Cavity Enhanced Absorption Spectroscopy Research Articles

Release of nitrous acid and nitrogen dioxide from nitrate photolysis in acidic aqueous solutions.

Nitrate (NO3(-)) is an abundant component of aerosols, boundary layer surface films, and surface water. Photolysis of NO3(-) leads to NO2 and HONO, both of which play important roles in tropospheric ozone and OH production. Field and laboratory studies suggest that NO3¯ photochemistry is a more important source of HONO than once thought, although a mechanistic understanding of the variables controlling this process is lacking. We present results of cavity-enhanced absorption spectroscopy measurements of NO2 and HONO emitted during photodegradation of aqueous NO3(-) under acidic conditions. Nitrous acid is formed in higher quantities at pH 2-4 than expected based on consideration of primary photochemical channels alone. Both experimental and modeled results indicate that the additional HONO is not due to enhanced NO3(-) absorption cross sections or effective quantum yields, but rather to secondary reactions of NO2 in solution. We find that NO2 is more efficiently hydrolyzed in solution when it is generated in situ during NO3(-) photolysis than for the heterogeneous system where mass transfer of gaseous NO2 into bulk solution is prohibitively slow. The presence of nonchromophoric OH scavengers that are naturally present in the environment increases HONO production 4-fold, and therefore play an important role in enhancing daytime HONO formation from NO3(-) photochemistry.

Time-resolved in situ detection of CO in a shock tube using cavity-enhanced absorption spectroscopy with a quantum-cascade laser near 4.6 µm.

Cavity-enhanced absorption spectroscopy (CEAS) using a mid-infrared DFB quantum-cascade laser is reported for sensitive time-resolved (10 μs) in situ CO measurements in a shock tube. Off-axis alignment and fast scanning of the laser wavelength were used to minimize coupling noise in a low-finesse cavity. An absorption gain factor of 91 was demonstrated, which enabled sub-ppm detection sensitivity for gas temperatures of 1000-2100K in a 15 cm diameter shock tube. This substantial improvement in detection sensitivity compared to conventional single-pass absorption measurements, shows great potential for the study of reaction pathways of high-temperature combustion kinetics mechanisms in shock tubes.

Optical re-injection in cavity-enhanced absorption spectroscopy

Non-mode-matched cavity-enhanced absorption spectrometry (e.g., cavity ringdown spectroscopy and integrated cavity output spectroscopy) is commonly used for the ultrasensitive detection of trace gases. These techniques are attractive for their simplicity and robustness, but their performance may be limited by the reflection of light from the front mirror and the resulting low optical transmission. Although this low transmitted power can sometimes be overcome with higher power lasers and lower noise detectors (e.g., in the near-infrared), many regimes exist where the available light intensity or photodetector sensitivity limits instrument performance (e.g., in the mid-infrared). In this article, we describe a method of repeatedly re-injecting light reflected off the front mirror of the optical cavity to boost the cavity's circulating power and deliver more light to the photodetector and thus increase the signal-to-noise ratio of the absorption measurement. We model and experimentally demonstrate the method's performance using off-axis cavity ringdown spectroscopy (OA-CRDS) with a broadly tunable external cavity quantum cascade laser. The power coupled through the cavity to the detector is increased by a factor of 22.5. The cavity loss is measured with a precision of 2 × 10(-10) cm(-1)/√Hz; an increase of 12 times over the standard off-axis configuration without reinjection and comparable to the best reported sensitivities in the mid-infrared. Finally, the re-injected CRDS system is used to measure the spectrum of several volatile organic compounds, demonstrating the improved ability to resolve weakly absorbing spectroscopic features.

