Atmospheric Formaldehyde Research Articles

A decade of satellite observations reveal significant increase in atmospheric formaldehyde from shipping in Indian Ocean

Atmospheric formaldehyde (HCHO) is a potential pollutant and very harmful to public health at higher doses. There are different sources for HCHO in the atmosphere, in which fuel combustion and biomass burning are predominant. The oxidation of hydroxyl radicals (OH) and methane are the chemical production pathways of HCHO in the troposphere. Here, we show a different source of HCHO emission to the atmosphere; the maritime shipping. The analyses using satellite measurements for the period 2005–2014 reveal large amounts of HCHO release along the ship routes in Indian Ocean, about 7–8 x1015 molec./cm2. This is nearly twice (150–200%) the ambient or background HCHO levels (about 4 × 1015 molec./cm2), when there is no ship emissions in the north Indian Ocean. The trend in HCHO concentrations over the Indian Ocean sea routes is about 0.008 × 1015 molec./cm2/year. The amount and the increasing trends of HCHO over the maritime routes in the north Indian Ocean are also comparable to those of the busiest sea-lanes in the world Oceans, such as the Panama Canal, Mediterranean Sea and Strait of Malacca. Our analyses, henceforth, suggest use of a better fuel for shipping to reduce the maritime pollution, as the polluted air can often be transported to the coastal regions and islands, which is a concern for public health in those regions.

Investigation and modeling of diurnal variation in suburban ambient formaldehyde concentration.

Formaldehyde (HCHO) is a naturally occurring compound found in ambient air which can induce cancer and sick-building syndrome. It plays an important role in the formation of OH radicals, which are connected to the formation of various airborne chemicals. Herein, we present a simple modeling for the simulation of diurnal variations in the HCHO concentration of ambient air. This was achieved using data collected during different seasons from November 2015 to March 2017 at a suburban location in Toyama City (Japan), where non-methane hydrocarbon (NMHC) levels were low at sub carbon ppm (ppmC) order. The modeling was based on the assumption that photochemical reactions of methane were the major factor of secondary HCHO formation. The model took into account the production and decomposition of HCHO by photochemical reactions as well as its loss due to other reactions such as dry deposition. Accordingly, the model's equation contained terms for solar radiation, temperature, and methane concentration. The results predicted using the model showed good agreement with the experimental data observed on fine days, i.e., except rainy, foggy, and heavily cloudy days. The relationships between HCHO concentration and solar radiation/temperature on different days as well as the seasonal variation of HCHO concentration were also interpreted by the proposed model. This study contributes to the evaluation of the pollution levels of formaldehyde. Moreover, the model may be used to demonstrate the impact of increasing methane levels, with regard to global warming and the background levels of HCHO in the atmosphere.

Contribution of mobile sources to secondary formation of carbonyl compounds

ABSTRACT In the 2014 National Air Toxics Assessment (NATA), the carbonyl compounds formaldehyde and acetaldehyde were identified as key cancer risk drivers and acrolein was identified as one of the three air toxics that drive most of the noncancer risk. In this assessment, averaged across the Continental United States, about 75% of ambient formaldehyde and acetaldehyde, and about 18% of acrolein, is formed secondarily. This study was conducted to estimate the potential contribution to these secondarily formed carbonyl compounds from mobile sources. To develop such estimates, we conducted several CMAQ runs, where emissions are set to zero for different mobile source sectors, to determine their potential contribution. Although zeroing out emissions from an individual sector can offer only a rough approximation of how the sector might contribute to overall secondary concentrations, our results suggest that across the U. S., mobile sources contribute about 6–18% to secondary formaldehyde, 0–10% to secondary acetaldehyde, and 0–70% to secondary acrolein, depending on location. Implications: Photochemical modeling of carbonyl compounds was conducted with emissions set to zero for various mobile source sectors to determine their contribution to secondary concentrations. Results indicated mobile sources contributed to total and secondary concentrations of formaldehyde, acetaldehyde, and acrolein in many locations across the U.S. with acrolein the dominant contributor in some locations. However, biogenic sources dominated secondary formaldehyde and acetaldehyde, and fires dominated secondary acrolein.

