Incoherent Broadband Cavity-enhanced Absorption Spectroscopy Research Articles

Revisiting the Ultraviolet Absorption Cross Section of Gaseous Nitrous Acid (HONO): New Insights for Atmospheric HONO Budget.

Nitrous acid (HONO) is an important source of hydroxyl radicals (OH) in the atmosphere. Precise determination of the absolute ultraviolet (UV) absorption cross section of gaseous HONO lays the basis for the accurate measurement of its concentration by optical methods and the estimation of HONO loss rate through photolysis. In this study, we performed a series of laboratory and field intercomparison experiments for HONO measurement between striping coil-liquid waveguide capillary cell (SC-LWCC) photometry and incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). Specified HONO concentrations prepared by an ultrapure standard HONO source were utilized for laboratory intercomparisons. Results show a consistent ∼22% negative bias in measurements of the IBBCEAS compared with a SC-LWCC photometer. It is confirmed that the discrepancies occurring between these techniques are associated with the overestimation of the absolute UV absorption cross sections through careful analysis of possible uncertainties. We quantified the absorption cross section of gaseous HONO (360-390 nm) utilizing a custom-built IBBCEAS instrument, and the results were found to be 22-34% lower than the previously published absorption cross sections widely used in HONO concentration retrieval and atmospheric chemical transport models (CTMs). This suggests that the HONO concentrations retrieved by optical methods based on absolute absorption cross sections may have been underestimated by over 20%. Plus, the daytime loss rate and unidentified sources of HONO may also have evidently been overestimated in pre-existing studies. In summary, our findings underscore the significance of revisiting the absolute absorption cross section of HONO and the re-evaluation of the previously reported HONO budgets.

Absorption cross-sections for the 5th and 6th vibrational overtones in a series of short chained alcohols using incoherent broadband cavity enhanced-absorption spectroscopy (IBBCEAS)

Absorption cross-sections for the 5th (6 ← 0) and 6th (7 ← 0) OH overtones for gas-phase methanol, ethanol, and isopropanol were measured using a slow flow cell and Incoherent Broadband Cavity-Enhanced Absorption Spectroscopy (IBBCEAS). Measurements were performed in two wavelength regions, 447–457 nm, and 508–518 nm, using two different instruments. The experimental results are consistent with previous computational predictions of the excitation energies for these transitions. Treating the OH stretch as a local mode allowed for calculation of the fundamental vibrational frequency (ωe), anharmonicity constant (ωexe), and the vertical dissociation energy (VDE) for each alcohol studied. The fundamental vibrational frequency is 3848 ± 18 cm−1, 3807 ± 55 cm−1, and 3813 ± 63 cm−1 for methanol, ethanol, and isopropanol, respectively. The anharmonicity constant was measured to be 84.8 ± 2.1 cm−1, 80.2 ± 5.9 cm−1, and 84.4 ± 6.8 cm−1 for methanol, ethanol, and isopropanol, respectively. The OH vertical dissociation energy was measured to be 499.4 ± 18.4 kJ/mol, 518.0 ± 56.7 kJ/mol, and 492.7 ± 59.9 kJ/mol. The spectroscopically measured values are compared to thermodynamically measured OH bond dissociation energies. The observed differences in previous measurements of the bond dissociation energies compared to the values reported herein can be explained due to the difference between vertical dissociation energies and bond dissociation energies. If the OH overtone stretching mode is excited in methanol to either the 5th or 6th overtone, the bimolecular reaction between methanol and O2 becomes thermodynamically feasible and could contribute to formation of methoxy and HO2 radical under the proper combination of pressure and temperature.

Intercomparison of NO3 under Humid Conditions with Open-Path and Extractive IBBCEAS in an Atmospheric Reaction Chamber

