HCHO Profiles Research Articles

Ground-based MAX-DOAS observations of tropospheric formaldehyde and nitrogen dioxide: Insights into ozone formation sensitivity

Tropospheric profiles of HCHO, NO2, and O3 are important for analyzing ozone formation mechanism. In this study, ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS), light detection and ranging (LIDAR), and in-situ measurements were simultaneously performed to diagnose ozone formation sensitivity at the Heshan Observatory in the Pearl River Delta (PRD) region from September to end October 2019. The profiles of tropospheric HCHO and NO2 were retrieved from MAX-DOAS measurements using an optimal estimation method. The retrieved surface HCHO and NO2 results were validated with 2,4-dinitrophenylhydrazine (DNPH) and Thermo 42i measurements, and the correlation coefficients (R) were 0.78 and 0.81, respectively. The retrieved tropospheric vertical column densities (VCDs) of HCHO and NO2 were compared with TROPOMI measurements, and the correlation coefficients (R) were 0.68 and 0.87, respectively. In addition, MAX-DOAS and LIDAR measurements were combined to diagnose a typical planetary boundary layer (PBL) ozone pollution episode from September 28 to October 10, 2019; this episode was analyzed using HCHO/NO2 ratio as an indicator and was found to be dominated by the VOC-sensitive regime. Moreover, the regime transition of ozone formation sensitivity was calculated using the surface HCHO/NO2 ratio and increased O3 from the MAX-DOAS and Thermo 49i measurements, with transition thresholds of 1.43 and 1.78, respectively. Based on this definition, the ozone formation sensitivity at Heshan Observatory varied from VOC-sensitive (< 0.2 km and > 0.8 km) to NOx-sensitive (0.3–0.7 km) to VOC-NOx-sensitive (0.2–0.3 km and 0.7–0.8 km). The results improve our understanding of ozone formation sensitivity in the PRD region.

Retrieval of tropospheric ozone profiles using ground-based MAX-DOAS

In recent years, surface ozone concentrations have increased in many cities in China. Ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) is a powerful technique for retrieving the profiles of tropospheric trace gases, such as NO2, SO2, and HCHO. However, since the difficulties in deducting the effects of stratospheric ozone, there are few studies on the retrieval of tropospheric ozone profiles using MAX-DOAS measurements. Here, we developed an accurate inversion method to retrieve tropospheric ozone concentrations during the PRIDE-GBA Campaign, wherein the ozone differential slant column densities (DSCDs) were retrieved in QDOAS software using the “time-interpolated zenith spectrum” as the reference spectrum. The tropospheric DSCDs (DSCDstrop) were then calculated by subtracting the simulated stratospheric DSCDs (DSCDsstr, simulated from the SCIATRAN model) from the DSCDs. Tropospheric ozone profiles were retrieved from the DSCDstrop using the optimal estimation method (OEM). The results showed that high values of tropospheric ozone were mainly distributed below 1 km, which is consistent with lidar measurements. In addition, the observed surface ozone concentrations were highly correlated with the in-situ measurements, with correlation coefficients (R) of 0.75 and 0.81, respectively. Combined with the retrieved NO2 and HCHO profiles using the MAX-DOAS measurements, we found that the planetary boundary layer ozone pollution of HeShan Observatory during the PRIDE-GBA Campaign are controlled by the NOx-limited regime. The results of this study indicate that the MAX-DOAS technique has the potential to retrieve tropospheric ozone profiles with high temporal and spatial resolution.

Impact Assessment of COVID-19 Lockdown on Vertical Distributions of NO2 and HCHO From MAX-DOAS Observations and Machine Learning Models.