Development of a cavity-enhanced aerosol albedometer

Abstract. We report on the development of a cavity-enhanced aerosol single-scattering albedometer based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) combined with an integrating sphere (IS) for simultaneous in situ measurements of aerosol scattering and extinction coefficients in an exact same sample volume. The cavity-enhanced albedometer employed a blue light-emitting-diode (LED)-based IBBCEAS approach for the measurement of wavelength-resolved aerosol optical extinction over the spectral range of 445–480 nm and an integrating sphere nephelometer coupled to the IBBCEAS setup for the measurement of aerosol scattering. The scattering signal was measured with a single-channel photomultiplier tube (PMT), providing an averaged value over a narrow bandwidth (full-width at half-maximum, FWHM, ~ 9 nm) in the spectral region of 465–474 nm. A scattering coefficient at a wavelength of 470 nm was deduced as an averaged scattering value over the spectral region of 465–474 nm and used for data analysis and instrumental performance comparison. Performance evaluation of the albedometer was carried out using laboratory-generated particles and ambient aerosol. The scattering and extinction measurements of monodisperse polystyrene latex (PSL) spheres generated in the laboratory proved excellent correlation between two channels of the albedometer. The retrieved refractive index (RI) of the PSL particles from the measured scattering and extinction efficiencies agreed well with the values reported in previously published papers. Aerosol light scattering and extinction coefficients, single-scattering albedo (SSA) and NO2 concentrations in an ambient sample were directly and simultaneously measured using the albedometer developed. The instrument developed was validated via an intercomparison of the measured aerosol scattering coefficients and NO2 trace gas concentrations to a TSI 3563 integrating nephelometer and a chemiluminescence detector, respectively.

Development and deployment of a cavity enhanced UV-LED spectrometer for measurements of atmospheric HONO and NO2 in Hong Kong

An optical analytical instrument based on light emitting diode (LED) incoherent broadband cavity enhanced absorption spectroscopy (LED-IBBCEAS) was developed for simultaneous measurements of HONO and NO2 in ambient air. Detection limits (for signal-to-noise ratio, SNR = 2) of 0.6 ppbv for HONO and 2 ppbv for NO2 were achieved with an optimum acquisition time of 120 s. Field intercomparison campaign at a suburban site of Tung Chung in Hong Kong was carried out. Daytime and nighttime concentrations of HONO and NO2 were recorded and compared with data from a long path absorption photometer (LOPAP) and a NOx analyzer equipped with a blue light converter. The test of such a LED-IBBCEAS setup by the measurement intercomparison with the well established HONO and NO2 measurement instruments, for the first time, in a real atmospheric environment, demonstrated the feasibility of the proposed technique for the measurement of environmental HONO and NO2 concentrations in a manner that is free of chemical and spectral interference. During the measurement period from 12:32 on May 12th to 12:32 on May 14th, 2012, the quantitative assessments from these techniques showed well agreed data. High temporal correlations of HONO with NOx and CO were observed, and possible formation sources of HONO are discussed. Occasional inconsistencies in the quantitative assessment of HONO were observed during the in-field campaign. The problems encountered by the IBBCEAS technique applied to field observation and the further improvements are discussed.

RF noise induced laser perturbation for improving the performance of non-resonant cavity enhanced absorption spectroscopy.

We present a novel strategy for suppressing mode structure which often degrades off-axis cavity enhanced absorption spectra. This strategy relies on promoting small, random fluctuations in the optical frequency by perturbing the injection current of the diode laser source with radio frequency (RF) bandwidth-limited white noise. A fast and compact oxygen sensor, constructed from a 764 nm vertical-cavity surface-emitting laser (VCSEL) and an optical cavity with re-entrant configuration, is employed to demonstrate the potential of this scheme for improving the sensitivity and robustness of a field-deployable cavity spectrometer. The RF spectral density of the current noise injected into the VCSEL has been measured, and correlated to the effects on the optical spectral signal-to-noise ratio (SNR) and laser linewidth for a range of re-entrant geometries. A fourfold gain in the SNR has been achieved using the RF noise perturbation for the optimal off-axis alignment, which led to a minimum detectable absorption (MDA) predicted from an Allan variance study as low as 4.3 × 10(-5) at 1 s averaging. For the optically forbidden oxygen transition under investigation, a limit of detection (SNR = 1) of 810 ppm was achieved for a 10 ms acquisition time. This performance level paves the way for a fast, sensitive, in-line oxygen spectrometer that lends itself to a range of applications in respiratory medicine.

Laser-based method and sample handling protocol for measuring breath acetone.