We report an open-path incoherent broadband cavity-enhanced absorption spectroscopy (OP-IBBCEAS) technique for in situ simultaneous optical monitoring of NO2, NO3, and H2O in a reaction chamber. The measurement precision values (1σ) are 2.9 ppbv and 2.9 pptv for NO2 and NO3 in 2 s, respectively, and the measurement uncertainties are 6% for NO2 and 14% for NO3. Intercomparison of measured concentrations of NO2 and NO3 by open-path and extractive IBBCEAS was carried out in the SAES-ARC reaction chamber during the reaction of NO2 with O3. The measurement accuracy of OP-IBBCEAS is verified by an NO2 intercomparison and the NO3 transmission efficiency of the extractive IBBCEAS is determined by comparison against the in situ NO3 measurement. The relationship between H2O absorption cross section and its mixing ratio at 295 K and 1 atm was analysed. Due to the spectral resolution of IBBCEAS system, the strong and narrow absorption lines of H2O are unresolved and exhibit non-Beer–Lambert Law behaviour. Therefore, a correction method is used to obtain the effective absorption cross section for fitting the H2O structure. An inappropriate H2O absorption cross section can cause an overestimation of NO3 concentration of about 28% in a humid atmosphere (H2O = 1.8%). This spectroscopic correction provides an approach to obtain accurate NO3 concentrations for open-path optical configurations, for example in chamber experiments or field campaigns. The measurement precision values are improved by a factor of 3 to 4 after applying Kalam filtering, achieving sub-ppbv (0.8 ppbv) and sub-pptv (0.9 pptv) performance in 2 s for NO2 and NO3, respectively.

Summer variability of the atmospheric NO2 : NO ratio at Dome C on the East Antarctic Plateau

Abstract. Previous Antarctic summer campaigns have shown unexpectedly high levels of oxidants in the lower atmosphere of the continental plateau and at coastal regions, with atmospheric hydroxyl radical (OH) concentrations up to 4 × 106 cm−3. Such high reactivity in the summer Antarctic boundary layer results in part from the emissions of nitrogen oxides (NOx ≡ NO + NO2) produced during photo-denitrification of the snowpack, but its underlying mechanisms are not yet fully understood, as some of the chemical species involved (NO2, in particular) have not yet been measured directly and accurately. To overcome this crucial lack of information, newly developed optical instruments based on absorption spectroscopy (incoherent broadband cavity-enhanced absorption spectroscopy, IBBCEAS) were deployed for the first time at Dome C (−75.10 lat., 123.33 long., 3233 m a.s.l.) during the 2019–2020 summer campaign to investigate snow–air–radiation interaction. These instruments directly measure NO2 with a detection limit of 30 pptv (parts per trillion by volume or 10−12 mol mol−1) (3σ). We performed two sets of measurements in December 2019 (4 to 9) and January 2020 (16 to 25) to capture the early and late photolytic season, respectively. Late in the season, the daily averaged NO2:NO​​​​​​​ ratio of 0.4 ± 0.4 matches that expected for photochemical equilibrium through Leighton's extended relationship involving ROx (0.6 ± 0.3). In December, however, we observed a daily averaged NO2:NO ratio of 1.3 ± 1.1, which is approximately twice the daily ratio of 0.7 ± 0.4 calculated for the Leighton equilibrium. This suggests that more NO2 is produced from the snowpack early in the photolytic season (4 to 9 December), possibly due to stronger UV irradiance caused by a smaller solar zenith angle near the solstice. Such a high sensitivity of the NO2:NO ratio to the sun's position is of importance for consideration in atmospheric chemistry models.

Incoherent broadband cavity-enhanced absorption spectroscopy for sensitive measurement of nutrients and microalgae.

Incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) can achieve sensitive measurements at trace concentrations for liquid phase marine samples. The IBBCEAS system consists of a cavity-enhancement module (CEM) and a transmission hyperspectral module (THM). The CEM has cavity-enhancement factors up to 78 at 550 nm. Measurements were obtained over a wide wavelength range (420-640 nm) with a halogen lamp, and the optical cavity was formed by two concave highly reflective mirrors (R=0.99). The minimum detectable absorption coefficient αmin of 7.3×10-7cm-1 at 550 nm corresponds to a limit of detection for nutrients of 780 pM. The spectral resolution of the THM is 3 nm in the wavelength range of 400 to 750 nm. We performed the IBBCEAS measurements for biological and chemical substances, including nutrients, microalgae, and Cy5 dye. The concentrations of nutrients in a deionized water environment and artificial seawater environment were measured at nanomolar levels; the concentration of microalgae phaeocystis was detected with 3.46×104/mL, and fluorescence substances such as Cy5 dye could be measured at 0.03 mg/L. Experimental results show that the IBBCEAS system has the capability for sensitive measurements of biological and chemical substances and has strong potential forin situ ecological marine environmental monitoring function.

