Measurements Of HCHO Research Articles

Alternative Analyzers for the Measurement of Gaseous Compounds During Type-Approval of Heavy-Duty Vehicles

Emissions standards describe the fuels, the procedures, and, among others, the analyzers to be used for the measurement of the different compounds during the type-approval of heavy-duty engines and vehicles. Traditionally, NOx, CO, hydrocarbons, and CO2 were the gaseous compounds measured within the Euro standard, with the later addition of CH4 and NH3. Euro 7, introduced in early 2024, expanded those compounds, requiring the measurement of N2O and HCHO. With an increasing number of molecules that need to be measured and introducing carbonless fuels, such as hydrogen, that present different requirements compared to carbon-based fuels, the test procedure needs to be updated. The performances of three laboratory-grade instruments and three portable emissions measurement systems based on Fourier-transformed infrared (FTIR) or quantum cascade laser infrared (QCL-IR) technologies were investigated while measuring from the tailpipe of a Diesel engine and a compressed natural gas (CNG) vehicle. All instruments presented good agreement when emissions of NOx, CO, CH4, NH3, N2O, HCHO, and CO2 were compared using: Z-score, F-test and two tail t-test of student. Water concentration measured by the four FTIRs was also in good agreement. Moreover, the dry emissions of CO2 and CO measured by the laboratory non-dispersive infrared (NDIR) and corrected using water were a few percentages different from those obtained using the regulated carbon-based approach. The results indicate that all the investigated systems are suitable for the measurement of the investigated gaseous compounds, including CO2 and H2O.

Assessment of Formaldehyde’s Impact on Indoor Environments and Human Health via the Integration of Satellite Tropospheric Total Columns and Outdoor Ground Sensors

Formaldehyde (HCHO) is harmful to human health and an adequate assessment of its concentrations, both in outdoor and indoor environments, is necessary in the context of sustainable policies designed to mitigate health risks. In this research, ground indoor and outdoor HCHO measurements are integrated with the analysis of tropospheric total columns obtained by satellite surveys to assess the concentrations of HCHO in a number of environments, exploiting the proximity of a World Meteorological Organization—Global Atmosphere Watch (WMO/GAW) observation site in Calabria, Southern Italy to a National Institute for Insurance against Accidents at Work (INAIL) department in the municipality of Lamezia Terme. The meteorological parameters used by the WMO station are also used to provide additional data and test new correlations. Using statistical significance tests, this study demonstrates the presence of a correlation between indoor and outdoor HCHO concentrations, thus showing that an exchange between indoor and outdoor formaldehyde does occur. Rooms located in the local INAIL building where indoor measurements took place also demonstrate degrees of susceptibility to HCHO exposure, which are correlated with the orientation of prevailing wind corridors in the area. The new findings constitute an unprecedented characterization of HCHO hazards in Calabria and provide regulators with new tools with which to mitigate formaldehyde-related risks.

Troposphere–stratosphere-integrated bromine monoxide (BrO) profile retrieval over the central Pacific Ocean