A robust method is demonstrated to measure acetone in human breath at sub parts-per-million by volume (ppmv) concentrations using diode laser cavity enhanced absorption spectroscopy. The laser operates in the near-infrared at about 1690 nm probing overtone transitions in acetone in a spectral region relatively free from interference from common breath species such as CO2, water, and methane. Using an optical cavity with a length of 45 cm, bound by mirrors of 99.997% reflectivity, a limit of detection of ∼180 parts-per-billion by volume (ppbv) (1σ) of breath acetone is achieved. The method is validated with measurements made with an ion-molecule reaction mass spectrometer. A technique to calibrate the optical cavity mirror reflectivity using a temperature dependent water vapor source is also described.

Cavity-Enhanced Overtone Spectroscopy of Methanol in Aprotic Solvents: Probing Solute–Solvent Interactions and Self-Associative Behavior

Methanol in aprotic solvents can serve as a case study for self-association via hydrogen-bonding, which is an important process in many biological and environmental systems. Incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS), which provides enhanced sensitivity relative to conventional single-pass absorption techniques, has been used to characterize the third "free" O-H stretching overtone of methanol in four aprotic solvents (CCl4, CHCl3, CH2Cl2, and C6H6), including the transition wavenumber, bandwidth, and molar absorptivity. The absorption band characteristics indicate an increasing degree of nonspecific methanol-solvent interaction with increasing solvent dielectric constant, except in the case of benzene, which shows evidence of a specific, H-π interaction. Density functional theory with the polarizable continuum model was used to complement the results by assessing the accuracy of computational methods for calculating anharmonic O-H stretching frequencies. Finally, the self-association of methanol in these solvents at 298 K was also investigated using the concentration dependence of the overtone absorption intensity. The propensity for methanol's self-association in the solvents studied increases in the order: CH2Cl2 ∼ CHCl3 < C6H6 < CCl4.

Sensitive and rapid laser diagnostic for shock tube kinetics studies using cavity-enhanced absorption spectroscopy.

We report the first application of cavity-enhanced absorption spectroscopy (CEAS) using a coherent light source for sensitive and rapid gaseous species time-history measurements in a shock tube. Off-axis alignment and fast scanning of the laser wavelength were used to minimize coupling noise in a low-finesse cavity. An absorption gain factor of 83 with a measurement time resolution of 20 µs was demonstrated for C2H2 detection using a near-infrared transition near 1537 nm, corresponding to a noise-equivalent detection limit of 20 ppm at 296 K and 76 ppm at 906 K at 50 kHz. This substantial gain in signal, relative to conventional single-pass absorption, will enable ultra-sensitive species detection in shock tube kinetics studies, particularly useful for measurements of minor species and for studies of dilute reactive systems.

Broadband Cavity-Enhanced Detection of Magnetic Field Effects in Chemical Models of a Cryptochrome Magnetoreceptor

Broadband cavity-enhanced absorption spectroscopy (BBCEAS) is shown to be a sensitive method for the detection of magnetic field effects (MFEs) in two flavin-based chemical reactions which are simple models for cryptochrome magnetoreceptors. The advantages of optical cavity-based detection and (pseudo-white-light) supercontinuum radiation have been combined to provide full spectral coverage across the whole of the visible spectrum (425 < λ < 700 nm). This region covers the absorbance spectra of flavin mononucleotide (FMN) and flavin adenine dinucleotide (FAD) as well as their photogenerated radicals. To illustrate the power of this technique, BBCEAS has been used to record the spectral dependence of MFEs for photoinduced radical pairs formed in the intermolecular reaction of FMN with lysozyme and the intramolecular photochemistry of FAD. These reactions have been chosen for their photochemical similarities to cryptochrome proteins which have been proposed as key to the magnetic compass sense of many animals including birds. In experiments performed using low protein concentrations (10 μM) and 1 mm optical path-lengths, absorbance changes as small as 1 × 10(-7) (representing <0.1%MFEs) have been detected with good signal-to-noise offering the prospect of sensitive MFE detection in cryptochrome.