Gas-phase CH-Overtone band spectra of methyl acetate and ethyl acetate via incoherent broad-band cavity-enhanced absorption spectroscopy

Gas-phase overtone bands of methyl acetate and ethyl acetate were detected for up to v = 6–0 by incoherent broad-band cavity-enhanced absorption spectroscopy. The signal-to-noise ratios of v = 4–0 were achieved to be 40–50 by the 100 s integration time, suggesting an application possibility of this spectroscopic technique for environmental monitoring. Profiles of the observed overtone bands were analyzed in detail with the aid of theoretical calculations and their remarkable peaks were assigned to the progressions starting from the symmetric CH-stretching bands. The harmonic frequencies, the anharmonicities, and the dissociation energies were derived.

A Demonstration of Broadband Cavity-Enhanced Absorption Spectroscopy at Deep-Ultraviolet Wavelengths: Application to Sensitive Real-Time Detection of the Aromatic Pollutants Benzene, Toluene, and Xylene.

Benzene, toluene, and xylene (BTX) are serious air pollutants emitted by the chemical industry. Real-time monitoring of these air pollutants would be a valuable tool to regulate emissions of these compounds and reduce the harm they cause to human health. Here, we demonstrate the first detection of BTX using incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). The instrument was operated in the deep-ultraviolet spectral region between 252 and 286 nm, where aromatic compounds have intense π → π* absorption bands. The mirror reflectivity was calibrated by two methods and exceeded 99.63% at 266 nm. At an integration time of 60 s, the 1σ measurement sensitivities were estimated to be 7.2 ppbv for benzene, 21.9 ppbv for toluene, 10.2 ppbv for m-xylene, and 4.8 ppbv for p-xylene, respectively. The absorption cross sections of BTX were measured in this work with an uncertainty of 10.0% at a resolution of 0.74 nm. The absorption cross sections reported in this work were in good agreement with those from earlier studies after accounting for differences in spectral resolution. To demonstrate the ability of the instrument to quantify complex mixtures, the concentrations of m-xylene and p-xylene have been retrieved under five different mixing ratios. Instrumental improvements and measurements strategies for use in different applications are discussed.

Detection of nitrous acid in the atmospheric simulation chamber SAPHIR using open-path incoherent broadband cavity-enhanced absorption spectroscopy and extractive long-path absorption photometry

Abstract. An instrument based on 20 m open-path incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) was established at the Jülich SAPHIR chamber in spring 2011. The setup was optimized for the detection of HONO and NO2 in the near-UV region 352–386 nm, utilizing a bright hot-spot Xe-arc lamp and a UV-enhanced charge-coupled device (CCD) detector. A 2σ detection limit of 26 pptv for HONO and 76 pptv for NO2 was achieved for an integration time of 1 min. Methacrolein (MACR) was also detected at mixing ratios below 5 ppbv with an estimated 2σ detection limit of 340 pptv for the same integration time. The IBBCEAS instrument's performance for HONO and NO2 detection was compared to that of extractive wet techniques, long-path absorption photometry (LOPAP), and chemiluminescence spectrometry (CLS) NOx detection, respectively. For the combined data sets an overall good agreement for both trend and absolute mixing ratios was observed between IBBCEAS and these established instruments at SAPHIR. Correlation coefficients r for HONO range from 0.930 to 0.994 and for NO2 from 0.937 to 0.992. For the single measurement of MACR r=0.981 is found in comparison to proton-transfer-reaction mass spectrometry (PTRMS).

Intercomparison of Ambient Nitrous Acid Measurements in a Shanghai Urban Site

Nitrous acid (HONO) is the major source of OH radicals in polluted regions and plays a key role in the nitrogen cycle of the atmosphere. Therefore, accurate measurements of HONO in the atmosphere is important. Long Path Absorption Photometer (LOPAP) is a common and highly sensitive method used for ambient HONO measurements. Incoherent Broadband Cavity Enhanced Absorption Spectroscopy (IBBCEAS) is a recent alternative for the detection of HONO with high temporal and spatial resolutions, which has shown a detection limit of 0.76 ppbv at a sampling average of 180 s. In this study, LOPAP and IBBCEAS-HONO instruments were deployed in a Shanghai Urban Site (Shanghai Academy of Environmental Sciences) and simultaneously recorded the data from both instruments for a quantitative intercomparison of the measured atmospheric HONO for four days from 30 December 2017–2 January 2018. The HONO concentration measured by IBBCEAS and LOPAP were well matched. The campaign average concentrations measured by IBBCEAS and LOPAP were 1.28 and 1.20 ppbv, respectively. The intercomparison results demonstrated that both the IBBCEAS-HONO instrument and LOPAP-HONO instrument are suitable for ambient monitoring of HONO in a polluted urban environment.

