HCHO Mixing Ratios Research Articles

Evaluating CHASER V4.0 global formaldehyde (HCHO) simulations using satellite, aircraft, and ground-based remote-sensing observations

Abstract. Formaldehyde (HCHO), a precursor to tropospheric ozone, is an important tracer of volatile organic compounds (VOCs) in the atmosphere. Two years (2019–2020) of HCHO simulations obtained from the global chemistry transport model CHASER at a horizontal resolution of 2.8° × 2.8° have been evaluated using the Tropospheric Monitoring Instrument (TROPOMI) and multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations. In situ measurements from the Atmospheric Tomography Mission (ATom) in 2018 were used to evaluate the HCHO simulations for 2018. CHASER reproduced the TROPOMI-observed global HCHO spatial distribution with a spatial correlation (r) of 0.93 and a negative bias of 7 %. The model showed a good capability to reproduce the observed magnitude of the HCHO seasonality in different regions, including the background conditions. The discrepancies between the model and satellite in the Asian regions were related mainly to the underestimated and missing anthropogenic emission inventories. The maximum difference between two HCHO simulations based on two different nitrogen oxide (NOx) emission inventories was 20 %. TROPOMI's finer spatial resolution than that of the Ozone Monitoring Instrument (OMI) sensor reduced the global model–satellite root-mean-square error (RMSE) by 20 %. The OMI- and TROPOMI-observed seasonal variations in HCHO abundances were consistent. The simulated seasonality showed better agreement with TROPOMI in most regions. The simulated HCHO and isoprene profiles correlated strongly (R=0.81) with the ATom observations. However, CHASER overestimated HCHO mixing ratios over dense vegetation areas in South America and the remote Pacific region (background condition), mainly within the planetary boundary layer (< 2 km). The simulated seasonal variations in the HCHO columns showed good agreement (R>0.70) with the MAX-DOAS observations and agreed within the 1σ standard deviation of the observed values. However, the temporal correlation (R∼0.40) was moderate on a daily scale. CHASER underestimated the HCHO levels at all sites, and the peak occurrences in the observed and simulated HCHO seasonality differed. The coarseness of the model's resolution could potentially lead to such discrepancies. Sensitivity studies showed that anthropogenic emissions were the highest contributor (up to ∼ 35 %) to the wintertime regional HCHO levels.

Leaf-Level Bidirectional Exchange of Formaldehyde on Deciduous and Evergreen Tree Saplings.

Gas-phase formaldehyde (HCHO) is formed in high yield from the oxidation of many volatile organic compounds (VOCs) and is commonly used as a constraint when testing the performance of VOC oxidation mechanisms in models. However, prior to using HCHO as a model constraint for VOC oxidation in forested regions, it is essential to have a thorough understanding of its foliar exchange. Therefore, a controlled laboratory setup was designed to measure the emission and dry deposition of HCHO at the leaf-level to red oak (Quercus rubra) and Leyland cypress (Cupressus × leylandii) tree saplings. The results show that HCHO has a compensation point (CP) that rises exponentially with temperature (22-35 °C) with a mean range of 0.3-0.9 ppbv. The HCHO CP results are also found to be independent of the studied tree species and 40-70% relative humidity. Given that HCHO mixing ratios in forests during the daytime are usually greater than 1 ppbv, the magnitude of the CP suggests that trees generally act as a net sink of HCHO. Additionally, the results show that HCHO foliar exchange is stomatally controlled and better matches a reactivity factor (f0) of 0 as opposed to 1 in conventional dry deposition parametrizations. At 30 °C, daytime HCHO dry deposition fluxes are reduced by upward of 50% when using f0 = 0 and a nonzero HCHO CP, although deposition remains the dominant canopy sink of HCHO. A reduced deposition sink also implies the increased importance of the gas-phase photolysis of HCHO as a source of HO2.