Abstract. Bromine monoxide (BrO) is relevant to atmospheric oxidative capacity, affecting the lifetime of greenhouse gases (i.e., methane, dimethylsulfide) and mercury oxidation. However, measurements of BrO radical vertical profiles are rare, and BrO is highly variable. As a result, the few available aircraft observations in different regions of the atmosphere are not easily reconciled. Autonomous multi-axis differential optical absorption spectroscopy (MAX-DOAS) instruments placed at remote mountaintop observatories (MT-DOAS) present a cost-effective alternative to aircraft, with the potential to probe the climate-relevant yet understudied free troposphere more routinely. Here, we describe an innovative full-atmosphere BrO and formaldehyde (HCHO) profile retrieval algorithm using MT-DOAS measurements at Mauna Loa Observatory (MLO – 19.536° N, 155.577° W; 3401 m a.s.l.). The retrieval is based on time-dependent optimal estimation and simultaneously inverts 190+ individual BrO (and formaldehyde, HCHO) SCDs (slant column densities; SCD = dSCD + SCDRef) from solar stray light spectra measured in the zenith and off-axis geometries at high and low solar zenith angles (92° > SZA > 30°) to derive BrO concentration profiles from 1.9 to 35 km with 7.5 degrees of freedom (DoFs). Two case study days are characterized by the absence (26 April 2017, base case) and presence of a Rossby-wave-breaking double tropopause (29 April 2017, RW-DT case). Stratospheric-BrO vertical columns are nearly identical on both days (VCD = (1.5 ± 0.2) × 1013 molec. cm−2), and the stratospheric-BrO profile peaks at a lower altitude during the RW-DT (1.6–2.0 DoFs). Tropospheric-BrO VCDs increase from (0.70 ± 0.14) × 1013 molec. cm−2 (base case) to (1.00 ± 0.14) × 1013 molec. cm−2 (RW-DT) owing to a 3-fold increase in BrO in the upper troposphere (1.7–1.9 DoFs). BrO at MLO increases from (0.23 ± 0.03) pptv (base case) to (0.46 ± 0.03) pptv (RW-DT) and is characterized by an added time resolution (∼ 3.8 DoFs). Up to (0.9 ± 0.1) pptv BrO is observed above MLO in the lower free troposphere in the absence of the double tropopause. We validate the retrieval using aircraft BrO profiles and in situ HCHO measurements aboard the NSF/NCAR GV aircraft above MLO (11 January 2014) that establish BrO peaks around 2.4 pptv above 13 km in the upper troposphere–lower stratosphere (UTLS) during a similar RW-DT event (0.83 × 1013 molec. cm2 tropospheric-BrO VCD above 2 km). The tropospheric-BrO profile measured using MT-DOAS (RW-DT case) and using the aircraft agree well (after averaging-kernel smoothing). Furthermore, these tropospheric-BrO profiles over the central Pacific Ocean are found to closely resemble those over the eastern Pacific Ocean (2–14 km) and are in contrast to those over the western Pacific Ocean, where a C-shaped tropospheric-BrO profile shape has been observed.

Four years of National Clean Air Programme (NCAP) in Indian cities: Assessment of the impact on surface ozone during the period 2018–2022

There is a significant increase in ozone at the surface and troposphere due to growing population, industrialisation and urbanisation. The initiation of National Clean Air Programme (NCAP) in 2019 marked a turning point in addressing air pollution in Indian cities. The Central Pollution Control Board (CPCB) ground-based measurements show a reduction in number of days with continuous exposure to 8 h surface ozone (MDA-8) exceeding 100 ppb since the implementation of NCAP. For instance, cities such as Visakhapatnam and Tirupati reported zero days of MDA-8 ozone surpassing 100 ppb in 2022. Also, a substantial reduction is observed in the frequency of MDA-8 ozone exceeding the 100 ppb threshold at other stations. The NO2 and PM2.5 measurements from CPCB show a decreasing trend at most stations, whereas satellite-based HCHO and NO2 measurements show negative (0–0.004 mol m−2 month−1) and positive (0–0.02 m−2 month−1) trends, respectively, during the period of 2019–2022. Therefore, although the implementation of NCAP is oriented towards reducing PM10 concentrations, it is also proven to be effective in curbing ozone pollution in most cities of India. This study, therefore, suggests to continue the efforts of NCAP and to implement tailored regulations for reducing ozone pollution in cities with high pollution.

A quantitative analysis of surgical smoke-derived particulate matter and formaldehyde exposure during spine surgery: a possible occupational hazard.

Since its introduction, electrocautery has served as a valuable surgical tool, enabling precise tissue cutting and effective hemostasis in spine surgery. While there have been numerous efforts to elucidate the possible hazardous effects of surgical smoke in various surgical fields, there has been very little discussion in the context of spine surgery. The objective of this study was to measure and conduct a quantitative analysis of the particulate matter (PM) of different sizes and of formaldehyde (HCHO) generated by smoke during spine surgeries. This study included a consecutive series of patients who underwent 1- or 2-level lumbar spinal fusion surgery between June and November 2021. Particle counts were measured using a particle counter, specifically focusing on six different sizes of PM (0.3, 0.5, 1, 2.5, 5, and 10 µm). Additionally, measurements were taken for HCHO in parts per million (ppm). Monopolar cautery was used in the surgical setting. Systematic measurements were conducted at specific time points during the surgical procedures to assess the levels of PM and HCHO. Furthermore, the efficacy of surgical smoke suction was evaluated by comparing the PM levels with and without adjacent placement of suction. This study involved 35 patients, with measurements of both PM and HCHO taken in 27 cases. The remaining 8 cases had measurements only for PM. In this study, statistically significant quantitative changes in various PM sizes were observed when electrocautery was used during spine surgery (12.3 ± 1.7 vs 1975.7 ± 422.8, 3.4 ± 0.5 vs 250.1 ± 45.7, and 1.9 ± 0.2 vs 78.1 ± 13.3, respectively, for 2.5-, 5-, and 10-µm PM; p < 0.05). The level of HCHO was also significantly higher (0.085 ± 0.006 vs 0.131 ± 0.014 ppm, p < 0.05) with electrocautery use. Utilization of adjacent suction of surgical smoke during electrocautery demonstrated a statistically significant reduction in PM levels. The findings of this study highlight the potential surgical smoke-related hazards that spine surgeons may be exposed to in the operating room. Implementing simple interventions, such as utilizing nearby suction, can effectively minimize the amount of toxic surgical smoke and mitigate these risks.