Responses to the COVID‐19 pandemic led to major reductions on air pollutant emissions in modern history. To date, there has been no comprehensive assessment for the impact of lockdowns on the vertical distributions of nitrogen dioxide (NO2) and formaldehyde (HCHO). Based on profiles from 0 to 2 km retrieved by Multi‐AXis‐Differential Optical Absorption Spectroscopy observation and a large volume of real‐time data at a suburb site in Shanghai, China, four types of machine learning models were developed and compared, including multiple linear regression, support vector machine, bagged trees (BT), and artificial neural network. Ultimately BT model was employed to reproduce NO2 and HCHO profiles with the best performance. Predictions with different meteorological and surface pollution scenarios were conducted from 2017 to 2019, for assessing the corresponding impacts on the changes of NO2 and HCHO profiles during COVID‐19 lockdown. The simulations illustrate that the NO2 decreased in 2020 by 43.8%, 45.5%, and 44.6%, relative to 2017, 2018, and 2019, respectively. For HCHO, the lockdown‐induced situation presented the declines of 28.6%, 32.1%, and 10.9%, respectively. In the comparisons of vertical distributions, NO2 maintained decreasing at all altitudes, while HCHO decreased at low altitudes and increased at high altitudes. During COVID‐19 lockdown, the reduction of NO2 and HCHO from the variation of surface pollutants was dominated below 0.5 km, while the relevant meteorological factors played a more significant role above 0.5 km.

Temporal Variation of NO2 and HCHO Vertical Profiles Derived from MAX-DOAS Observation in Summer at a Rural Site of the North China Plain and Ozone Production in Relation to HCHO/NO2 Ratio

We performed a comprehensive and intensive field experiment including ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurement at Raoyang (115°44′ E, 38°14′ N; 20 m altitude) in summer (13 June–20 August) 2014. The NO2 and HCHO profiles retrieved by MAX-DOAS take on different vertical distribution shapes, with the former declining with the increasing altitude and the latter having an elevated layer. The average levels of vertical column densities (VCDs) and near-surface volume mixing ratios (VMRs) were 1.02 ± 0.51 × 1016 molec·cm−2 and 3.23 ± 2.70 ppb for NO2 and 2.32 ± 0.56 × 1016 molec·cm−2 and 5.62 ± 2.11 ppb for HCHO, respectively. The NO2 and HCHO levels are closely connected with meteorological conditions, with the larger NO2 VCDs being associated with lower temperature, higher relative humidity (RH) and lower planetary boundary layer height (PBLH). With respect to the diurnal variations of vertical distribution, the NO2 in the residual layer gradually disappeared from 1.2 km height to the surface during the period of 7:00–11:00 Beijing time (BJ), and the near-surface NO2 had larger VMRs in the early morning and evening than in the later morning and afternoon. An elevated HCHO layer was observed to occur persistently with the lifted layer height rising from ~0.5 km to ~1.0 km before 10:00 BJ; the near-surface HCHO VMRs gradually increased and peaked around 10:00 BJ. The ratios of HCHO to NO2 (RHCHO-NO2) were generally larger than two in the boundary layer from 11:00 BJ until 19:00 BJ, the time period when ozone photochemistry was most active. Thus, ozone (O3) production was mainly in the NOx-limited regime during the observation campaign, which was closely related to relatively high temperatures and low RH. The O3 production regimes also changed with the wind’s direction. These results are significant to reveal the formation mechanism of O3 pollution and develop strategies for controlling the O3 photochemical pollution over the North China Plain.

Inferring vertical variability and diurnal evolution of O3 formation sensitivity based on the vertical distribution of summertime HCHO and NO2 in Guangzhou, China

The vertical distributions of formaldehyde (HCHO) and nitrogen dioxide (NO2) and their indicative roles in ozone (O3) sensitivity are important for designing O3 mitigation strategies. Using hyperspectral remote sensing observations, tropospheric vertical profiles of HCHO, NO2, and aerosol extinction were investigated in Guangzhou, China from July to September 2019. On both O3 non-exceedance and polluted days, the HCHO and aerosol vertical profiles exhibited similar Gaussian shapes, but the NO2 profile exhibited an exponential decreasing shape. HCHO and aerosol were especially sensitive to O3 pollution, with higher values generally occurring at approximately noon and late afternoon at higher altitudes. We attempted to study the diurnal evolution of O3 sensitivity at different altitudes based on the HCHO to NO2 ratio (FNR) vertical profile. The FNR thresholds marking the transition regime (2.5 < FNR < 4.0) were derived from the relationship between the increase in O3 (∆O3) and FNR. Our results showed that O3 sensitivity tends to be VOC-limited both at lower (below approximately 0.4 km) and higher (above approximately 1.8 km) altitudes throughout the daytime. In the middle altitudes, the photochemical formation of O3 was mainly in the transition/NOx-limited regime in the morning and afternoon but in the VOC-limited regime at noontime. The relationship between TROPOMI column FNR and near-surface O3 sensitivity was further investigated. Compared with the MAX-DOAS near-surface FNR, slightly higher values of column FNR would increase the number of days classified as transition regimes, which was mainly caused by the inhomogeneous vertical distribution of HCHO and NO2 in the lower troposphere. This study provides an improved understanding of vertical variability and diurnal evolution of O3 formation sensitivity.