The influence of vegetation drought stress on formaldehyde and ozone distributions over a central European city

To estimate the effect of vegetation stress and changes in biogenic volatile organic compound (BVOC) emissions on urban ozone (O3) levels we perform a systematic, observation-based analysis of the relationship between formaldehyde (HCHO) mixing ratios, meteorological parameters, measurement-based drought indicators and O3 over the central European city of Vienna, Austria. In addition, numerical models SURface EXternalisée (SURFEX), Model of Emissions of Gases and Aerosols from Nature (MEGAN) Vers.2.1 and 3 and MOdèle de Chimie A Grande Echelle (MOCAGE) are combined to estimate the soil moisture, the spatial distribution and drought response of isoprene emissions, and the resulting distribution of HCHO in the atmosphere. To analyse the effect of drought during spring and summer we contrast observations during dry and reference years. Our results show that the observed HCHO can be explained using the simulated isoprene emissions as well as observed and simulated vegetation drought responses. HCHO mixing ratios differ strongly between dry and reference seasons. Spring-time precipitation deficits facilitate reduced HCHO mixing ratios due to delayed and weakened plant growth. In consequence also O3 burdens are lowered due to reduced BVOC precursor emissions. These reductions occur despite radiation levels being higher than during the reference year, illustrating the strong potential of spring-time BVOC emissions to modulate urban O3 burdens. Conversely, during summer elevated O3 levels occur during local drought conditions. These are driven by advected isoprene originating from nearby forest areas, which are not affected by drought. Our results regarding elevated summer-time O3 burdens under vegetation heat and drought stress are in good agreement with previous work.

Diagnosis of Ozone Formation Sensitivities in Different Height Layers via MAX‐DOAS Observations in Guangzhou

AbstractDiagnosing the vertical distributions of ozone formation sensitivities within the boundary layers is the prerequisite for formulating proper ozone control strategies. From 1 January 2020, to 20 August 2021, a multi‐function MAX‐DOAS instrument was set up in Guangzhou to detect the NO2 and HCHO vertical profiles. The ozone formation sensitivities in different height layers were diagnosed using the FNRsec, which was defined as the ratio of secondary HCHO to NO2 VMRs (HCHOsec/NO2). The secondary sources in ambient HCHO participate in the photochemical reactions directly, and the FNRsec can indicate the ozone formation sensitivities more accurately. Therefore, the secondary source was separated from ambient HCHO via a multi‐linear regression method, and its relative contribution was approximately 66.9 ± 6.3%. The sensitivity thresholds of ozone formation were determined by the slope of the linear regression analysis for O3 versus the normalized secondary HCHO or NO2 mixing ratios for different FNRsec ranges, which were 0.22 and 0.36. For the ground layer, the VOC‐limited, transitional, and NOx‐limited regimes accounted for 40.66%, 32.42%, and 26.92%, respectively. Diurnally, the ground layer was usually in the VOC‐limited regime in morning, but in the transitional regime in noon and afternoon. Vertically, the ozone formation sensitivity changed with altitude from VOC‐limited (0.02–0.22 km) to transitional (0.22–0.42 km) to NOx‐limited (0.42–2.02 km). These findings can help formulate proper ozone control strategies in time according to the varying local conditions.

Comparison of formaldehyde measurements by Hantzsch, CRDS and DOAS in the SAPHIR chamber

Abstract. Three instruments that use different techniques to measure gaseous formaldehyde (HCHO) concentrations were compared in experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich. One instrument (AL4021, Aero-Laser GmbH) detects HCHO using the wet-chemical Hantzsch reaction (for efficient gas-phase stripping), chemical conversion and fluorescence measurement. An internal HCHO permeation source allows for daily calibrations. This instrument was characterized by sulfuric acid titration (overall accuracy 8.6 %) and yields measurements with a time resolution of 90 s and a limit of detection (3σ) of 0.3 ppbv. In addition, a new commercial instrument that makes use of cavity ring-down spectroscopy (CRDS) determined the concentrations of HCHO, water vapour, and methane (G2307, Picarro, Inc.). Its limit of detection (3σ) is specified as 0.3 ppbv for an integration time of 300 s, and its accuracy is limited by the drift of the zero signal (manufacturer specification 1.5 ppbv). A custom-built high-resolution laser differential optical absorption spectroscopy (DOAS) instrument provided HCHO measurements with a limit of detection (3σ) of 0.9 ppbv and an accuracy of 7 %​​​​​​​ using an optical multiple reflection cell. The measurements were conducted from June to December 2019 in experiments in which either ambient air flowed through the chamber or the photochemical degradation of organic compounds in synthetic air was investigated. Measured HCHO concentrations were up to 8 ppbv. Various mixtures of organic compounds, water vapour, nitrogen oxides and ozone were present in these experiments. Results demonstrate the need to correct the baseline in measurements performed by the Hantzsch instrument to compensate for drifting background signals. Corrections were equivalent to HCHO mixing ratios in the range of 0.5–1.5 ppbv. The baseline of the CRDS instrument showed a linear dependence on the water vapour mixing ratio with a slope of (-11.20±1.60) ppbv %−1 below and (-0.72±0.08) ppbv %−1 above a water vapour mixing ratio of 0.2 %. In addition, the intercepts of these linear relationships drifted within the specification of the instrument (1.5 ppbv) over time but appeared to be equal for all water mixing ratios. Regular zero measurements are needed to account for the changes in the instrument zero. After correcting for the baselines of measurements by the Hantzsch and the CRDS instruments, linear regression analysis of measurements from all three instruments in experiments with ambient air indicated good agreement, with slopes of between 0.98 and 1.08 and negligible intercepts (linear correlation coefficients R2>0.96). The new small CRDS instrument measures HCHO with good precision and is accurate if the instrument zero is taken into account. Therefore, it can provide measurements with similar accuracy to the DOAS instrument but with slightly reduced precision compared to the Hantzsch instrument.