Glyoxal in a nocturnal atmosphere measured by incoherent broadband cavity-enhanced absorption spectroscopy

Glyoxal in a nocturnal atmosphere measured by incoherent broadband cavity-enhanced absorption spectroscopy

Nitrous acid (HONO) emission factors for diesel vehicles determined using a chassis dynamometer

Vehicle exhaust gases are important sources of nitrous acid (HONO). In this study, HONO in diesel vehicle exhaust was measured by incoherent broadband cavity-enhanced absorption spectroscopy using a chassis dynamometer system. The mean HONO concentrations in exhaust gases emitted by passenger cars and light-duty trucks were high when the after treatment devices were not fully working during the warming up period. The HONO/NOx ratio is a good index of HONO formation. The HONO/NOx ratios were 9.7 × 10−3–18.1 × 10−3, and were higher than what we found in a previous study. The estimated HONO emission factors were 7.71–64.70 mg (kg fuel)−1, and were lower than were found in previous studies. The results indicated that the frequency particulate matter is removed from a diesel particle filter affects the HONO concentration in the emitted gases and the HONO emission factor.

Intercomparison of IBBCEAS, NitroMAC and FTIR analyses for HONO, NO<sub>2</sub> and CH<sub>2</sub>O measurements during the reaction of NO<sub>2</sub> with H<sub>2</sub>O vapour in the simulation chamber CESAM

Abstract. We report on applications of the ultraviolet-light-emitting-diode-based incoherent broadband cavity-enhanced absorption spectroscopy (UV-LED-IBBCEAS) technique for optical monitoring of HONO, NO2 and CH2O in a simulation chamber. Performance intercomparison of UV-LED-IBBCEAS with a wet chemistry-based NitroMAC sensor and a Fourier transform infrared (FTIR) spectrometer has been carried out on real-time simultaneous measurement of HONO, NO2 and CH2O concentrations during the reaction of NO2 with H2O vapour in CESAM (French acronym for Experimental Multiphasic Atmospheric Simulation Chamber). The 1σ (signal-to-noise ratio (SNR) = 1) detection limits of 112 pptv for NO2, 56 pptv for HONO and 41 ppbv for CH2O over 120 s were found for the UV-LED-IBBCEAS measurement. On the contrary to many set-ups where cavities are installed outside the simulation chamber, we describe here an original in situ permanent installation. The intercomparison results demonstrate that IBBCEAS is a very well suitable technique for in situ simultaneous measurements of multiple chemically reactive species with high sensitivity and high precision even if the absorption bands of these species are overlapped. It offers excellent capacity for non-invasive optical monitoring of chemical reactions without any perturbation. For the application to simulation chambers, it has the advantage to provide a spatially integrated measurement across the reactor and hence to avoid point-sampling-related artefacts.

The measurement of δ13C in respiratory gases based on incoherent broadband cavity enhanced absorption spectroscopy

The change of stable isotope ratio of carbon dioxide (δ13CO2) in respiratory gases of patients before and after taking medicine can be used to judge whether Helicobacter pylori exists in patients’ intestines and stomach. The 4.3 μm band of blackbody radiation source and infrared dual path structure are selected for measurement, the incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) technology was used to change the structure of the light path on one side of 13CO2 to make sure that the absorption intensity of 13CO2 and 12CO2 was in the same order of magnitude. The influence of different types of optical cavity, coating method of lens and reflectivity of mirror on effective optical path were compared in this article and the effective optical path length was the largest when the semi-stable cavity with 90% reflectivity and Ge coating material was used. The standard deviation of the measurement results was 0.191‰, which met the requirements of the precision and accuracy of the measurement index in medical detection. The system had the advantages of high precision, small volume, and accurate measurement results, which is of great significance for medical auxiliary detection.