Vertical distribution and temporal evolution of formaldehyde and glyoxal derived from MAX-DOAS observations: The indicative role of VOC sources

Formaldehyde (HCHO) and glyoxal (CHOCHO) are important oxidization intermediates of most volatile organic compounds (VOCs), but their vertical evolution in urban areas is not well understood. Vertical profiles of HCHO, CHOCHO, and nitrogen dioxide (NO2) were retrieved from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations in Hefei, China. HCHO and CHOCHO vertical profiles prefer to occur at higher altitudes compared to NO2, which might be caused by the photochemistry-oxidation of longer-lived VOCs at higher altitudes. Monthly means of HCHO concentrations were higher in summer, while enhanced amounts of NO2 were mainly observed in winter. CHOCHO exhibited a hump-like seasonal variation, with higher monthly-averaged values not only occurred in warm months (July-August) but also in cold months (November-December). Peak values mainly occurred during noon for HCHO but emerged in the morning for CHOCHO and NO2, suggesting that HCHO is stronger link to photochemistry than CHOCHO. We further use the glyoxal to formaldehyde ratio (GFR) to investigate the VOC sources at different altitudes. The lowest GFR value is almost found in the altitude from 0.2 to 0.4 km, and then rises rapidly as the altitude increases. The GFR results indicate that the largest contributor of the precursor VOC is biogenic VOCs at lower altitudes, while at higher altitudes is anthropogenic VOCs. Our findings provide a lot more insight into VOC sources at vertical direction, but more verification is recommended to be done in the future.

Long-term MAX-DOAS measurements of NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, HCHO, and aerosols and evaluation of corresponding satellite data products over Mohali in the Indo-Gangetic Plain

Abstract. We present comprehensive long-term ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of aerosols, nitrogen dioxide (NO2), and formaldehyde (HCHO) from Mohali (30.667∘ N, 76.739∘ E; ∼310 m above mean sea level), located in the densely populated Indo-Gangetic Plain (IGP) of India. We investigate the temporal variation in tropospheric columns, surface volume mixing ratio (VMR), and vertical profiles of aerosols, NO2, and HCHO and identify factors driving their ambient levels and distributions for the period from January 2013 to June 2017. We observed mean aerosol optical depth (AOD) at 360 nm, tropospheric NO2 vertical column density (VCD), and tropospheric HCHO VCD for the measurement period to be 0.63 ± 0.51, (6.7 ± 4.1) × 1015, and (12.1 ± 7.5) × 1015 molecules cm−2, respectively. Concerning the tropospheric NO2 VCDs, Mohali was found to be less polluted than urban and suburban locations of China and western countries, but comparable HCHO VCDs were observed. For the more than 4 years of measurements during which the region around the measurement location underwent significant urban development, we did not observe obvious annual trends in AOD, NO2, and HCHO. High tropospheric NO2 VCDs were observed in periods with enhanced biomass and biofuel combustion (e.g. agricultural residue burning and domestic burning for heating). Highest tropospheric HCHO VCDs were observed in agricultural residue burning periods with favourable meteorological conditions for photochemical formation, which in previous studies have shown an implication for high ambient ozone also over the IGP. Highest AOD is observed in the monsoon season, indicating possible hygroscopic growth of the aerosol particles. Most of the NO2 is located close to the surface, whereas significant HCHO is present at higher altitudes up to 600 m during summer indicating active photochemistry at high altitudes. The vertical distribution of aerosol, NO2, and HCHO follows the change in boundary layer height (BLH), from the ERA5 dataset of European Centre for Medium-Range Weather Forecasts, between summer and winter. However, deep convection during the monsoon transports the pollutants at high altitudes similar to summer despite a shallow ERA5 BLH. Strong gradients in the vertical profiles of HCHO are observed during the months when primary anthropogenic sources dominate the formaldehyde production. High-resolution MODIS AOD measurements correlate well but were systematically higher than MAX-DOAS AODs. The ground-based MAX-DOAS measurements were used to evaluate three NO2 data products and two HCHO data products of the Ozone Monitoring Instrument (OMI) for the first time over India and the IGP. NO2 VCDs from OMI correlate reasonably with MAX-DOAS VCDs but are lower by ∼30 %–50 % due to the difference in vertical sensitivities and the rather large OMI footprint. OMI HCHO VCDs exceed the MAX-DOAS VCDs by up to 30 %. We show that there is significant scope for improvement in the a priori vertical profiles of trace gases, which are used in OMI retrievals. The difference in vertical representativeness was found to be crucial for the observed biases in NO2 and HCHO surface VMR intercomparisons. Using the ratio of NO2 and HCHO VCDs measured from MAX-DOAS, we have found that the peak daytime ozone production regime is sensitive to both NOx and VOCs in winter but strongly sensitive to NOx in other seasons.