Atmospheric formaldehyde, glyoxal and their relations to ozone pollution under low- and high-NOx regimes in summertime Shanghai, China

With the increasing concerns on summertime atmospheric photochemical pollution, the diagnosis and prevention of ozone pollution have been paid close attention. Both formaldehyde (HCHO) and glyoxal (CHOCHO) are ubiquitous oxidation intermediates of volatile organic compounds (VOCs). The ratio of glyoxal to formaldehyde (RGF) is used as a metric for VOCs emission sources. In this study, the mixing ratios of HCHO and CHOCHO have been measured by the active differential optical absorption spectroscopy (DOAS) method in the urban area of Shanghai during summertime in 2018, as well as other trace gases. The average levels of HCHO and CHOCHO are 3.31 ± 1.43 ppbv and 0.164 ± 0.073 ppbv, respectively. The similar diurnal patterns and high correlation between HCHO, CHOCHO and ozone levels implied that daytime photochemical processes are the dominant formation pathway for these trace gases. We find that with increased NOx levels, HCHO shows higher ozone formation potential relative to glyoxal. The RGF ratio increases with temperature and decreases with NO2 levels. By investigating the coupling of typical VOCs species such as acetylene, toluene and isoprene with HCHO and CHOCHO, RGF is found to be strongly impacted by the ambient VOCs profiles, suggesting that RGF should be used with caution when linking it to a given VOC precursor source. Finally, the RGF variations with ozone pollution episodes and weather processes are also discussed.

Effect of Boundary Layer Evolution on Nitrogen Dioxide (NO2) and Formaldehyde (HCHO) Concentrations at a High-altitude Observatory in Western India

ABSTRACT Nitrogen dioxide (NO2) and formaldehyde (HCHO) are some of the most important trace gases in the atmosphere, acting as precursors for ozone formation and as pollutants at high concentrations. Although several observations of these species have been reported in the boundary layer, observations at high altitude sites are limited, especially in India. This study reports observations of NO2 and HCHO using the Multi AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) technique at the High Altitude Cloud Physics Laboratory (HACPL), Mahabaleshwar in the rural Western Ghats region of India. Measurements were conducted during the pre-monsoon season between 25th April and 30th May 2018. The average NO2 mixing ratio was 0.19 ± 0.06 ppb (range: 0.03 ppb to 0.69 ppb). Typically, NO2 mixing ratios were found to increase from early in morning and reached a maximum in the afternoon, contrary to an expected diurnal profile dominated by photochemistry. The average HCHO mixing ratio was 1.6 ± 0.61 ppb (range: 0.16 ppb–4.5 ppb). HCHO mixing ratios also showed an increase from early in the morning and reach a maximum at ~3 pm in the afternoon after which a decrease was observed, peaking much later than expected from a photochemistry dominated profile. Using observations of the boundary layer height, back trajectories and the known photochemistry, we conclude that the observed diurnal variation in these two species is dominated by the mixing of emissions from the base of the mountain, resulting from the evolution of the boundary layer at the HACPL site.