Quantification of iodine monoxide based on incoherent broadband cavity enhanced absorption spectroscopy

The quantitative method of iodine monoxide radical (IO) using incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) in the 435–465 nm band is described in this paper. In order to obtain the concentration of IO accurately, the parameters such as the mirror reflectivity, effective cavity length and sample loss of the IBBCEAS system are evaluated. Using the difference of Rayleigh scattering between nitrogen and helium, the reflectivity curve of the high-reflection mirror is obtained. The reflectivity <i>R</i> of the mirror at 436.1 nm of the IO absorption peak is about 0.99982, and the effective absorption optical path reaches 3.83 km under vacuum condition. According to the absorption of O<sub>4</sub>, the effective cavity length of the modified system is 60.7 cm. The Allan deviation is used to evaluate the performance of the system, and the standard deviation is used to analyze the detection sensitivity of the system. When the time resolution is 60 s, the detection sensitivity (2<i>σ</i>) of the system for IO and NO<sub>2</sub> are 1.9 pptv and 20 pptv (part per trillion by volume), respectively. The iodine dissolved in potassium iodide (KI) solution is taken out by the bubbling method and react with ozone after photolysis to produce a stable concentration of IO sample gas. The IO loss in the sampling tube is calibrated, and the results show that the sampling tube has no significant effect on the IO loss. The IBBCEAS system is used to determine the linearity of IO, and the correlation coefficient <i>R</i><sup>2</sup> between the measured concentration of IO and the proportioned concentration in a concentration range from 39 to 530 pptv is 0.99. The IO produced by the reaction of iodine released from kelp with ozone is measured.

Implementation of an incoherent broadband cavity-enhanced absorption spectroscopy technique in an atmospheric simulation chamber for in situ NO<sub>3</sub> monitoring: characterization and validation for kinetic studies

Abstract. An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) technique has been developed for the in situ monitoring of NO3 radicals at the parts per trillion level in the CSA simulation chamber (at LISA). The technique couples an incoherent broadband light source centered at 662 nm with a high-finesse optical cavity made of two highly reflecting mirrors. The optical cavity which has an effective length of 82 cm allows for up to 3 km of effective absorption and a high sensitivity for NO3 detection (up to 6 ppt for an integration time of 10 s). This technique also allows for NO2 monitoring (up to 9 ppb for an integration time of 10 s). Here, we present the experimental setup as well as tests for its characterization and validation. The validation tests include an intercomparison with another independent technique (Fourier-transform infrared, FTIR) and the absolute rate determination for the reaction trans-2-butene + NO3, which is already well documented in the literature. The value of (4.13 ± 0.45) × 10−13 cm3 molecule−1 s−1 has been found, which is in good agreement with previous determinations. From these experiments, optimal operation conditions are proposed. The technique is now fully operational and can be used to determine rate constants for fast reactions involving complex volatile organic compounds (VOCs; with rate constants up to 10−10 cm3 molecule−1 s−1).

Design and characteristics of a cavity-enhanced Fourier-transform spectrometer based on a supercontinuum source.

We report the in-house fabrication of a high-resolution Fourier-transform spectrometer (FTS) for the spectroscopy of molecules in the gas phase at resolutions down to 0.002 cm-1 working in the spectral range from 5880 cm-1 (1.7 μm) to 15 380 cm-1 (650 nm). The FTS employs a supercontinuum as a broadband light source and a He:Ne laser with a homemade frequency-stabilization scheme as the spatial reference for the sampling of the interferogram on a constant optical path difference (OPD) grid. The sampling of the two lasers is performed at constant time intervals, and the resampling process is performed at the software level. The resampling of the interferogram on a constant OPD grid relies on cubic approximations of the He:Ne interference pattern to determine its zero-crossings. The use of an invariant in the sampling process allows us to perform on-the-fly data treatment. Both the hardware aspect and the data processing are described with, in each case, an original approach. We also report the successful coupling of the FTS with a high finesse optical cavity with effective mirror reflectivities of 99.76%, allowing us to reach sensitivities down to 6.5 × 10-8 cm-1 with a root-mean-square accuracy of 0.0017 cm-1 on the position of the Doppler-broadened transitions with a mean transition width of 0.046 cm-1 for spectra recorded at a spectral resolution of 0.015 cm-1. The sensitivity of the instrument per spectral element, once normalized, represents the best sensitivity reported in the literature for Fourier-transform incoherent broadband cavity-enhanced absorption spectroscopy with a supercontinuum light source.