Monitoring formaldehyde in a shock tube with a fast dual-comb spectrometer operating in the spectral range of 1740\u20131790\xa0cm\u20131

A dual-frequency-comb spectrometer based on two quantum-cascade lasers is applied to kinetics studies of formaldehyde (HCHO) in a shock tube. Multispectral absorption measurements are carried out in a broad spectral range of 1740–1790 cm–1 at temperatures of 800–1500 K and pressures of 2–3 bar. The formation of HCHO from thermal decomposition of 1,3,5-trioxane (C3H6O3, 0.9% diluted in argon) and the subsequent oxidation of formaldehyde is monitored with a time resolution of 4 µs. The rate coefficient of the decomposition of C3H6O3 (i.e., HCHO formation) is found to be k1 = 6.0 × 1015 exp(− 205.58 kJ mol−1/RT) s–1. For the oxidation studies, mixtures of 0.36% C3H6O3 and 1% O2 in argon are used. The information of all laser lines, along with the consideration of individual signal variance of each line, is utilized for kinetic and spectral analysis. The experimental kinetic profiles of HCHO are compared with simulations based on the mechanisms of Zhou et al. (Combust Flame, 197:423–438, 2018) and Cai and Pitsch (Combust Flame, 162:1623–1637, 2015).

Investigation of HCHO Catalytic Oxidation over Platinum using Planar Laser-Induced Fluorescence

Planar laser-induced fluorescence is employed as noninvasive in situ technique to investigate the oxidation of formaldehyde over platinum. Two-dimensional absolute HCHO concentration distributions over a catalyst-coated plate are visualized in a parallel wall channel. The experimental results are compared with corresponding numerical simulations using ANSYS-Fluent with a detailed surface reaction mechanism. The influence of temperature, Pt-loading and mass flow rate on HCHO profiles are investigated experimentally and numerically in steady state. In the temperature range of 373 – 673 K, the HCHO distribution measured is well predicted by the model. A slow transition from a kinetically controlled regime to a mass transfer limited regime can be observed at 573 K in this study. It is found that the local HCHO concentration in the catalytic channel is governed by a combined effect of chemical kinetics, diffusive mass transfer, and flow field.

Quantitative measurements of formaldehyde in the low-temperature oxidation of iso-octane using mid-infrared absorption spectroscopy

Time-resolved quantitative measurements of formaldehyde (HCHO) in the low-temperature oxidation of iso-octane using a rapid compression machine have been performed with mid-infrared laser absorption spectroscopy. Due to the weak interference of the broadband absorption of iso-octane, a two-color detection scheme was applied to HCHO detection. The cross-sections of HCHO and iso-octane in two colors were measured using the rapid compression machine in the temperature range of 450–737 K and pressure range of 100–700 kPa. The time-resolved quantitative HCHO profiles in the low-temperature oxidation of iso-octane at 0.77 MPa, 645 K, and an equivalence ratio of 1.0 were successfully obtained. The calculated HCHO profiles using the latest chemical kinetic model of iso-octane show the same tendency as the experimental profiles.