MAX-DOAS measurements of NO<sub>2</sub>, SO<sub>2</sub>, HCHO, and BrO at the Mt. Waliguan WMO GAW global baseline station in the Tibetan Plateau

Abstract. Mt. Waliguan Observatory (WLG) is a World Meteorological Organization (WMO) Global Atmosphere Watch (GAW) global baseline station in China. WLG is located at the northeastern part of the Tibetan Plateau (36∘17′ N, 100∘54′ E, 3816 m a.s.l.) and is representative of the pristine atmosphere over the Eurasian continent. We made long-term ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements at WLG during the period 2012–2015. In this study, we retrieve the differential slant column densities (dSCDs) and estimate the tropospheric background mixing ratios of different trace gases, including NO2, SO2, HCHO, and BrO, using the measured spectra at WLG. Averaging of 10 original spectra is found to be an “optimum option” for reducing both the statistical error of the spectral retrieval and systematic errors in the analysis. The dSCDs of NO2, SO2, HCHO, and BrO under clear-sky and low-aerosol-load conditions are extracted from measured spectra at different elevation angles at WLG. By performing radiative transfer simulations with the model TRACY-2, we establish approximate relationships between the trace gas dSCDs at 1∘ elevation angle and the corresponding average tropospheric background volume mixing ratios. Mixing ratios of these trace gases in the lower troposphere over WLG are estimated to be in a range of about 7 ppt (January) to 100 ppt (May) for NO2, below 0.5 ppb for SO2, between 0.4 and 0.9 ppb for HCHO, and lower than 0.3 ppt for BrO. The chemical box model simulations constrained by the NO2 concentration from our MAX-DOAS measurements show that there is a little net ozone loss (−0.8 ppb d−1) for the free-tropospheric conditions and a little net ozone production (0.3 ppb d−1) for the boundary layer conditions over WLG during summertime. Our study provides valuable information and data sets for further investigating tropospheric chemistry in the background atmosphere and its links to anthropogenic activities.

Spatial variation of sources and photochemistry of formaldehyde in Wuhan, Central China

In August 2016, ambient formaldehyde (HCHO) and related parameters were measured simultaneously at a suburban site (Wujiashan, WJS), an urban site (Ziyang, ZY) and a roadside site (Hankou, HK) in Wuhan, Central China. The mixing ratios of HCHO at WJS (2.1 ± 0.2 ppbv) were comparable (p > 0.05) to those at ZY (2.2 ± 0.4 ppbv) and lower (p < 0.01) than those at HK (3.4 ± 0.5 ppbv). Secondary formation made the greatest contributions to ambient HCHO at WJS (61.9 ± 5.9%) and ZY (69.3 ± 7.3%), while vehicle exhaust (i.e., diesel and CNG exhaust, gasoline exhaust) (47.2 ± 10.4%) was the dominant HCHO source at HK. Vehicle exhaust was also the dominant primary source of HCHO at WJS and ZY, accounting for 16.0 ± 4.0%, and 21.9 ± 8.0%, respectively. Biogenic emissions made a non-negligible contribution at suburban site WJS (9.8 ± 3.2%). The precursors of the secondary HCHO were investigated using a photochemical box model. Alkenes and aromatics were found to be the most important contributors to secondary HCHO. The impact of observed HCHO on the production of hydroperoxy radical (HO2) and ozone (O3) were also assessed. The photochemical reactions of HCHO (i.e., the photolysis and OH-initiated oxidation of HCHO) accounted for 10.5 ± 0.6%, 10.6 ± 0.8% and 14.8 ± 0.9% to the formation of HO2 at WJS, ZY and HK, respectively, and reducing HCHO led to a considerable decrease in O3 formation. This study demonstrates the important roles of vehicle exhaust and secondary formation in the sources of HCHO, which have significant photochemical relevance. Attention should be paid to HCHO to control the photochemical pollution in Wuhan effectively.

Vertical profiles of NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, SO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;, HONO, HCHO, CHOCHO and aerosols derived from MAX-DOAS measurements at a rural site in the central western North China Plain and their relation to emission sources and effects of regional transport