Real-time measurements of endogenous carbon monoxide production in isolated pig lungs

Ischemia-reperfusion injuries are a critical determinant of lung transplantation success. The endogenous production of carbon monoxide (CO) is triggered by ischemia-reperfusion injuries. Our aim was, therefore, to assess the feasibility of exhaled CO measurements during the ex vivo evaluation of lungs submitted to ischemia-reperfusion injuries. Five pigs were euthanized and their lungs removed after pneumoplegia. After cold storage (30 min, 4°C), the lungs were connected to an extracorporeal membrane oxygenation circuit, slowly warmed-up, and ventilated. At the end of a 45-min steady state, CO measurements were performed by optical-feedback cavity-enhanced absorption spectroscopy, a specific laser-based technique for noninvasive and real-time low gas concentration measurements. Exhaled CO concentration from isolated lungs reached 0.45±0.19 ppmv and was above CO concentration in ambient air and in medical gas. CO variations peaked during the expiratory phase. Changes in CO concentration in ambient air did not alter CO concentrations in isolated lungs. Exhaled CO level was also found to be uncorrelated to heme oxygenase (HO-1) gene expression. These results confirm the feasibility of accurate and real-time CO measurement in isolated lungs. The presented technology could help establishing the exhaled CO concentration as a biomarker of ischemia-reperfusion injury in ex vivo lung perfusion.

Rate Coefficients of C1 and C2 Criegee Intermediate Reactions with Formic and Acetic Acid Near the Collision Limit: Direct Kinetics Measurements and Atmospheric Implications

Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH2OO and CH3CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH3COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10−10 cm3 s−1, several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.

Very high finesse optical-feedback cavity-enhanced absorption spectrometer for low concentration water vapor isotope analyses

So far, cavity-enhanced absorption spectroscopy (CEAS) has been based on optical cavities with a high finesse F that, however, has been limited by mirror reflectivity and by cavity transmission considerations to a few times 10,000. Here, we demonstrate a compact near-infrared optical-feedback CEAS instrument for water vapor isotope ratio measurements, with F>140,000. We show that this very high finesse can be effectively exploited to improve the detection sensitivity to the full extent predicted by the increased effective path length to reach a noise equivalent absorption sensitivity of 5.7×10(-11) cm(-1) Hz(-1/2) for a full spectrum registration (including possible effects of interference fringes and fit model inadequacies).

Formation of gas-phase carbonyls from heterogeneous oxidation of polyunsaturated fatty acids at the air–water interface and of the sea surface microlayer

Abstract. Motivated by the potential for reactive heterogeneous chemistry occurring at the ocean surface, gas-phase products were observed when a reactive sea surface microlayer (SML) component, i.e. the polyunsaturated fatty acids (PUFA) linoleic acid (LA), was exposed to gas-phase ozone at the air–seawater interface. Similar oxidation experiments were conducted with SML samples collected from two different oceanic locations, in the eastern equatorial Pacific Ocean and from the west coast of Canada. Online proton-transfer-reaction mass spectrometry (PTR-MS) University of Colorado light-emitting diode cavity-enhanced differential optical absorption spectroscopy (LED-CE-DOAS) were used to detect oxygenated gas-phase products from the ozonolysis reactions. The LA studies indicate that oxidation of a PUFA monolayer on seawater gives rise to prompt and efficient formation of gas-phase aldehydes. The products are formed via the decomposition of primary ozonides which form upon the initial reaction of ozone with the carbon–carbon double bonds in the PUFA molecules. In addition, two highly reactive dicarbonyls, malondialdehyde (MDA) and glyoxal, were also generated, likely as secondary products. Specific yields relative to reactant loss were 78%, 29%, 4% and &lt; 1% for n-hexanal, 3-nonenal, MDA and glyoxal, respectively, where the yields for MDA and glyoxal are likely lower limits. Heterogeneous oxidation of SML samples confirm for the first time that similar carbonyl products are formed via ozonolysis of environmental samples.