Validation of OMI HCHO Products Using MAX-DOAS observations from 2010 to 2016 in Xianghe, Beijing: Investigation of the Effects of Aerosols on Satellite Products

Formaldehyde (HCHO) is one of the most abundant hydrocarbons in the atmosphere. Its absorption features in the 320–360 nm range allow its concentration in the atmosphere to be retrieved from space. There are two versions of HCHO datasets derived from the Ozone Monitoring Instrument (OMI)—one provided by the Royal Belgian Institute for Space Aeronomy (BIRA-IASB) and one provided by the National Aeronautics and Space Administration (NASA)—referred to as OMI-BIRA and OMI-NASA, respectively. We conducted daily comparisons of OMI-BIRA and multi-axis differential optical absorption spectrometry (MAX-DOAS), OMI-NASA and MAX-DOAS, and OMI-BIRA and OMI-NASA and monthly comparisons of OMI-BIRA and MAX-DOAS and OMI-NASA and MAX-DOAS. Daily comparisons showed a strong impact of effective cloud fraction (eCF), and correlations were better for eCF &lt; 0.1 than for eCF &lt; 0.3. By contrast, the monthly and multi-year monthly mean values yielded correlations of R2 = 0.60 and R2 = 0.95, respectively, for OMI-BIRA and MAX-DOAS, and R2 = 0.45 and R2 = 0.78 for OMI-NASA and MAX-DOAS, respectively. Therefore, use of the monthly mean HCHO datasets is strongly recommended. We conducted a sensitivity test for HCHO air mass factor (AMF) calculations with respect to the HCHO profile, the aerosol extinction coefficient (AEC), the HCHO profile–AEC combination, the aerosol optical depth (AOD), and the single scattering albedo (SSA) to explicitly account for the aerosol optical effects on the HCHO AMF. We found that the combination of AEC and HCHO profiles can account for 23–39% of the HCHO AMF variation. Furthermore, a high load of absorptive aerosols can exert a considerable effect (−53%) on the AMF. Finally, we used the HCHO monthly mean profiles from Goddard Earth Observing System coupled to Chemistry (GEOS-Chem), seasonal mean AECs from Cloud-Aerosol LIDAR with Orthogonal Polarization (CALIOP) and monthly climatologies of AOD and SSA from the OMAERUV (OMI level-2 near UV aerosol data product) dataset at Xianghe station to determine the aerosol correction. The results reveal that aerosols can account for +6.37% to +20.7% of the HCHO monthly change. However, the changes are greatest in winter and are weaker in summer and autumn, indicating that the aerosol correction is more applicable under high-AAOD conditions and that there may be other reasons for the significant underestimation between satellite and MAX-DOAS observations.

Observations of ozone vertical profiles and corresponding precursors in the low troposphere in Beijing, China

A comprehensive investigation of ozone, its precursors as well as aerosols in the low troposphere was conducted over the University of Chinese Academy of Sciences site (abbreviated as UCAS site, a northern suburban site) in Beijing during the period of October 26 to November 6, 2014, with a focus on the comparison between polluted and clean conditions. The vertical profiles of ozone and aerosol extinction coefficients in the low troposphere were measured by differential absorption lidar, and the tropospheric vertical column densities (VCDs) as well as vertical profiles of HCHO and NO2 were measured by ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS). O3 in the boundary layer (0.3–1.0 km) had a positive gradient with height and presented a stratified structure at night on haze days, in contrast to a uniform distribution during clean episodes. The polluted conditions were characterized by higher levels of atmospheric pollutants (O3, aerosol, HCHO and NO2) and more dynamic variations with respect to clean periods. During lightly to moderately polluted periods, elevated concentrations of O3 within the boundary layer were observed with a maximum exceeding 60 ppbv. In haze days, the air masses from urban Beijing and southern Hebei industrial and urbanized areas could bring large amounts of precursors, enhancing O3 formation over the lidar site. The photochemical production of O3 within the boundary layer was controlled by a VOC-limited regime in haze days and turned into a mixed-VOC-NOx-limited regime on clean days. According to sensitivity analysis, when air masses came from southern polluted regions, the sensitivity of ozone production was dominated by VOC-limited regime. The reduction of VOC emissions from urban Beijing and Hebei industrial and urbanized areas would favor the mitigation of O3 pollution at UCAS site.