Abstract. A multi-axis differential optical absorption spectroscopy (MAX-DOAS) instrument was deployed in May and June 2016 at a monitoring station (37.18∘ N, 114.36∘ E) in the suburban area of Xingtai, which is one of the most polluted cities in the North China Plain (NCP), during the Atmosphere-Aerosol-Boundary Layer-Cloud (A2BC) experiment and Air chemistry Research In Asia (ARIAs) joint experiments to derive tropospheric vertical profiles of NO2, SO2, HONO, HCHO, CHOCHO and aerosols. Aerosol optical depths derived from MAX-DOAS were found to be consistent with collocated sun-photometer measurements. Also the derived near-surface aerosol extinction and HCHO mixing ratio agree well with the coincident visibility meter and in situ HCHO measurements, with mean HCHO near-surface mixing ratios of ∼3.5 ppb. Underestimations of MAX-DOAS results compared to in situ measurements of NO2 (∼60 %) and SO2 (∼20 %) are found expectedly due to vertical and horizontal inhomogeneity of trace gases. Vertical profiles of aerosols and NO2 and SO2 are reasonably consistent with those measured by a collocated Raman lidar and aircraft spirals over the station. The deviations can be attributed to differences in sensitivity as a function of altitude and substantial horizontal gradients of pollutants. Aerosols, HCHO and CHOCHO profiles typically extended to higher altitudes (with 75 % integrated column located below ∼1.4 km) than NO2, SO2 and HONO did (with 75 % integrated column below ∼0.5 km) under polluted conditions. Lifted layers were systematically observed for all species (except HONO), indicating accumulation, secondary formation or long-range transport of the pollutants at higher altitudes. Maximum values routinely occurred in the morning for NO2, SO2 and HONO but occurred at around noon for aerosols, HCHO and CHOCHO, mainly dominated by photochemistry, characteristic upslope–downslope circulation and planetary boundary layer (PBL) dynamics. Significant day-to-day variations are found for all species due to the effect of regional transport and changes in synoptic pattern analysed with the backward propagation approach based on HYSPLIT trajectories. Low pollution was often observed for air masses from the north-west (behind cold fronts), and high pollution was observed from the southern areas such as industrialized Wu'an. The contribution of regional transport for the pollutants measured at the site during the observation period was estimated to be about 20 % to 30 % for trace gases and about 50 % for aerosols. In addition, agricultural burning events impacted the day-to-day variations in HCHO, CHOCHO and aerosols. It needs to be noted that although several MAX-DOAS measurements of trace gases and aerosols in the NCP area have been reported in previous studies, this study is the first work to derive a comprehensive set of vertical profiles of NO2, SO2, HONO, HCHO, CHOCHO and aerosols from measurements of one MAX-DOAS instrument. Also, so far, the validation of MAX-DOAS profile results by comparison with various surface in situ measurements as well as profile measurements from lidar and aircraft is scarce. Moreover, the backward propagation approach for characterizing the contributions of regional transport of pollutants from different regions was applied to the MAX-DOAS results of trace gases and aerosols for the first time.

Simultaneous Observations of Nitrogen Dioxide, Formaldehyde and Ozone in the Indo-Gangetic Plain

ABSTRACT This study reports the concentrations of nitrogen dioxide (NO2) and formaldehyde (HCHO), retrieved using the Multi AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) technique and collocated observations of surface ozone (O3) conducted over the Indo-Gangetic Plain (IGP) during the 2014 monsoon period as part of the Cloud Aerosol Interaction and Precipitation Enhancement Experiment (CAIPEEX). The average daytime NO2 mixing ratio was 0.81 ± 0.20 ppbv (parts per billion by volume) (range: 0.08–6.06 ppbv). NO2 was observed to decrease during the morning between 06:00 and 09:00 local time and then stabilise for the rest of the day. The average daytime HCHO mixing ratio was 1.93 ± 0.60 ppbv (range: 0.32–8.81 ppbv). Unlike NO2, HCHO, driven by daytime photochemical formation from hydrocarbon precursors, increased during the early morning. The average O3 mixing ratio was 30.0 ± 13.0 ppbv (range: 2.7–81.9 ppbv) during the daytime and 22.5 ± 10.2 ppbv (range: 1–63 ppbv) during the nighttime. Analyses of the back trajectories indicatedfound that the NO2 mixing ratios during CAIPEEX-2014 were affected by long-range transport from thermal power plants situated about 110 km to the south but the HCHO mixing ratios and O3 production were influenced by local emissions. These observations suggest that in rural IGP, ozone concentrations are affected by local emission rather than by long-range transport.

Summertime high resolution variability of atmospheric formaldehyde and non-methane volatile organic compounds in a rural background area