Inferring global surface HCHO concentrations from multisource hyperspectral satellites and their application to HCHO-related global cancer burden estimation

Formaldehyde (HCHO) is a toxic and hazardous air pollutant that widely exists in atmosphere. Insufficient spatial and temporal coverage of surface HCHO measurements is limiting studies on surface HCHO-related air quality management and health risk assessment. This study develops a method to derive global ground-level HCHO concentrations from satellite-based tropospheric HCHO columns using TM5-simulated surface-to-column conversion factor with coarse spatial resolution. The method improves the factor more representative in finer grids by constraining TM5-simulated vertical profile shapes with satellite HCHO columns. The surface HCHO concentrations derived by the Ozone Mapping and Profiler Suite (OMPS) show good correlation with in situ HCHO measurements (R = 0.59) from the U.S. Environmental Protection Agency surface network. We investigated how surface HCHO relates to urbanization and population aggregation over seven regions with high HCHO pollution. The results show urban HCHO increases as a power function with population size in China, India, and West Asia. HCHO concentrations in rural aeras also present strong log–log relationship with population aggregation in China, India, the United States, and Europe. Moreover, OMPS-derived ground-level HCHO concentrations were used to estimate global cancer burden caused by long-term outdoor HCHO exposure. The results show that up to 418188 more people worldwide will develop this cancer during the human life cycle. The global cancer burden is mainly from the South-East Asia region (33.11 %) and the Western Pacific region (22.95 %). This cancer occurrence in India and China is ranked 1st and 2nd in the world due to the large population size and serious HCHO pollution. Besides, global surface HCHO concentrations and cancer burden derived from the Environmental Trace Gases Monitoring Instrument which is China’s first hyperspectral space-based spectrometer are found similar patterns with that from OMPS. Our results provide new insight into the impact of population urbanization on HCHO pollution and global outdoor HCHO-caused health risks.

Real-Time Measurements of Formaldehyde Emissions from Modern Vehicles

Formaldehyde (HCHO), a carcinogenic carbonyl compound and precursor of tropospheric ozone, can be found in vehicle exhaust. Even though the continuous monitoring of HCHO has been recommended, the real-world emissions from the road transport sector are not commonly available. The main reason for this knowledge gap has been the difficulty to measure HCHO in real-time and during real-world testing. This, for instance, increases the uncertainty of the O3 simulated by air quality models. The present study investigates real-time HCHO measurements comparing three Fourier Transform InfraRed spectrometers (FTIRs) and one Quantum Cascade Laser InfraRed spectrometer (QCL-IR) directly sampling from the exhaust of one gasoline passenger car, one Diesel commercial vehicle and one Diesel heavy-duty vehicle, all meeting recent European emission standards (Euro 6/VI). Non-negligible emissions of HCHO were measured from the Diesel light-duty vehicle, with emissions increasing as temperature decreased. Relatively low emissions were measured for the gasoline car and the Diesel heavy-duty vehicle. The results showed a good correlation between the different instruments under all the conditions tested (in most cases R2 &gt; 0.9). Moreover, it was shown that HCHO can be accurately measured during on-road and real-world-like tests using instruments based on FTIR and QCL-IR technologies.

