Broadband Cavity Enhanced Absorption Spectroscopy Research Articles

A portable nitrogen dioxide instrument using cavity-enhanced absorption spectroscopy

Abstract. The Portable (2.7 kg) Cavity-enhanced Absorption of Nitrogen Dioxide (PCAND) instrument for measuring in situ nitrogen dioxide (NO2) was developed using incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). An LED light source centered at 408 nm was coupled to a cavity 15 cm in length, achieving an effective optical pathlength of ∼520 m. Precision was measured as 94 pptv (1 s). To date, we have flown this instrument on three balloon test flights. This instrument records data on an SD card and outputs data (via an RS232 port) to external devices including a commercial radiosonde (iMet) for real-time data downlink.

The observation of atmospheric HONO by wet-rotating-denuder ion chromatograph in a coastal city: Performance and influencing factors

Due to the significance of atmospheric HONO as a reservoir for radicals and the presence of substantial unknown sources of HONO, there is a pressing need for accurate and consistent measurement of its concentration. In this study, we compared the measurements obtained from the monitor for aerosols and gases in ambient air (MARGA) based on wet chemical method with those from the incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) based on optical method to assess the suitability of the MARGA instrument for accurate HONO detection. The diurnal patterns obtained by the two instruments are similar, with peaks at 8 a.m. and lows at 5 p.m. Over the course of the observation period, it was often observed that HONO concentrations recorded by the MARGA instrument consistently exceeded those obtained through the IBBCEAS technique, accounting for approximately 91.33% of the total observation time. Throughout the entire observation period, the R2 value between the two instruments was 0.49, indicating relatively good correlation. However, with a slope of only 0.27, it suggests poor agreement between the two instruments. Furthermore, the R2 and slopes between the two instruments vary with the seasons and day-night. The larger the quartile values of NO2, NH3, and BC, the greater the slopes of both MARGA and IBBCEAS instruments, and the higher the concentrations of NO2, NH3, and BC (indicator of semivolatile oxidizable hydrocarbons), the greater the differences between the two instruments, all indicating that NH3 may promote the reaction of NO2 with semivolatile oxidizable hydrocarbons to produce HONO. The O3 with its strong oxidizing properties may cause underestimation in the MARGA instrument by oxidizing NO2− to NO3− in the absorbing solution. It is challenging to derive a universal correction formula due to the interference of various chemical substances. Hence, MARGA should not be used for HONO research in the future.

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.

Experimental observation of the ν1+3ν3 combination bands of 16O14N18O and 18O14N18O in the near infrared spectral region

The first observation of the ν1+3ν3 combination band of the nitrogen dioxide isotopologue 16O14N18O is presented. The band was measured using Fourier-Transform Incoherent Broad-Band Cavity Enhanced Absorption Spectroscopy (FT-IBBCEAS) in the region between 5870 cm−1 and 5940 cm−1. To confirm the assignment, the band was simulated using a standard asymmetric top Watson Hamiltonian using extrapolated rotational and centrifugal distortion constants. Furthermore, the first experimental observation of the ν1+3ν3 band of the 18O14N18O isotopologue is also reported. The positions of ro-vibrational lines of the ν1+3ν3 band of the naturally most abundant isotopologue 16O14N16O were used for wavenumber calibration of line positions.

A mini broadband cavity enhanced absorption spectrometer for nitrogen dioxide measurement on the unmanned aerial vehicle platform

We developed a small size and light weight analyzer based on the broadband cavity enhanced absorption spectroscopy for measuring nitrogen dioxide (NO2) with high spatial-temporal resolution and high accuracy. The instrument utilizes a LED centered at 450 nm, a short optical cavity, and a spectrometer to determine the extinction coefficients span 435–465 nm, allowing us to retrieve the mixing ratio of NO2 by absorption cross-section. The measurement precision (1σ) for NO2 is 98 ppt in 2 s under laboratory conditions. The uncertainty is estimated at 6% mainly attributed to cross-section and the mirror reflectivity. Good consistency was achieved by comparing with commercial chemiluminescence detector and cavity attenuation phase shift spectrometer (CAPS) (both R2 = 0.99). We further mounted the instrument on an unmanned aerial vehicle (UAV), and maintained the UAV flight at the height of 20 m, the comparative measurement with a CAPS set in a neighbor building with the same sampling height showed a good correlation (R2 = 0.97), which confirmed the instrumental feasibility and stability on the UAV platform. At last, we present a successful NO2 vertical measurement test, the good performance indicates this portable technique has great potential for vertical measurement. In particular, the mini-CEAS technique can further extend to measure the vertical profiles of other trace gas species (such as nitrous acid) with strong optical structural absorptions, which would largely promote the understanding of atmospheric chemistry on a vertical scale.

Broadband Cavity-Enhanced Absorption Spectroscopy (BBCEAS) Coupled with an Interferometer for On-Band and Off-Band Detection of Glyoxal.