Investigations of the Diurnal Variation of Vertical HCHO Profiles Based on MAX-DOAS Measurements in Beijing: Comparisons with OMI Vertical Column Data

An investigation into the diurnal characteristics of vertical formaldehyde (HCHO) profiles was conducted based on multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements in Beijing during the CAREBEIJING campaign, covering a month-long period through August and September 2006. Vertical HCHO profiles were retrieved based on a combined differential optical absorption spectroscopy (DOAS) technique and an optimal estimation method (OEM). The HCHO volume-mixing ratio (VMR) was found to be highest in the layer from the surface up to an altitude of 1 km and to decrease with altitude above this layer. In all retrieved profiles, HCHO was not detected in the layer from 3–4 km. Over the diurnal cycle, the HCHO VMR values were generally highest at 15:00 local time (LT) and were lower in the morning and late afternoon. The mean HCHO VMRs were 6.17, 1.82, and 0.80 ppbv for the 0–1, 1–2, and 2–3-km layers, respectively, at 15:00 LT, whereas they were 3.54 (4.79), 1.06 (1.43), and 0.46 (0.63) ppbv for the 0–1, 1–2, and 2–3-km layers, respectively, at 09:00 (17:00) LT. The HCHO VMRs reached their highest values at 15:00 LT on August 19, which were 17.71, 5.20, and 2.31 ppbv for the 0–1, 1–2, and 2–3-km layers, respectively. This diurnal pattern implies that the photo-oxidation of volatile organic compounds (VOCs) was most active at 15:00 LT for several days during the campaign period. In a comparison of the derived HCHO VCDs with those obtained from the Ozone Monitoring Instrument (OMI) measurements, the HCHO vertical column density (VCD) values obtained from the OMI measurements tend to be smaller than those from the MAX-DOAS.

Retrievals of formaldehyde from ground-based FTIR and MAX-DOAS observations at the Jungfraujoch station and comparisons with GEOS-Chem and IMAGES model simulations

Abstract. As an ubiquitous product of the oxidation of many volatile organic compounds (VOCs), formaldehyde (HCHO) plays a key role as a short-lived and reactive intermediate in the atmospheric photo-oxidation pathways leading to the formation of tropospheric ozone and secondary organic aerosols. In this study, HCHO profiles have been successfully retrieved from ground-based Fourier transform infrared (FTIR) solar spectra and UV-visible Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) scans recorded during the July 2010–December 2012 time period at the Jungfraujoch station (Swiss Alps, 46.5° N, 8.0° E, 3580 m a.s.l.). Analysis of the retrieved products has revealed different vertical sensitivity between both remote sensing techniques. Furthermore, HCHO amounts simulated by two state-of-the-art chemical transport models (CTMs), GEOS-Chem and IMAGES v2, have been compared to FTIR total columns and MAX-DOAS 3.6–8 km partial columns, accounting for the respective vertical resolution of each ground-based instrument. Using the CTM outputs as the intermediate, FTIR and MAX-DOAS retrievals have shown consistent seasonal modulations of HCHO throughout the investigated period, characterized by summertime maximum and wintertime minimum. Such comparisons have also highlighted that FTIR and MAX-DOAS provide complementary products for the HCHO retrieval above the Jungfraujoch station. Finally, tests have revealed that the updated IR parameters from the HITRAN 2012 database have a cumulative effect and significantly decrease the retrieved HCHO columns with respect to the use of the HITRAN 2008 compilation.

Inversion of tropospheric profiles of aerosol extinction and HCHO and NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; mixing ratios from MAX-DOAS observations in Milano during the summer of 2003 and comparison with independent data sets