On rural background areas atmospheric formaldehyde (HCHO) is important for its abundance and chemical reactivity, directly linked to the tropospheric ozone formation processes. HCHO is also toxic and carcinogenic to humans. Atmospheric HCHO was continuously measured in summer 2016 during 81 days (N = 6722, average: 1.42 ppbv) in a rural background area in Northern Spain, Valderejo Natural Park (VNP) using a Hantzsch fluorimetric system. To better characterize the photochemical processes the database was completed with hourly measurements of 63 Non-Methane Hydrocarbons (NMHC) performed by gas chromatography and other common atmospheric pollutants and meteorological parameters.HCHO mixing ratios were highly correlated with ozone and isoprene. Cloudy and rainy days, with low temperature and radiation, led to low HCHO mixing ratios, with maxima (<2 ppbv) registered around 14 UTC. On days with increased radiation and temperature HCHO maxima occurred slightly later (<6 ppbv, ≈16:00 UTC). During clear summer days with high temperature and radiation, two HCHO peaks were registered daily, one synchronized with the radiation maximum (≈3–4 ppbv, ≈13:00 UTC) and an absolute maximum (<10 ppbv, ≈18:00 UTC), associated with the addition of HCHO coming into VNP due to inbound transport of old polluted air masses.In the ozone episode studied, the processes of accumulation and recharge of ozone and of HCHO ran in parallel, leading to similar daily patterns of variation. Finally, HCHO mixing ratios measured in VNP were compared with other measurements at rural, forested, and remote sites all over the world, obtaining similar values.

Impact of high-resolution a priori profiles on satellite-based formaldehyde retrievals

Abstract. Formaldehyde (HCHO) is either directly emitted from sources or produced during the oxidation of volatile organic compounds (VOCs) in the troposphere. It is possible to infer atmospheric HCHO concentrations using space-based observations, which may be useful for studying emissions and tropospheric chemistry at urban to global scales depending on the quality of the retrievals. In the near future, an unprecedented volume of satellite-based HCHO measurement data will be available from both geostationary and polar-orbiting platforms. Therefore, it is essential to develop retrieval methods appropriate for the next-generation satellites that measure at higher spatial and temporal resolution than the current ones. In this study, we examine the importance of fine spatial and temporal resolution a priori profile information on the retrieval by conducting approximately 45 000 radiative transfer (RT) model calculations in the Los Angeles Basin (LA Basin) megacity. Our analyses suggest that an air mass factor (AMF, a factor converting observed slant columns to vertical columns) based on fine spatial and temporal resolution a priori profiles can better capture the spatial distributions of the enhanced HCHO plumes in an urban area than the nearly constant AMFs used for current operational products by increasing the columns by ∼ 50 % in the domain average and up to 100 % at a finer scale. For this urban area, the AMF values are inversely proportional to the magnitude of the HCHO mixing ratios in the boundary layer. Using our optimized model HCHO results in the Los Angeles Basin that mimic the HCHO retrievals from future geostationary satellites, we illustrate the effectiveness of HCHO data from geostationary measurements for understanding and predicting tropospheric ozone and its precursors.

A new non-resonant laser-induced fluorescence instrument for the airborne in situ measurement of formaldehyde

Abstract. A new in situ instrument for gas-phase formaldehyde (HCHO), COmpact Formaldehyde FluorescencE Experiment (COFFEE), is presented. COFFEE utilizes non-resonant laser-induced fluorescence (NR-LIF) to measure HCHO, with 300 mW of 40 kHz 355 nm laser output exciting multiple HCHO absorption features. The resulting HCHO fluorescence is collected at 5 ns resolution, and the fluorescence time profile is fit to yield the ambient HCHO mixing ratio. Typical 1σ precision at ∼ 0 pptv HCHO is 150 pptv for 1 s data. The compact instrument was designed to operate with minimal in-flight operator interaction and infrequent maintenance (1–2 times per year). COFFEE fits in the wing pod of the Alpha Jet stationed at the NASA Ames Research Center and has successfully collected HCHO data on 27 flights through 2017 March. The frequent flights, combined with a potentially long-term data set, makes the Alpha Jet a promising platform for validation of satellite-based column HCHO.

Formaldehyde in the Tropical Western Pacific: Chemical sources and sinks, convective transport, and representation in CAM-Chem and the CCMI models.

Formaldehyde (HCHO) directly affects the atmospheric oxidative capacity through its effects on HOx. In remote marine environments, such as the Tropical Western Pacific (TWP), it is particularly important to understand the processes controlling the abundance of HCHO because model output from these regions is used to correct satellite retrievals of HCHO. Here, we have used observations from the CONTRAST field campaign, conducted during January and February 2014, to evaluate our understanding of the processes controlling the distribution of HCHO in the TWP as well as its representation in chemical transport/climate models. Observed HCHO mixing ratios varied from ~500 pptv near the surface to ~75 pptv in the upper troposphere. Recent convective transport of near surface HCHO and its precursors, acetaldehyde and possibly methyl hydroperoxide, increased upper tropospheric HCHO mixing ratios by ~33% (22 pptv); this air contained roughly 60% less NO than more aged air. Output from the CAM-Chem chemistry transport model (2014 meteorology) as well as nine chemistry climate models from the Chemistry-Climate Model Initiative (free-running meteorology) are found to uniformly underestimate HCHO columns derived from in situ observations by between 4 and 50%. This underestimate of HCHO likely results from a near factor of two underestimate of NO in most models, which strongly suggests errors in NOx emissions inventories and/or in the model chemical mechanisms. Likewise, the lack of oceanic acetaldehyde emissions and potential errors in the model acetaldehyde chemistry lead to additional underestimates in modeled HCHO of up to 75 pptv (~15%) in the lower troposphere.