Quantitative measurement of formaldehyde formed in combustion processes using gas chromatography analytical approach

ABSTRACT We report here the development, validation, and application of a reliable analytical approach to calibrate gaseous formaldehyde (HCHO) using gas chromatography coupled with flame ionization detector and methanizer (GC-FID-methanizer). Contrary to the classical GC-FID, GC-FID-methanizer allows HCHO measurements and presents a higher detection sensitivity for other oxygenated products. Therefore, it becomes a common analytical technique used in the combustion community. However, a common challenge encountered while using GC-FID-methanizer is that the conversion efficiency reduces over time of use and consequently the initial response factor of HCHO based on methanizer is no longer applicable. Therefore, we have developed a direct HCHO calibration method that consists of using of an aqueous liquid mixture with known concentration of formaldehyde and acetaldehyde as an internal standard. A detailed protocol of this proposed method was established. The method was tested and evaluated in (1) two GC-FID-methanizers (one with low and one with high conversion efficiency, respectively) and (2) a calibrated GC-Mass Spectrometry system. Finally, the method was successfully applied in a study devoted to the characterization of furanic biofuel flames and the impact of biofuel combustion on pollutant formation, including HCHO.

Investigation of long–term trends and major sources of atmospheric HCHO over India

Atmospheric formaldehyde (HCHO) has significant adverse health effects at higher concentrations. It is an unstable and inflammable organic compound, and is an index for atmospheric pollution. Although the ambient HCHO is due to methane oxidation, the localised enhancement in HCHO is mostly from the emissions of non-methane volatile organic compounds (NMVOCs). Therefore, assessment of spatial and temporal changes in NMVOCs are key for monitoring air quality and climate change. Here, we analyze two decades of atmospheric HCHO measurements and investigate the HCHO sources in India using satellite observations in 1997–2020. The measurements show very high HCHO concentrations in the Indo-Gangetic Plain (IGP), and south and east India, about 8–12 × 1015 molec. cm−2. The northwest region shows moderate concentrations, but Kashmir and northern regions of northeast show very small values of about 1–2 × 1015 molec. cm−2. Our analyses reveal significant increase in HCHO over India in all seasons, with the highest trends during March–May, about 0.3–0.5 × 1015 molec. cm−2 yr−1; suggesting the spread of pollution even to rural regions. Many ports and mining areas exhibit high positive HCHO trends, which also show new source regions and transport pathways of pollution. Furthermore, the analyses for the COVID-19 lockdown period expose significant contributions from sources other than anthropogenic origin (e.g. biogenic and pyrogenic). Therefore, this study indicates the need of new policy interventions for controlling Volatile Organic Compound (VOC) pollution in rural and urban India, and at the international seaports of Indian Ocean.

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&gt;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.

Comparison of formaldehyde tropospheric columns in Australia and New Zealand using MAX-DOAS, FTIR and TROPOMI

Abstract. South-eastern Australia has been identified by modelling studies as a hotspot of biogenic volatile organic compound (VOC) emissions; however, long-term observational VOC studies are lacking in this region. Here, 2.5 years of multi-axis differential optical absorption spectroscopy (MAX-DOAS) formaldehyde (HCHO) measurements in Australasia are presented, from Broadmeadows, in northern Melbourne, Australia, and from Lauder, a rural site in the South Island of New Zealand. Across the measurement period from December 2016 to November 2019, the mean formaldehyde columns measured by the MAX-DOAS were 2.50±0.61×1015 molec. cm−2 at Lauder and 5.40±1.59×1015 molec. cm−2 at Broadmeadows. In both locations, the seasonal cycle showed a pronounced peak in Austral summer (December–January–February) consistent with temperature-dependent formaldehyde production from biogenic precursor gases. The amplitude of the seasonal cycle was 0.7×1015 molec. cm−2 at Lauder, and it was 2.0×1015 molec. cm−2 at Broadmeadows. The Lauder MAX-DOAS HCHO measurements are compared with 27 months of co-located Fourier transform infrared (FTIR) observations. The seasonal variation of Lauder MAX-DOAS HCHO, smoothed by the FTIR averaging kernels, showed good agreement with the FTIR measurements, with a linear regression slope of 1.03 and an R2 of 0.66 for monthly averaged formaldehyde partial columns (0–4 km). In addition to ground-based observations, a clear way to address the VOC measurement gap in areas such as Australasia is with satellite measurements. Here, we demonstrate that the TROPOspheric Monitoring Instrument (TROPOMI) can be used to distinguish formaldehyde hotspots in forested and agricultural regions of south-eastern Australia. The MAX-DOAS measurements are also compared to TROPOMI HCHO vertical columns at Lauder and Melbourne; very strong monthly average agreement is found for Melbourne (regression slope of 0.61 and R2 of 0.95) and a strong agreement is found at Lauder (regression slope of 0.73 and R2 of 0.61) for MAX-DOAS vs. TROPOMI between May 2018 and November 2019. This study, the first long-term satellite comparison study using MAX-DOAS in the Southern Hemisphere, highlights the improvement offered by TROPOMI's high resolution over previous satellite products and provides the groundwork for future studies using ground-based and satellite DOAS for studying VOCs in Australasia.