Abstract. We present aerosol and trace gas profiles derived from MAX-DOAS observations. Our inversion scheme is based on simple profile parameterisations used as input for an atmospheric radiative transfer model (forward model). From a least squares fit of the forward model to the MAX-DOAS measurements, two profile parameters are retrieved including integrated quantities (aerosol optical depth or trace gas vertical column density), and parameters describing the height and shape of the respective profiles. From these results, the aerosol extinction and trace gas mixing ratios can also be calculated. We apply the profile inversion to MAX-DOAS observations during a measurement campaign in Milano, Italy, September 2003, which allowed simultaneous observations from three telescopes (directed to north, west, south). Profile inversions for aerosols and trace gases were possible on 23 days. Especially in the middle of the campaign (17–20 September 2003), enhanced values of aerosol optical depth and NO2 and HCHO mixing ratios were found. The retrieved layer heights were typically similar for HCHO and aerosols. For NO2, lower layer heights were found, which increased during the day. The MAX-DOAS inversion results are compared to independent measurements: (1) aerosol optical depth measured at an AERONET station at Ispra; (2) near-surface NO2 and HCHO (formaldehyde) mixing ratios measured by long path DOAS and Hantzsch instruments at Bresso; (3) vertical profiles of HCHO and aerosols measured by an ultra light aircraft. Depending on the viewing direction, the aerosol optical depths from MAX-DOAS are either smaller or larger than those from AERONET observations. Similar comparison results are found for the MAX-DOAS NO2 mixing ratios versus long path DOAS measurements. In contrast, the MAX-DOAS HCHO mixing ratios are generally higher than those from long path DOAS or Hantzsch instruments. The comparison of the HCHO and aerosol profiles from the aircraft showed reasonable agreement with the respective MAX-DOAS layer heights. From the comparison of the results for the different telescopes, it was possible to investigate the internal consistency of the MAX-DOAS observations. As part of our study, a cloud classification algorithm was developed (based on the MAX-DOAS zenith viewing directions), and the effects of clouds on the profile inversion were investigated. Different effects of clouds on aerosols and trace gas retrievals were found: while the aerosol optical depth is systematically underestimated and the HCHO mixing ratio is systematically overestimated under cloudy conditions, the NO2 mixing ratios are only slightly affected. These findings are in basic agreement with radiative transfer simulations.

Formaldehyde columns from the Ozone Monitoring Instrument: Urban versus background levels and evaluation using aircraft data and a global model.

[1] We combine aircraft measurements (Second Texas Air Quality Study, Megacity Initiative: Local and Global Research Observations, Intercontinental Chemical Transport Experiment: Phase B) over the United States, Mexico, and the Pacific with a 3-D model (GEOS-Chem) to evaluate formaldehyde column (ΩHCHO) retrievals from the Ozone Monitoring Instrument (OMI) and assess the information they provide on HCHO across local to regional scales and urban to background regimes. OMI ΩHCHO correlates well with columns derived from aircraft measurements and GEOS-Chem (R = 0.80). For the full data ensemble, OMI's mean bias is -3% relative to aircraft-derived ΩHCHO (-17% where ΩHCHO > 5 × 1015 molecules cm-2) and -8% relative to GEOS-Chem, within expected uncertainty for the retrieval. Some negative bias is expected for the satellite and model, given the plume sampling of many flights and averaging over the satellite and model footprints. Major axis regression for OMI versus aircraft and model columns yields slopes (95% confidence intervals) of 0.80 (0.62-1.03) and 0.98 (0.73-1.35), respectively, with no significant intercept. Aircraft measurements indicate that the normalized vertical HCHO distribution, required by the satellite retrieval, is well captured by GEOS-Chem, except near Mexico City. Using measured HCHO profiles in the retrieval algorithm does not improve satellite-aircraft agreement, suggesting that use of a global model to specify shape factors does not substantially degrade retrievals over polluted areas. While the OMI measurements show that biogenic volatile organic compounds dominate intra-annual and regional ΩHCHO variability across the United States, smaller anthropogenic ΩHCHO gradients are detectable at finer spatial scales (∼20-200 km) near many urban areas.

Summertime Ambient Formaldehyde in Five U.S. Metropolitan Areas: Nashville, Atlanta, Houston, Philadelphia, and Tampa

First, we briefly review the atmospheric chemistry and previous intercomparison measurements for HCHO, with special reference to the diffusion scrubber Hantzsch reaction based fluorescence instrument used in the field studies reported herein. Then we discuss summertime HCHO levels in five major U.S. cities measured over 1999-2002, primarily from ground-based measurements. Land-sea breeze circulations play a major role in observed concentrations in coastal cities. Very high HCHO peak mixing ratios were observed in Houston (>47 ppb) where the overall median mixing ratio was 3.3 ppb; the corresponding values in Atlanta were approximately >18 and 7.9 ppb, respectively. The peak and median mixing ratios (9.3 and 2.3 ppb) were the lowest for Tampa, where the land-sea breeze also played an important role. In several cities, replicate HCHO measurements were made by direct spectroscopic instruments; the instruments were located kilometers from each other and addressed very different heights (e.g., 106 vs 10 m). Even under these conditions, there was remarkable qualitative and often quantitative agreement between the different instruments, when they were all sampling the same air mass within a short period of each other. Local chemistry dominates how HCHO is formed and dissipated. The high concentrations in Houston resulted from emissions near the ship channel; the same formaldehyde plume was measured at two sites and clearly ranged over tens of kilometers. Local micrometeorology is another factor. HCHO patterns measured at a high-rise site in downtown Nashville were very much in synchrony with other ground sites 12 km away until July 4 celebrations whence HCHO concentrations at the downtown site remained elevated for several days and nights. The formation and dissipation of HCHO in the different cities are discussed in terms of other concurrently measured species and meteorological vectors. The vertical profiles of HCHO in and around Tampa under several different atmospheric conditions are presented. The extensive data set represented in this paper underscores that urban HCHO measurements can now be made easily; the agreement between disparate instruments (that are independently calibrated or rely on the absolute absorption cross section) further indicates that such measurements can be done reliably and accurately for this very important atmospheric species. The data set presented here can be used as a benchmark for future measurements if the use of formaldehyde precursors such as methanol or methyl tert-butyl ether (MTBE) as oxygenated fuel additives increases in the future.