A smog chamber comparison of a microfluidic derivatisation measurement of gas-phase glyoxal and methylglyoxal with other analytical techniques

Abstract. A microfluidic lab-on-a-chip derivatisation technique has been developed to measure part per billion (ppbV) mixing ratios of gaseous glyoxal (GLY) and methylglyoxal (MGLY), and the method is compared with other techniques in a smog chamber experiment. The method uses o-(2, 3, 4, 5, 6-pentafluorobenzyl) hydroxylamine (PFBHA) as a derivatisation reagent and a microfabricated planar glass micro-reactor comprising an inlet, gas and fluid splitting and combining channels, mixing junctions, and a heated capillary reaction microchannel. The enhanced phase contact area-to-volume ratio and the high heat transfer rate in the micro-reactor resulted in a fast and highly efficient derivatisation reaction, generating an effluent stream ready for direct introduction to a gas chromatograph-mass spectrometer (GC-MS). A linear response for GLY was observed over a calibration range 0.7 to 400 ppbV, and for MGLY of 1.2 to 300 ppbV, when derivatised under optimal reaction conditions. The analytical performance shows good accuracy (6.6% for GLY and 7.5% for MGLY), suitable precision (&lt;12.0%) with method detection limits (MDLs) of 75 pptV for GLY and 185 pptV for MGLY, with a time resolution of 30 min. These MDLs are below or close to typical concentrations of these compounds observed in ambient air. The feasibility of the technique was assessed by applying the methodology to quantify α-dicarbonyls formed during the photo-oxidation of isoprene in the EUPHORE chamber. Good correlations were found between microfluidic measurements and Fourier Transform InfraRed spectroscopy (FTIR) with a correlation coefficient (r2) of 0.84, Broadband Cavity Enhanced Absorption Spectroscopy (BBCEAS) (r2 = 0.75), solid phase micro extraction (SPME) (r2 = 0.89), and a photochemical chamber box modelling calculation (r2 = 0.79) for GLY measurements. For MGLY measurements, the microfluidic technique showed good agreement with BBCEAS (r2 = 0.87), SPME (r2 = 0.76), and the modeling simulation (r2 = 0.83), FTIR (r2 = 0.72) but displayed a discrepancy with Proton-Transfer Reaction Time-of-Flight Mass Spectrometry (PTR-ToF-MS) with r2 value of 0.39.

An instrument for measurements of BrO with LED-based Cavity-Enhanced Differential Optical Absorption Spectroscopy

Abstract. The chemistry of the troposphere and specifically the global tropospheric ozone budget is affected by reactive halogen species such as bromine monoxide (BrO) or chlorine monoxide (ClO). Especially BrO plays an important role in the processes of ozone destruction, disturbance of NOx and HOx chemistry, oxidation of dimethyl sulfide (DMS), and the deposition of elementary mercury. In the troposphere BrO has been detected in polar regions, at salt lakes, in volcanic plumes, and in the marine boundary layer. For a better understanding of these processes, field measurements as well as reaction chamber studies are performed. In both cases instruments with high spatial resolution and high sensitivity are necessary. A Cavity-Enhanced Differential Optical Absorption Spectroscopy (CE-DOAS) instrument with an open path measurement cell was designed and applied. For the first time, a CE-DOAS instrument is presented using an UV LED in the 325–365 nm wavelength range. In laboratory studies, BrO as well as HONO, HCHO, O3, and O4 could be reliably determined at detection limits of 20 ppt for BrO, 9.1 ppb for HCHO, 970 ppt for HONO, and 91 ppb for O3, for five minutes integration time. The best detection limits were achieved for BrO (11 ppt), HCHO (5.1 ppb), HONO (490 ppt), and O3 (59 ppb) for integration times of 81 minutes or less. Comparison with established White system (WS) DOAS and O3 monitor measurements demonstrate the reliability of the instrument.

Planetary laser spectrometer for sensitive in situ detection of water at 1881 nm

We describe the design and capabilities of a highly sensitive prototype tunable diode laser spectrometer for detecting water vapor and its isotopologues in the 1881nm region. It is a compact instrument based on wavelength modulated cavity enhanced absorption spectroscopy and can measure a fractional optical absorption of ~10−5 for a pathlength of ~4km, corresponding to ~10−8mbar of water vapor (improvable to 10−9mbar). The spectrometer would be suitable for searching for fingerprints of ancient climates on Mars and potential habitats of life in the Solar system. It would be useful for appraising water deposits on the Moon and asteroids, and characterizing the isotopic composition. Lunar deployment could provide ground truth to the recent orbital measurements, and help to discover records of the early bombardment history of the inner Solar system buried at the poles and clarify the mechanism for the generation of water in the illuminated regions.