TROPOMI–Sentinel-5 Precursor formaldehyde validation using an extensive network of ground-based Fourier-transform infrared stations

Abstract. TROPOMI (the TROPOspheric Monitoring Instrument), on board the Sentinel-5 Precursor (S5P) satellite, has been monitoring the Earth's atmosphere since October 2017 with an unprecedented horizontal resolution (initially 7 km2×3.5 km2, upgraded to 5.5 km2×3.5 km2 in August 2019). Monitoring air quality is one of the main objectives of TROPOMI; it obtains measurements of important pollutants such as nitrogen dioxide, carbon monoxide, and formaldehyde (HCHO). In this paper we assess the quality of the latest HCHO TROPOMI products versions 1.1.(5-7), using ground-based solar-absorption FTIR (Fourier-transform infrared) measurements of HCHO from 25 stations around the world, including high-, mid-, and low-latitude sites. Most of these stations are part of the Network for the Detection of Atmospheric Composition Change (NDACC), and they provide a wide range of observation conditions, from very clean remote sites to those with high HCHO levels from anthropogenic or biogenic emissions. The ground-based HCHO retrieval settings have been optimized and harmonized at all the stations, ensuring a consistent validation among the sites. In this validation work, we first assess the accuracy of TROPOMI HCHO tropospheric columns using the median of the relative differences between TROPOMI and FTIR ground-based data (BIAS). The pre-launch accuracy requirements of TROPOMI HCHO are 40 %–80 %. We observe that these requirements are well reached, with the BIAS found below 80 % at all the sites and below 40 % at 20 of the 25 sites. The provided TROPOMI systematic uncertainties are well in agreement with the observed biases at most of the stations except for the highest-HCHO-level site, where it is found to be underestimated. We find that while the BIAS has no latitudinal dependence, it is dependent on the HCHO concentration levels: an overestimation (+26±5 %) of TROPOMI is observed for very low HCHO levels (&lt;2.5×1015 molec. cm−2), while an underestimation (-30.8%±1.4 %) is found for high HCHO levels (&gt;8.0×1015 molec. cm−2). This demonstrates the great value of such a harmonized network covering a wide range of concentration levels, the sites with high HCHO concentrations being crucial for the determination of the satellite bias in the regions of emissions and the clean sites allowing a small TROPOMI offset to be determined. The wide range of sampled HCHO levels within the network allows the robust determination of the significant constant and proportional TROPOMI HCHO biases (TROPOMI =+1.10±0.05 ×1015+0.64±0.03 × FTIR; in molecules per square centimetre). Second, the precision of TROPOMI HCHO data is estimated by the median absolute deviation (MAD) of the relative differences between TROPOMI and FTIR ground-based data. The clean sites are especially useful for minimizing a possible additional collocation error. The precision requirement of 1.2×1016 molec. cm−2 for a single pixel is reached at most of the clean sites, where it is found that the TROPOMI precision can even be 2 times better (0.5–0.8×1015 molec. cm−2 for a single pixel). However, we find that the provided TROPOMI random uncertainties may be underestimated by a factor of 1.6 (for clean sites) to 2.3 (for high HCHO levels). The correlation is very good between TROPOMI and FTIR data (R=0.88 for 3 h mean coincidences; R=0.91 for monthly means coincidences). Using about 17 months of data (from May 2018 to September 2019), we show that the TROPOMI seasonal variability is in very good agreement at all of the FTIR sites. The FTIR network demonstrates the very good quality of the TROPOMI HCHO products, which is well within the pre-launch requirements for both accuracy and precision. This paper makes suggestions for the refinement of the TROPOMI random uncertainty budget and TROPOMI quality assurance values for a better filtering of the remaining outliers.