Evaluation of GOME satellite measurements of tropospheric NO2 and HCHO using regional data from aircraft campaigns in the southeastern United States

We compare tropospheric measurements of nitrogen dioxide (NO2) and formaldehyde (HCHO) from the Global Ozone Monitoring Experiment (GOME) satellite instrument with in situ measurements over eastern Texas and the southeast United States. On average, the GOME and in situ measurements of tropospheric NO2 and HCHO columns are consistent despite pronounced sampling differences. The geometric mean in situ to GOME ratios over the campaign are 1.08 for NO2 and 0.84 for HCHO, with corresponding geometric standard deviations of 1.27 and 1.38. The correlation of the observed column spatial variability between the two NO2 measurement sets is encouraging before (r2 = 0.54, n = 18) and after (r2 = 0.67, n = 18) correcting for a sampling bias. Mean relative vertical profiles of HCHO and NO2 calculated with a global three‐dimensional model (GEOS‐CHEM) and used in the GOME retrieval are highly consistent with in situ measurements; differences would affect the retrieved NO2 and HCHO columns by a few percent. GOME HCHO columns over eastern Texas include contributions from anthropogenic volatile organic compound (VOC) emissions but are dominated by biogenic VOC emissions at the regional scale in August–September when HCHO columns are within 20% of those over the southeastern United States. In situ measurements show that during summer the lowest 1500 m (the lower mixed layer) contains 75% of the tropospheric NO2 column over Houston and Nashville, and 60% of the HCHO column over Houston. Future validation of space‐based measurements of tropospheric NO2 and HCHO columns over polluted regions should include coincident in situ measurements that span the entire satellite footprint, especially in the heterogeneous mixed layer.

HCHO in Antarctic snow: Preservation in ice cores and air‐snow exchange

Formaldehyde (HCHO) measurements in snow and shallow firn at three Antarctic sites gave concentrations around 6 ppbw in surface snow and 1 ppbw and lower below 1–2 m depth. The variable concentration patterns in shallow snow and firn result from temperature‐dependent uptake and release of HCHO in response to annual temperature cycles. Deeper concentrations are constant with depth, and apparently reflect average atmospheric concentrations. This implies that after accounting for differences in temperature and accumulation, changes in ice‐core HCHO concentrations with depth should linearly reflect changes in atmospheric HCHO over time. Modeling of observed HCHO profiles in the snow implies that degassing of HCHO from surface snow likely contributes a significant fraction of the HCHO found in the boundary layer in spring and summer at all three sites. Based on modeling of air‐snow exchange and atmospheric photochemistry, summer HCHO levels are estimated to be on the order of 100–200 pptv.

Performance of a 2,4-DNPH coated annular denuder/HPLC system for formaldehyde monitoring in air

The performance of annular denuders coated with 2,4-dinitrophenylhydrazine for collection of atmospheric HCHO has been evaluated by HPLC/UV analysis of samples coming from laboratory tests and field experiments. A number of parameters, such as collection efficiency at varying air humidity, detection limit, operative capacity and temporal self-consistency have been investigated to optimize the denuder behaviour under different weather conditions and to obtain short-term concentration profiles of HCHO. Deviations between measurements made simultaneously by the DNPH denuder method and differential optical absorption spectrometry (DOAS) have been found to average approximately 30% in the 0–5 ppb HCHO concentration range.