Impact of evolving isoprene mechanisms on simulated formaldehyde: An inter-comparison supported by in situ observations from SENEX

Isoprene oxidation schemes vary greatly among gas-phase chemical mechanisms, with potentially significant ramifications for air quality modeling and interpretation of satellite observations in biogenic-rich regions. In this study, in situ observations from the 2013 SENEX mission are combined with a constrained 0-D photochemical box model to evaluate isoprene chemistry among five commonly used gas-phase chemical mechanisms: CB05, CB6r2, MCMv3.2, MCMv3.3.1, and a recent version of GEOS-Chem. Mechanisms are evaluated and inter-compared with respect to formaldehyde (HCHO), a high-yield product of isoprene oxidation. Though underestimated by all considered mechanisms, observed HCHO mixing ratios are best reproduced by MCMv3.3.1 (normalized mean bias = −15%), followed by GEOS-Chem (−17%), MCMv3.2 (−25%), CB6r2 (−32%) and CB05 (−33%). Inter-comparison of HCHO production rates reveals that major restructuring of the isoprene oxidation scheme in the Carbon Bond mechanism increases HCHO production by only ∼5% in CB6r2 relative to CB05, while further refinement of the complex isoprene scheme in the Master Chemical Mechanism increases HCHO production by ∼16% in MCMv3.3.1 relative to MCMv3.2. The GEOS-Chem mechanism provides a good approximation of the explicit isoprene chemistry in MCMv3.3.1 and generally reproduces the magnitude and source distribution of HCHO production rates. We analytically derive improvements to the isoprene scheme in CB6r2 and incorporate these changes into a new mechanism called CB6r2-UMD, which is designed to preserve computational efficiency. The CB6r2-UMD mechanism mimics production of HCHO in MCMv3.3.1 and demonstrates good agreement with observed mixing ratios from SENEX (−14%). Improved simulation of HCHO also impacts modeled ozone: at ∼0.3 ppb NO, the ozone production rate increases ∼3% between CB6r2 and CB6r2-UMD, and rises another ∼4% when HCHO is constrained to match observations.

Estimates of free-tropospheric NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; and HCHO mixing ratios derived from high-altitude mountain MAX-DOAS observations at midlatitudes and in the tropics

Abstract. In this study, mixing ratios of NO2 (XNO2) and HCHO (XHCHO) in the free troposphere are derived from two multi-axis differential optical absorption spectroscopy (MAX-DOAS) data sets collected at Zugspitze (2650 m a.s.l., Germany) and Pico Espejo (4765 m a.s.l., Venezuela). The estimation of NO2 and HCHO mixing ratios is based on the modified geometrical approach, which assumes a single-scattering geometry and a scattering point altitude close to the instrument altitude. Firstly, the horizontal optical path length (hOPL) is obtained from O4 differential slant column densities (DSCDs) in the horizontal (0°) and vertical (90°) viewing directions. Secondly, XNO2 and XHCHO are estimated from the NO2 and HCHO DSCDs at the 0° and 90° viewing directions and averaged along the obtained hOPLs. As the MAX-DOAS instrument was performing measurements in the ultraviolet region, wavelength ranges of 346–372 and 338–357 nm are selected for the DOAS analysis to retrieve NO2 and HCHO DSCDs, respectively. In order to compare the measured O4 DSCDs and moreover to perform some sensitivity tests, the radiative transfer model SCIATRAN with adapted altitude settings for mountainous terrain is operated to simulate synthetic spectra, on which the DOAS analysis is also applied. The overall agreement between measured and synthetic O4 DSCDs is better for the higher Pico Espejo station than for Zugspitze. Further sensitivity analysis shows that a change in surface albedo (from 0.05 to 0.7) can influence the O4 DSCDs, with a larger absolute difference observed for the horizontal viewing direction. Consequently, the hOPL can vary by about 5 % throughout the season, for example when winter snow cover fully disappears in summer. Typical values of hOPLs during clear-sky conditions are 19 km (14 km) at Zugspitze and 34 km (26.5 km) at Pico Espejo when using the 346–372 (338–357 nm) fitting window. The estimated monthly values of XNO2 (XHCHO), averaged over these hOPLs during clear-sky conditions, are in the range of 60–100 ppt (500–950 ppt) at Zugspitze and 8.5–15.5 ppt (255–385 ppt) at Pico Espejo. Interestingly, multi-year-averaged monthly means of XNO2 and XHCHO increase towards the end of the dry season at the Pico Espejo site, suggesting that both trace gases are frequently lifted above the boundary layer as a result of South American biomass burning.