Formaldehyde in Rainwater in Sakai City, Japan: Continuous Observation, Concentration, and Aqueous Photoproduction

Formaldehyde (HCHO) is an important component in tropospheric chemistry, but the study of HCHO in rainwater is limited. This is the first report of continuous measurement of HCHO in rainwater. HCHO in rainwater was continuously measured using a modified chemiluminescence method at Sakai City, Osaka, Japan. The continuous measurement was conducted in the 2018 rainy season (Baiu) of Japan. A total of 20 rain events have been observed, and the averaged HCHO concentration of each rain event was 0.13–2.75 μM. The maximum concentration was 9.91 μM. Diurnal variation of HCHO in rainwater showed the distinctively high concentration in nighttime and no correlation with local ambient gaseous HCHO, implying another source such as aqueous photoproduction and transportation rather than scavenging. The photo-irradiation experiment revealed that photoproduction of HCHO is one of the important sources of HCHO in rainwater with the maximum production rate of 2.43 μM h−1. Besides, the backward trajectory indicated that there could have a link with the air mass original location. Furthermore, microorganism activity can play a role as a sink of HCHO in rainwater that could consume HCHO with digestion rate up to 3.2 μM h−1.

MAX-DOAS measurements of tropospheric NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; and HCHO in Nanjing and a comparison to ozone monitoring instrument observations

Abstract. In this paper, we present long-term observations of atmospheric nitrogen dioxide (NO2) and formaldehyde (HCHO) in Nanjing using a Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) instrument. Ground-based MAX-DOAS measurements were performed from April 2013 to February 2017. The MAX-DOAS measurements of NO2 and HCHO vertical column densities (VCDs) are used to validate ozone monitoring instrument (OMI) satellite observations over Nanjing. The comparison shows that the OMI observations of NO2 correlate well with the MAX-DOAS data with Pearson correlation coefficient (R) of 0.91. However, OMI observations are on average a factor of 3 lower than the MAX-DOAS measurements. Replacing the a priori NO2 profiles by the MAX-DOAS profiles in the OMI NO2 VCD retrieval would increase the OMI NO2 VCDs by ∼30 % with correlation nearly unchanged. The comparison result of MAX-DOAS and OMI observations of HCHO VCD shows a good agreement with R of 0.75 and the slope of the regression line is 0.99. An age-weighted backward-propagation approach is applied to the MAX-DOAS measurements of NO2 and HCHO to reconstruct the spatial distribution of NO2 and HCHO over the Yangtze River Delta during summer and winter time. The reconstructed NO2 fields show a distinct agreement with OMI satellite observations. However, due to the short atmospheric lifetime of HCHO, the backward-propagated HCHO data do not show a strong spatial correlation with the OMI HCHO observations. The result shows that the MAX-DOAS measurements are sensitive to the air pollution transportation in the Yangtze River Delta, indicating the air quality in Nanjing is significantly influenced by regional transportation of air pollutants. The MAX-DOAS data are also used to evaluate the effectiveness of air pollution control measures implemented during the Youth Olympic Games 2014. The MAX-DOAS data show a significant reduction of ambient aerosol, NO2 and HCHO (30 %–50 %) during the Youth Olympic Games. Our results provide a better understanding of the transportation and sources of pollutants over the Yangtze River Delta as well as the effect of emission control measures during large international events, which are important for the future design of air pollution control policies.

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.

Effect of Seasonal Variation on the Levels and Behaviours of Formaldehyde in the Atmosphere of a Suburban Area in Cairo, Egypt

Formaldehyde (HCHO) is a carcinogenic pollutant, has an active role in tropospheric photochemistry, and can be affected by seasonal variations. To our knowledge, this is the first comprehensive study of the effect of seasonal variation on the levels and behaviours of HCHO in the atmosphere of a suburban area (15 May City) in Cairo. Daytime and nighttime measurements of HCHO were performed from March 2014 to February 2015. The highest average daily concentrations of HCHO were found in summer and the lowest in winter. The difference was statistically significant (p≤0.001). Daily average HCHO concentrations in spring, summer, autumn and winter were higher than the corresponding values in many polluted cities in the world. This was true for both weekdays and weekends. HCHO was higher in daytime than nighttime on weekdays and weekends, and the differences in mean concentrations were statistically significant (p ≤0.001), except during the autumn and winter on weekends. Therefore, the contribution of photochemical reactions in the observed levels of HCHO might be greater than that of traffic emissions. This was further proved by the significant positive correlation found between daytime HCHO concentrations and temperature. HCHO concentrations were higher on weekdays than weekends, the differences in mean concentrations were statistically significant (p≤0.001). This may be attributed to higher emission of HCHO from higher traffic intensity during daytime. Significant positive correlations (p≤0.001) were found between daytime and nighttime HCHO concentrations, both on weekdays and weekends suggesting that HCHO comes from the same sources.