Glyoxal (CHOCHO) is a trace gas in the atmosphere, often used as an indicator of biogenic emissions. It is frequently compared to formaldehyde concentrations, which serve as indicators of anthropogenic emissions, to gain insights into the characteristics of the environmental source. This study employed broadband cavity-enhanced absorption spectroscopy to detect gaseous CHOCHO, methylglyoxal, and NO2. Two different detection methods are compared. Spectrograph and CCD Detection: This approach involves coupling the system to a spectrograph with a charge-coupled device (CCD) detector. It achieved a 1 min 1-σ detection limit of 2.5 × 108 molecules/cm3, or 10 parts per trillion (ppt). Methylglyoxal and NO2 achieved 1 min 1-σ detection limits of 34 ppt and 22 ppt, respectively. Interferometer and PMT Detection: In this method, an interferometer is used in conjunction with a photomultiplier tube (PMT) detector. It resulted in a 2 min 1-σ detection limit of 1.5 × 1010 molecules/cm3, or 600 ppt. The NO2 2 min 1-σ detection limit was determined to be 900 ppt. Concentrations of methylglyoxal were difficult to determine using this method, as they appeared to be below the detection limit of the instrument. This study discusses the advantages and limitations of each of these detection methods.

Laboratory Performance Evaluation of a Low-Cost Electrochemical Formaldehyde Sensor.

Formaldehyde is a known human carcinogen and an important indoor and outdoor air pollutant. However, current strategies for formaldehyde measurement, such as chromatographic and optical techniques, are expensive and labor intensive. Low-cost gas sensors have been emerging to provide effective measurement of air pollutants. In this study, we evaluated eight low-cost electrochemical formaldehyde sensors (SFA30, Sensirion®, Staefa, Switzerland) in the laboratory with a broadband cavity-enhanced absorption spectroscopy as the reference instrument. As a group, the sensors exhibited good linearity of response (R2 > 0.95), low limit of detection (11.3 ± 2.07 ppb), good accuracy (3.96 ± 0.33 ppb and 6.2 ± 0.3% N), acceptable repeatability (3.46% averaged coefficient of variation), reasonably fast response (131-439 s) and moderate inter-sensor variability (0.551 intraclass correlation coefficient) over the formaldehyde concentration range of 0-76 ppb. We also systematically investigated the effects of temperature and relative humidity on sensor response, and the results showed that formaldehyde concentration was the most important contributor to sensor response, followed by temperature, and relative humidity. The results suggest the feasibility of using this low-cost electrochemical sensor to measure formaldehyde concentrations at relevant concentration ranges in indoor and outdoor environments.

Novel Broadband Cavity-Enhanced Absorption Spectrometer for Simultaneous Measurements of NO2 and Particulate Matter.

A novel instrument based on broadband cavity-enhanced absorption spectroscopy has been developed using a supercontinuum broadband light source, which showcases its ability in simultaneous measurements of the concentration of NO2 and the extinction of particulate matter. Side-by-side intercomparison was carried out with the reference NOx analyzer for NO2 and OPC-N2 particle counter for particulate matter, which shows a good linear correlation with r2 > 0.90. The measurement limits (1σ) of the developed instrument were experimentally determined to be 230 pptv in 40 s for NO2 and 1.24 Mm-1 for the extinction of particulate matter in 15 s. This work provides a promising method in simultaneously monitoring atmospheric gaseous compounds and particulate matter, which would further advance our understanding on gas-particle heterogeneous interactions in the context of climate change and air quality.

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.

Quantification of iron and copper ions in some edible oils using broadband cavity enhanced absorption spectroscopy (BBCEAS)

AbstractBackgroundThe first application of liquid‐phase broadband cavity‐enhanced absorption spectroscopy (BBCEAS) measurements in food science was made to determine the presence of iron and copper metal in some edible oils. Metal ions in trace amounts, such as iron and copper, have an effect on the oxidative stability of edible oils. The creation of unwanted chemicals is accelerated in the presence of transition metals such as iron and copper, which act as a catalyst in the decomposition of hydrogen peroxides. In general, the rate of oxidation of edible oils can be accelerated, even with trace levels of metal ions. This has an effect on the flavour, odour, and taste of edible oils. As a result, it is critical to determine trace metal concentrations when evaluating oil quality in terms of freshness, stability, and storage.ResultsIn this work, for the first time, Iron and copper metal were detected in olive oil, sunflower oil, frying rapeseed oil, cold‐pressed olive oil, and cold‐pressed rapeseed oil samples using BBCEAS. Sensitivity and limit of detection (LOD) of conventional spectrophotometer of analysis have been reported as 4.42 × 10−4 cm−1 Hz−½ and 3.3 × 10−2 for Iron and 4.39 × 10−4 cm−1 Hz−½ and 2.8 × 10−2 mg/L for copper. The results of BBCEAS measurements standard solutions produced sensitivity (αmin[t]) and LOD values of 8.86 × 10−6 cm−1 Hz−½ and 2.38 × 10−4 mg/L for Iron and 4.5 × 10−6 cm−1 Hz−½ and 2.1 × 10−4 mg/L for copper, respectively.ConclusionOverall, the results obtained in this work represent a 116‐fold improvement for iron and 78‐fold for copper in sensitivity compared to conventional absorption spectroscopy measurements. The BBCEAS measurements of iron metal in the edible oil samples did not detect the metal in the olive and sunflower oil samples but did detect it in the other oil samples at parts per billion (ppb) levels. Copper was found to be present in all oil samples. The study demonstrates the suitability of applying the BBCEAS technique to food analysis.