First analysis of the 2ν1 + 3ν3 band of NO2 at 7192.159 cm−1

The first investigation of the very weak 2ν1+3ν3 absorption band of nitrogen dioxide, 14N16O2, located at 7192.1587(1) cm−1 was performed using Fourier-transform incoherent broadband cavity-enhanced absorption spectroscopy (FT-IBBCEAS) in the 7080–7210cm−1 spectral range. The assigned 2ν1+3ν3 lines involve energy levels of the (203) vibrational state with rotational quantum numbers up to Ka=7 and N=47. Furthermore, due to local resonances involving energy levels from the (2,2,2)⇔(2,0,3) and (5,1,0)⇔(2,0,3) states, several transitions were also observed for the 2ν1+2ν2+2ν3 and 5ν1+ν3 dark bands, respectively. The energy levels were satisfactorily reproduced within their experimental uncertainty using a theoretical model which takes explicitly into account the Coriolis interactions between the levels of the (2,0,3) vibrational state and those of (2,2,2) and of (5,1,0). As a consequence, precise vibrational energies, rotational, and coupling constants were achieved for the triad {(5,0,1), (2,2,2), (2,0,3)} of interacting states of 14N16O2. This theoretical model also accounts for the electron spin-rotation resonances within the (2,0,3), (2,2,2) and (5,1,0) vibrational states. However, owing to the limited experimental resolution (∼0.075cm−1), it was not possible to observe the spin-rotation doublet structure. As a consequence, the spin-rotation constants in the {(2,2,2), (2,0,3), (5,1,0)} excited states were maintained fixed to their ground state values in this study. Using these parameters a comprehensive list of line positions and line intensities was generated for the 2ν1+3ν3 band of NO2.

N2O的离轴腔增强吸收光谱检测技术

Based on the Off-axis Cavity Enhanced Absorption Spectroscopy(OA-CEAS)technique,a high sensitivity pollution gas detection system was made by using a tunable near infrared diode laser as light source and a high finesse optical cavity with two plan-concave mirrors of reflectivity of 97.97% as absorption cell.The absorption spectra of N2O gas mixtures centered at 6 561.39cm-1 were obtained. The relationship between the absorption intensity and gaseous concentration was obtained by recording the absorption spectra of N2O gas mixtures at different concentration.The line-width of absorption spectroscopy vs the gas pressure and the detection limit was discussed as well.The minimum detection concentration was found to be 86ppm using this cavity enhanced absorption spectroscopy system. Indicating the cavity enhanced absorption spectroscopy is a sensitive,easy manipulated,robust and simplified technique,which can be used for rapid gas analysis.

Uptake of Gas Phase Nitrous Acid onto Boundary Layer Soil Surfaces

Nitrous acid (HONO) is an important OH radical source that is formed on both ground and aerosol surfaces in the well-mixed boundary layer. Large uncertainties remain in quantifying HONO sinks and determining the mechanism of HONO uptake onto surfaces. We report here the first laboratory determination of HONO uptake coefficients onto actual soil under atmospheric conditions using a coated-wall flow tube coupled to a highly sensitive chemical ionization mass spectrometer (CIMS). Uptake coefficients for HONO decrease with increasing RH from (2.5 ± 0.4) × 10(-4) at 0% RH to (1.1 ± 0.4) × 10(-5) at 80% RH. A kinetics model of competitive adsorption of HONO and water onto the particle surfaces fits the dependence of the HONO uptake coefficients on the initial HONO concentration and relative humidity. However, a multiphase resistor model based on the physical and chemical processes affecting HONO uptake is more flexible as it accounts for the pH dependence of HONO uptake and bulk diffusion in the soil matrix. Fourier transform infrared (FTIR) spectrometry and cavity-enhanced absorption spectroscopy (CEAS) studies indicate that NO and N2O (16% and 13% yield, respectively) rather than NO2 are the predominant gas phase products, while NO2(-) and NO3(-) were detected on the surface post-exposure. Results are compared to uptake coefficients inferred from models and field measurements, and the atmospheric implications are discussed.