Time series prediction of CO2, TVOC and HCHO based on machine learning at different sampling points

This paper presents novel findings about the prediction of TVOC and HCHO using the machine learning approach. Continuous measurements of CO2, TVOC and HCHO were conducted in five rooms of SDE, NUS. The collection data was trained and tested by 4 machine learning algorithms including support vector machine (SVM), Gaussian processes (GP), M5P and backpropagation neural network (BPNN). Overall, SVM scored the highest in performance evaluation because it has the highest average prediction accuracy and fewer overfitting in the test data. High predictability due to large autocorrelation was observed in the pattern analysis of CO2 and TVOC. Accurate results were achieved by SVM for CO2 and TVOC, with mean MAPE of being 1.87% and 2.30%, respectively. In contrast, low autocorrelation indicated the hidden mode of HCHO data was more difficult to capture than CO2 and TVOC. The small R2 between predicted and actual values of HCHO demonstrated low predictability, ranging from 0.0008 to 0.0215.

Characterization of trace gas emissions at an intermediate port

Abstract. Growing ship traffic in Atlantic Canada strengthens the local economy but also plays an important role in greenhouse gas and air pollutant emissions in this coastal environment. A mobile open-path Fourier transform infrared (OP-FTIR; acronyms defined in Appendix A) spectrometer was set up in Halifax Harbour (Nova Scotia, Canada), an intermediate harbour integrated into the downtown core, to measure trace gas concentrations in the vicinity of marine vessels, in some cases with direct or near-direct marine combustion plume intercepts. This is the first application of the OP-FTIR measurement technique to real-time, spectroscopic measurements of CO2, CO, O3, NO2, NH3, CH3OH, HCHO, CH4 and N2O in the vicinity of harbour emissions originating from a variety of marine vessels, and the first measurement of shipping emissions in the ambient environment along the eastern seaboard of North America outside of the Gulf Coast. The spectrometer, its active mid-IR source and its detector were located on shore while the passive retroreflector was on a nearby island, yielding a 455 m open path over the ocean (910 m two-way). Atmospheric absorption spectra were recorded during day, night, sunny, cloudy and substantially foggy or precipitating conditions, with a temporal resolution of 1 min or better. A weather station was co-located with the retroreflector to aid in the processing of absorption spectra and the interpretation of results, while a webcam recorded images of the harbour once per minute. Trace gas concentrations were retrieved from spectra by the MALT non-linear least squares iterative fitting routine. During field measurements (7 days in July–August 2016; 12 days in January 2017) AIS information on nearby ship activity was manually collected from a commercial website and used to calculate emission rates of shipping combustion products (CO2, CO, NOx, HC, SO2), which were then linked to measured concentration variations using ship position and wind information. During periods of low wind speed we observed extended (∼9 h) emission accumulations combined with near-complete O3 titration, both in winter and in summer. Our results compare well with a NAPS monitoring station ∼1 km away, pointing to the extended spatial scale of this effect, commonly found in much larger European shipping channels. We calculated total marine sector emissions in Halifax Harbour based on a complete AIS dataset of ship activity during the cruise ship season (May–October 2015) and the remainder of the year (November 2015–April 2016) and found trace gas emissions (tonnes) to be 2.8 % higher on average during the cruise ship season, when passenger ship emissions were found to contribute 18 % of emitted CO2, CO, NOx, SO2 and HC (0.5 % in the off season due to occasional cruise ships arriving, even in April). Similarly, calculated particulate emissions are 4.1 % higher during the cruise ship season, when passenger ship emissions contribute 18 % of the emitted particulate matter (PM) (0.5 % in the off season). Tugs were found to make the biggest contribution to harbour emissions of trace gases in both cruise ship season (23 % NOx, 24 % SO2) and the off season (26 % of both SO2 and NOx), followed by container ships (25 % NOx and SO2 in the off season, 21 % NOx and SO2 in cruise ship season). In the cruise ship season cruise ships were observed to be in third place regarding trace gas emissions, whilst tankers were in third place in the off season, with both being responsible for 18 % of the calculated emissions. While the concentrations of all regulated trace gases measured by OP-FTIR as well as the nearby in situ NAPS sensors were well below maximum hourly permissible levels at all times during the 19-day measurement period, we find that AIS-based shipping emissions of NOx over the course of 1 year are 4.2 times greater than those of a nearby 500 MW stationary source emitter and greater than or comparable to all vehicle NOx emissions in the city. Our findings highlight the need to accurately represent emissions from the shipping and marine sectors at intermediate ports integrated into urban environments. Emissions can be represented as pseudo-stationary and/or pseudo-line sources.

NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; and HCHO measurements in Korea from 2012 to 2016 from Pandora spectrometer instruments compared with OMI retrievals and with aircraft measurements during the KORUS-AQ campaign

Abstract. Nine Pandora spectrometer instruments (PSI) were installed at eight sites in South Korea as part of the KORUS-AQ (Korea U.S.-Air Quality) field study integrating information from ground, aircraft, and satellite measurements for validation of remote sensing air-quality studies. The PSI made direct-sun measurements of total vertical column NO2, C(NO2), with high precision (0.05 DU, where 1 DU =2.69×1016 molecules cm−2) and accuracy (0.1 DU) that were retrieved using spectral fitting techniques. Retrieval of formaldehyde C(HCHO) total column amounts were also obtained at five sites using the recently improved PSI optics. The C(HCHO) retrievals have high precision, but possibly lower accuracy than for NO2 because of uncertainty about the optimum spectral window for all ground-based and satellite instruments. PSI direct-sun retrieved values for C(NO2) and C(HCHO) are always significantly larger than OMI (AURA satellite Ozone Monitoring Instrument) retrieved C(NO2) and C(HCHO) for the OMI overpass local times (KST=13.5±0.5 h). In urban areas, PSI C(NO2) 30-day running averages are at least a factor of two larger than OMI averages. Similar differences are seen for C(HCHO) in Seoul and nearby surrounding areas. Late afternoon values of C(HCHO) measured by PSI are even larger, implying that OMI early afternoon measurements underestimate the effect of poor air quality on human health. The primary cause of OMI underestimates is the large OMI field of view (FOV) that includes regions containing low values of pollutants. In relatively clean areas, PSI and OMI are more closely in agreement. C(HCHO) amounts were obtained for five sites, Yonsei University in Seoul, Olympic Park, Taehwa Mountain, Amnyeondo, and Yeoju. Of these, the largest amounts of C(HCHO) were observed at Olympic Park and Taehwa Mountain, surrounded by significant amounts of vegetation. Comparisons of PSI C(HCHO) results were made with the Compact Atmospheric Multispecies Spectrometer CAMS during overflights on the DC-8 aircraft for Taehwa Mountain and Olympic Park. In all cases, PSI measured substantially more C(HCHO) than obtained from integrating the CAMS altitude profiles. PSI C(HCHO) at Yonsei University in Seoul frequently reached 0.6 DU and occasionally exceeded 1.5 DU. The semi-rural site, Taehwa Mountain, frequently reached 0.9 DU and occasionally exceeded 1.5 DU. Even at the cleanest site, Amnyeondo, C(HCHO) occasionally exceeded 1 DU.

Investigation of a potential HCHO measurement artifact from ISOPOOH.

Recent laboratory experiments have shown that a first generation isoprene oxidation product, ISOPOOH, can decompose to methyl vinyl ketone (MVK) and methacrolein (MACR) on instrument surfaces, leading to overestimates of MVK and MACR concentrations. Formaldehyde (HCHO) was suggested as a decomposition co-product, raising concern that in situ HCHO measurements may also be affected by an ISOPOOH interference. The HCHO measurement artifact from ISOPOOH for the NASA In Situ Airborne Formaldehyde instrument (ISAF) was investigated for the two major ISOPOOH isomers, (1,2)-ISOPOOH and (4,3)-ISOPOOH, under dry and humid conditions. The dry conversion of ISOPOOH to HCHO was 3±2% and 6±4% for (1,2)-ISOPOOH and (4,3)-ISOPOOH, respectively. Under humid (RH= 40-60%) conditions, conversion to HCHO was 6±4% for (1,2)-ISOPOOH and 10±5% for (4,3)-ISOPOOH. The measurement artifact caused by conversion of ISOPOOH to HCHO in the ISAF instrument was estimated for data obtained on the 2013 September 6 flight of the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) campaign. Prompt ISOPOOH conversion to HCHO was the source for <4% of the observed HCHO, including in the high-isoprene boundary layer. Time-delayed conversion, where previous exposure to ISOPOOH affects measured HCHO later in flight, was conservatively estimated to be < 10% of observed HCHO and is significant only when high ISOPOOH sampling periods immediately precede periods of low HCHO.