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.

Spectral Behaviour of the low concentrations of Coumarin 334 with Broadband Cavity Enhanced Absorption Spectroscopy

The current research is a spectroscopic study of Coumarin 334 dissolved in methanol. The range of concentrations of the prepared stock solution was (3.39x10-9 to 2.03x10-8) M. Some optical characteristics of this dye were investigated such as absorbance and transmission spectra, absorption coefficient, refractive and extinction coefficients, oscillation and dispersion energies, and energy band gap. The absorbance spectra were recorded at 452 nm using Broad Band Cavity Enhanced Absorption Spectroscopy (BBCEAS) which depends on increasing the path length of the traveling light from the source to the detector. The minimum absorbance amount was 0.07 with a low concentration of 3.39x10-9 M. As a result, the other optical properties were calculated on the basis of the lowest values of absorbance. The energy band gap, which is important to detect the electronic band structure of the material, was determined; it was found to be equal to ~2.55 eV. The low values of the concentration made less collision between the molecules in the materials and the incident light. This led to a reduction in the background noise and in the percentages of losses. Furthermore, the dispersion and single oscillator energies, which help to calculate the average strength of the inter-band optical transitions and to prepare the quantifiable information about the band structure of the material, were calculated to reduce with the increasing concentrations. The refractive and extinction coefficients were determined because they are considered important factors for the optical materials and found to increase with the increasing concentrations. As a result, the study of the optical behavior of Coumarin 334 highlighted the promising materials for photonics applications at very low concentrations. All these properties are considered the main factors to determine the usefulness of the materials in advanced applications and to develop the performance of the devices which depend on the optical characteristics.

Detection of Sulfur Dioxide by Broadband Cavity-Enhanced Absorption Spectroscopy (BBCEAS).

Sulfur dioxide (SO2) is an important precursor for the formation of atmospheric sulfate aerosol and acid rain. We present an instrument using Broadband Cavity-Enhanced Absorption Spectroscopy (BBCEAS) for the measurement of SO2 with a minimum limit of detection of 0.75 ppbv (3-) using the spectral range 305.5–312 nm and an averaging time of 5 min. The instrument consists of high-reflectivity mirrors (0.9985 at 310 nm) and a deep UV light source (Light Emitting Diode). The effective absorption path length of the instrument is 610 m with a 0.966 m base length. Published reference absorption cross sections were used to fit and retrieve the SO2 concentrations and were compared to fluorescence standard measurements for SO2. The comparison was well correlated, R2 = 0.9998 with a correlation slope of 1.04. Interferences for fluorescence measurements were tested and the BBCEAS showed no interference, while ambient measurements responded similarly to standard measurement techniques.

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.

Measurements of atmospheric HONO and NO<sub>2</sub> utilizing an open-path broadband cavity enhanced absorption spectroscopy based on an iterative algorithm

Nitrous acid (HONO), as an important precursor of hydroxyl (OH) radical, has a low concentration, short lifetime, easy loss and high reactivity in the atmosphere. Thus, the high sensitivity detection of atmospheric HONO is a challenge. In this paper, we report an open-path broadband cavity enhanced absorption spectroscopy (OP-BBCEAS) system based on the iterative algorithm for simultaneous measurement of atmospheric HONO and NO<sub>2</sub>. In the conventional BBCEAS system, a pump is used to drive the ambient air into the optical cavity through the filter membrane for measurement, which can reduce the influence of aerosol particle extinction. However, the influence of wall loss and secondary formation caused by the optical cavity and sampling should be considered for reactive component measurements. The OP-BBCEAS with open-path configuration is adopted in this paper to avoid being influenced by wall effect. The effective absorption optical path is calculated by the iterative retrieval algorithm through multiple iterations, and the absorption of HONO and NO<sub>2</sub> are then quantified by the spectral fitting method of differential optical absorption spectroscopy, which removes the broadband change influence of the Mie scattering extinction by aerosol particles and the light intensity fluctuation. The atmospheric HONO and NO<sub>2</sub> with light (PM<sub>2.5</sub> < 75 μg/m<sup>3</sup>) and moderate (PM<sub>2.5</sub> > 75 μg/m<sup>3</sup>) aerosol loading are measured by the OP-BBCEAS system based on iterative algorithm, and compared with the counterparts by the conventional close-path BBCEAS system. The concentrations of HONO and NO<sub>2</sub> measured by the two BBCEAS systems are in good agreement (<i>R</i><sup>2</sup> > 0.99) for different PM<sub>2.5</sub> concentration levels, and the measurement differences of HONO and NO<sub>2</sub> concentrations (HONO ≤ 4.0%, NO<sub>2</sub> ≤ 6.5%) are less than the systematic measurement errors (HONO: 8.1%, NO<sub>2</sub>: 7.5%), which verifies the feasibility of iterative algorithm applied to OP-BBCEAS system for atmospheric measurement.