A compact incoherent broadband cavity-enhanced absorption spectrometer for trace detection of nitrogen oxides, iodine oxide and glyoxal at levels below parts per billion for field applications

Abstract. We present a compact, affordable and robust instrument based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) for simultaneous detection of NOx, IO, CHOCHO and O3 in the 400–475 nm wavelength region. The instrument relies on the injection of a high-power LED source in a high-finesse cavity (F∼33 100), with the transmission signal being detected by a compact spectrometer based on a high-order diffraction grating and a charge-coupled device (CCD) camera. A minimum detectable absorption of 2.0×10-10 cm−1 was achieved within ∼22 min of total acquisition, corresponding to a figure of merit of 1.8×10-10 cm−1 Hz-1/2 per spectral element. Due to the multiplexing broadband feature of the setup, multi-species detection can be performed with simultaneous detection of NO2, IO, CHOCHO and O3 achieving detection limits of 11, 0.3, 10 ppt (parts per trillion) and 47 ppb (parts per billion) (1σ) within 22 min of measurement, respectively (half of the time is spent on the acquisition of the reference spectrum in the absence of the absorber, and the other half is spent on the absorption spectrum). The implementation on the inlet gas line of a compact ozone generator based on electrolysis of water allows for the measurement of NOx (NO+NO2) and therefore an indirect detection of NO with detection limits for NOx and NO of 10 and 21 ppt (1σ), respectively. The device has been designed to fit in a 19 in., 3U (5.25 in.) rack-mount case; weighs 15 kg; and has a total electrical power consumption of <300 W. The instrument can be employed to address different scientific objectives such as better constraining the oxidative capacity of the atmosphere, studying the chemistry of highly reactive species in atmospheric chambers as well as in the field and looking at the sources of glyoxal in the marine boundary layer to study possible implications on the formation of secondary aerosol particles.

Incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS)-based strategy for direct measurement of aerosol extinction in a lidar blind zone.

In this Letter, the development of a custom-designed incoherent broadband cavity enhanced absorption spectrometer (IBBCEAS) and its application to in situ measurement of aerosol extinction near the ground surface are described in an effort to address the issue of missing data in the light detection and ranging (lidar) blind zone in the first hundreds of meters of the observation range. Combined measurements of aerosol extinction at the same location using lidar remote sensing at 355 nm and in situ IBBCEAS operating in the UV spectral region around 370 nm showed results with a good correlation (${{\rm R}^2} = {0.90}$R2=0.90) between the two measurement techniques. This Letter highlights a new strategy for near-end lidar calibration, using a ground-based compact and robust IBBCEAS located at the lidar measurement site to determine the vertical profile of the aerosol extinction coefficient with a higher accuracy.

Sensitive Detection of Ambient Formaldehyde by Incoherent Broadband Cavity Enhanced Absorption Spectroscopy.

Formaldehyde (HCHO) is the most abundant atmospheric carbonyl compound and plays an important role in the troposphere. However, HCHO detection via traditional incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS) is limited by short optical path lengths and weak light intensity. Thus, a new light-emitting diode (LED)-based IBBCEAS was developed herein to measure HCHO in ambient air. Two LEDs (325 and 340 nm) coupled by a Y-type fiber bundle were used as an IBBCEAS light source, which provided both high light intensity and a wide spectral fitting range. The reflectivity of the two cavity mirrors used herein was 0.99965 (1 - reflectivity = 350 ppm loss) at 350 nm, which corresponded with an effective optical path length of 2.15 km within a 0.84 m cavity. At an integration time of 30 s, the measurement precision (1σ) for HCHO was 380 parts per trillion volume (pptv), and the corresponding uncertainty was 8.3%. The instrument was successfully deployed for the first time in a field campaign and delivered results that correlated well with those of a commercial wet-chemical instrument based on Hantzsch fluorimetry (R2 = 0.769). The combined light source based on a Y-type fiber bundle overcomes the difficulty of measuring ambient HCHO via IBBCEAS in near-ultraviolet range, which may extend IBBCEAS technology to measure other atmospheric trace gases with high precision.

New bands of deuterated nitrous acid (DONO) in the near-infrared using FT-IBBCEAS

The first measurements of near-infrared bands of deuterated nitrous acid (DONO) are presented. The measurements were made using Fourier-Transform Incoherent Broad-Band Cavity-Enhanced Absorption Spectroscopy (FT-IBBCEAS) in the 5800–7800 cm−1 region. Two bands of trans-DONO centred at 6212.029 and 7692.496 cm−1 were observed and assigned to the 2ν1+ν3 combination and 3ν1 overtone vibrations, respectively. Their rotational band structure was satisfactorily reproduced using PGOPHER. For cis-DONO the 3ν1 band was observed at ~7302.5 cm−1. In addition, new bands centred at 6142.5 cm−1 and 7607.6 cm−1 were quite confidently assigned to the 2ν1+ν3 and 3ν1 vibrations of deuterated nitric acid, DNO3, respectively.