenic emissions of species such as isoprene and monoterpenes arehighest in IMS, leading to higher O₃ levels and hence higher OH.Generally, the IMS VOC concentrations show a similar seasonality to themeasurements at most locations. In general though, IMS tends to underestimatethe NH wintertime VOC maximum and overestimate the NH summertime VOCminimum. Such an overestimate in summer could be due to IMSunderestimating OH levels, or an overestimation of VOC emissions or possiblya problem with model transport, all of these possibilities are explored.Except for n-pentane, the model underprediction of a VOC maximum during theNH winter month strongly suggests a missing emission mechanism in the modelor an underestimate of an existing one. It is very likely that there is alack of time varying emission sources in the model to account for theseasonal change in emission behaviour such as increasing energy usage (e.g.,electricity and gas), road transportation, engine performance, and otheranthropogenic factors which show strong seasonal characteristics. Theanomalous overprediction of wintertime n-pentane compared with its closesummertime prediction with the measurements suggest that emissions in thiscase may be too high.     

The investigations of aerosol particle formation in urban background area of Helsinki

In this study the possible conditions for new aerosol particle formation in a background area of Helsinki have been analysed. The measurements of aerosol particle size distribution, main gaseous pollutant compounds, UV spectra and meteorological parameters were performed during April–May 1993. The main interest was concentrated on the investigations of photochemical OH radical formation, the oxidation of gas phase SO₂ to H₂SO₄ and the formation of H₂SO₄---H₂O aerosol particles. The measurements were analysed using a model for OH radical formation and aerosol dynamics. The analysis of aerosol size distributions was carried out using positive matrix factorization. The main conclusion is that based on our model analysis no evidence of new particle formation in the vicinity of the measurement station was found. However, the high concentrations of aerosol particles in the ultrafine size range indicate that some other particle formation pathways are to be considered.     

Intercomparison of Two Hydroxyl Radical Measurement Techniques at the Atmosphere Simulation Chamber SAPHIR

At the atmosphere simulation chamber SAPHIR in Jülich both Laser-Induced Fluorescence Spectroscopy (LIF) and Long-Path Differential Optical Laser Absorption Spectroscopy (DOAS) are operational for the detection of OH radicals at tropospheric levels. The two different spectroscopic techniques were compared within the controlled environment of SAPHIR based on all simultaneous measurements acquired in 2003 (13 days). Hydroxyl radicals were scavenged by added CO during four of these days in order to experimentally check the calculated precisions at the detection limit. LIF measurements have a higher precision (σ= 0.88×10⁶ cm^–3) and better time resolution (Δt = 60 s), but the DOAS method (σ= 1.24×10⁶ cm^–3, Δt = 135 s) is regarded as primary standard for comparisons because of its good accuracy. A high correlation coefficient of r = 0.95 was found for the whole data set highlighting the advantage of using a simulation chamber. The data set consists of two groups. The first one includes 3 days, where the LIF measurements yield (1 – 2) ×10⁶ cm^–3 higher OH concentrations than observed by the DOAS instrument. The experimental conditions during these days are characterized by increased NO_x concentration and a small dynamic range in OH. Excellent agreement is found within the other group of 6 days. The regression to the combined data of this large group yields unity slope without a significant offset.     

Three-Dimensional Calculation of Photolysis Frequencies in the Presence of Clouds and Impact on Photochemistry

For atmospheric photochemistry, clouds can significantly affect actinic flux distributions. In this paper, we examine the effects of convective clouds on the three-dimensional distribution of the spectral actinic flux and on photolysis frequencies for various chemical species. Three-dimensional solutions of the UV-VIS radiative transfer equation are produced using the Spherical Harmonic Discrete Ordinary Method solution technique. This solver uses as input the 3-D cloud characteristics simulated by a dynamical cloud model. The ultraviolet and visible spectra are divided into 5 intervals in order to explore the wavelength dependency of the cloud effect on the actinic flux. Results show that the distribution of the actinic flux over the cloud domain is far from homogeneous and depends primarily on the cloud extinction associated with the hydrometeors. Maximum actinic flux is found at the top edge of the cloud and is related to scattering by ice crystals. The actinic flux is enhanced by a factor of 2 to 5, compared to clear air values, above, at the top edge, and around the cloud. The 3-D actinic flux is used to calculate the photolysis rates for some chemical species (e.g. NO₂, O₃, and HCHO). Forcomputing photolysis rates, a discretized spectral representation of the absorption wavelengths is used in the model. The calculated photolysis rates are distributed inhomogeneously throughout the cloud, and maxima are found in regions where the actinic flux is enhancement is large. Temperature effects on absorption are found in the photolysis frequencies of some species. Finally, the potential importance of this photolysis enhancement on photochemistry is studied using box model simulations. Results show that enhanced OH concentrations are found in the upper troposphere (120–200%) overthe clouds and changes in ozone production rates (+15%) are obtained in quasi-steady state conditions.     

Parameterization of Ozone Photolysis Frequency in the Lower Troposphere Using Data from Photodiode Array Detector Spectrometers

Spectroradiometers using photodiode array detectors (PDAs) are increasingly applied for airborne and ground-based atmospheric measurements of spectral actinic flux densities due to their high time resolution (less than one second). However they have limited sensitivity of ultraviolet (UV) radiation for wavelengths less than about 305 nm. This results in uncertainties of ozone photolysis frequencies derived from spectral actinic flux density measurements using PDA spectrometers. To overcome this limitation a parameterization method is introduced which extrapolates the data towards the wavelength range of limited sensitivity of the PDA spectrometers (less than about 305 nm). The parameterization is based on radiative transfer simulations and is valid for measurements in the lower troposphere. The components of the suggested parameterization are the lower threshold wavelength of the PDA spectrometer, the slant ozone column (ratio of the total ozone column and the cosine of the solar zenith angle), and the ambient temperature. Tests of the parameterization with simulated actinic flux density spectra have revealed an uncertainty of the derived ozone photolysis frequency of ±5%. Field comparisons of the parameterization results with independent measurements of the ozone photolysis frequency were within ±10% for solar zenith angles less than 70^∘. Finally the parameterization was applied to airborne measurements to emphasize the advantage of high time resolution of PDA spectrometers to study ozone photolysis frequency fields in inhomogeneous cloud condtitions.     

Discrimination of ice from water in clouds by optical remote sensing

Water and ice, although nearly transparent in the visible, absorb weakly in the near infrared, and spectral absorption differs for the two phases, especially in the wavelength region between 1.55 and 1.75 μm. Multiple scattering in clouds amplifies absorption, so that cloud reflectance or transmittance measurements would enable the interfence of thermodynamic phase. A ground-based near-infrared radiometer, which measures the relative spectral reflectance from sides of clouds in the wavelength range 0.63 to 1.9 μm, was built and used to obtain spectra from cumulus congestus and cumulonimbus clouds. Results from measurements in summer 1985 seem to indicate that such a ground-based technique can accurately determine the phase of clouds.     

Prototype FAGE determination of NO2

A low pressure laser-excited-fluorescence technique (FAGE) for the direct determination of atmospheric NO₂ has been developed. Using a frequency-doubled Nd-YAG pump laser and a signal collection time of 20 s (10 s each signal and background) a detection limit of 450 pptv is calculated under laboratory conditions. Improved sensitivities will be possible with a higher repetition rate laser and lower fluorescence cell pressures.