Formaldehyde production from isoprene oxidation across NOx regimes.

The chemical link between isoprene and formaldehyde (HCHO) is a strong, non-linear function of NOx (= NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall photochemical mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the Southeast U.S., we quantify HCHO production across the urban-rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly-emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1 - 2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv-1), while background HCHO increases by a factor of 2 (from 1.6 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a measurement-constrained 0-D steady state box model. Both models reproduce the NOx dependence of the prompt HCHO yield, illustrating that models with updated isoprene oxidation mechanisms can adequately capture the link between HCHO and recent isoprene emissions. On the other hand, both models under-estimate background HCHO mixing ratios, suggesting missing HCHO precursors, inadequate representation of later-generation isoprene degradation and/or under-estimated hydroxyl radical concentrations. Detailed process rates from the box model simulation demonstrate a 3-fold increase in HCHO production across the range of observed NOx values, driven by a 100% increase in OH and a 40% increase in branching of organic peroxy radical reactions to produce HCHO.

Analysis of ambient formaldehyde in the eastern region of India along Indo-Gangetic Plain.

Ambient levels of formaldehyde (HCHO) were measured in the tropical urban mega city of Kolkata from July 2012 to April 2014, based on USEPA Compendium Method TO-11A using 2,4-dinitrophenylhydrazine (2,4-DNPH). The samples were analyzed by isocratic reverse-phase high-performance liquid chromatography (HPLC) with an ultraviolet detector at a wavelength of 360 nm. High values of HCHO were recorded at our site. The highest and average HCHO mixing ratio measured for the entire study period was 803 and 217 ppbv respectively. Seasonal wind regimes have been found to influence the seasonal pattern of HCHO mixing ratio at this site resulting in relatively higher mixing ratio of HCHO during the pre-monsoon periods as compared to the others. Apart from these, sampling-based measurements of CH4 and continuous measurements of ozone (O3) and CO were also performed with the objective to study the interrelationship of HCHO with these species. The results suggest the presence of highly complex chemistry among them.

Atmospheric fluxes and photo-oxidation of methane in the mangrove environment of the Sundarbans, NE coast of India; A case study from Lothian Island

Atmospheric fluxes of CH4 across different boundaries and its photo-oxidation were measured in the Sundarbans mangrove forest during June 2010–December 2011. The annual mean CH4 emission rate from intertidal sediment and adjacent estuarine surfaces were 7.06 and 0.14mgm−2d−1, respectively. Together these sources contribute 10.89Gg of CH4 annually to the atmosphere, of which 99.17% was from sediment. The atmospheric CH4 mixing ratio varied between 1.693 and 2.251ppmv, having an average of 2.004ppmv. CH4 exchange flux from this mangrove biosphere to the atmosphere was 0.086mgm−2d−1, contributing 0.30Gg of CH4 annually. The annual average rate of CH4 photo-oxidation in the forest atmosphere was 3.25×10−9mgcm−3d−1 with maximum oxidation occurring during the monsoon period and minimum oxidation occurring during the post-monsoon period. Total CH4 photo-oxidation within the atmospheric boundary layer of the Sundarbans was 9.26Gg annually, which acts as sink for 85.03% of the emitted CH4. The HCHO and O3 mixing ratios in the forest atmosphere ranged between 2.14±0.06–4.08±1.61ppbv and 14.66±1.88–37.90±0.91ppbv, respectively, having maximal pre-monsoon and minimal monsoon periods. The CH4 photo-oxidation mediated productions of HCHO and O3 within the atmospheric boundary layer were 17.5 and 139Ggyr−1, respectively. A ‘sources and sinks dependent’ mathematical model for atmospheric CH4 proposed in this study can explain the seasonal variability of CH4 and showed significant correlation with the observed values of this regional atmosphere.