Environmental assessment of the impact of the meteorological conditions on technogenic formaldehyde and carbon black pollution of the air in Voronezh

Based on the Voronezh hydrometeorological service official statistics analysis, the pollutants (formaldehyde and carbon black) dynamics regularities depending on the various meteorological parameters combination - air temperature, wind speed, relative humidity. A positive relationship was established between atmospheric pollution growth with formaldehyde and air temperature. As the wind speed and the air relative humidity increase, the formaldehyde and soot concentration in the urban atmosphere, as a rule, decreases. The carcinogenic risk maximum permissible level to public health, causing concern, has been established. The obtained patterns can be used to predict the city’s atmosphere technogenic pollution level depending on meteorological conditions. Based on the official statistic analysis from the Voronezh Hydrometeorological Service, the pollutants (formaldehyde and carbon black) dynamics patterns are investigated depending on various meteorological parameters’ combination - air temperature, wind speed, relative air humidity. A positive relationship has been established between the increase in atmospheric pollution with formaldehyde and air temperature. With increasing wind speed and relative humidity, the formaldehyde and soot concentration in the city atmosphere, as a rule, decrease. The maximum permissible carcinogenic risk level to public health has been established, causing concern. The obtained patterns can be used to predict the city’s atmosphere technogenic pollution level, depending on meteorological conditions.

Release of formaldehyde and other organic compounds from nitrogen fertilizers

In addition to nitrogen, carbonyl compounds such as formaldehyde, acetaldehyde, isobutyraldehyde and crotonaldehyde can be released from slow release fertilizers based on urea-aldehyde by hydrolytic or biotic processes. A possible relevance of such releases in the practical application of corresponding products was investigated in laboratory experiments. In the first part, emissions of organic compounds from the pure products were determined in desiccators under static conditions in dry and water-saturated air as well as during direct contact with water. Significant emissions of isobutyraldehyde were found for products containing isobutylidene diurea. Several formulations emitted acetaldehyde and formaldehyde, especially in the case of higher air humidity and when solved in water. However, crotonaldehyde was not detected in the desiccator air. Other organic components such as herbicides or their degradation products and nitrification inhibitors were released from fertilizers containing these compounds.In further experiments, sticks and granules were applied into potting soil and the release of organic compounds in emission chambers was examined under dynamic conditions. No substances that could be directly attributed to the fertilizers were detected in these experiments. However, relevant emission rates of formaldehyde were observed for the spray fertilizers containing urea-formaldehyde after application to tomato plants. The possible contribution of these emissions to atmospheric formaldehyde concentrations is discussed. Finally, the formaldehyde concentrations in a greenhouse for private use are estimated. It is likely that immediately after spray application of a urea-formaldehyde fertilizer increased formaldehyde concentrations in the breathing air of the greenhouse occur.

Pollution Characteristics of Atmospheric Carbonyls in Urban Linfen in Winter

Atmospheric carbonyls (aldehyde and ketone compounds) can be precursors for ozone and PM2.5, and they play an essential role in atmospheric chemistry. Linfen is a basin between mountains on the east and west, and there are many coking plants on the north and south sides of its urban area. The special topography and unfortunate industrial layout have frequently contributed to serious air pollution in Linfen. In order to investigate the pollution characteristics of atmospheric carbonyls in winter in urban Linfen, the carbonyl compounds were collected from the Municipal Committee site (MC) and the Yaowangtai site (YWT) from 16 to 25 January 2019, and their concentrations were analyzed by a high performance liquid chromatography-ultraviolet detector (HPLC-UV). The results show that formaldehyde, acetaldehyde, and acetone were the most abundant compounds, accounting for more than 70% of the total mass concentration of carbonyls in urban Linfen. Levels of these three carbonyls increased during the morning and evening traffic rush hours. The mass concentration of formaldehyde at both sites reached peak values at around noon (10:00–14:00). In addition, the mass concentrations of formaldehyde, acetaldehyde, and acetone were positively correlated with CO mass concentrations, whereas only formaldehyde and acetaldehyde were positively correlated with temperature. Therefore, atmospheric formaldehyde in urban Linfen’s winter mainly came from vehicle exhaust emissions and the secondary generation of photochemical reactions. Most of the acetaldehyde came from vehicle exhaust emissions, and photochemical reactions also partially contributed to it. For acetone, vehicle exhaust emissions were the main source. In addition, coking industry emissions from Northern Linfen′s Hongtong County may also have contributed to the atmospheric carbonyls in the urban area of Linfen. For the first time, this study found that formaldehyde showed different behavior to acetaldehyde and acetone; that is, the nighttime decrease in formaldehyde mass concentration was greater than that of acetaldehyde and acetone.

Spatio-temporal distribution and source partitioning of formaldehyde over Ethiopia and Kenya

Abstract Understanding the local sources of atmospheric formaldehyde (HCHO) is a key step in accurately determining the inversion of biogenic volatile organic compounds (BVOCs). This study aims to clarify the main sources and emission patterns of local total HCHO column densities over Ethiopia and Kenya. Between 2005 and 2015, the total monthly HCHO varied from 3.7 × 1015 molecules/cm2 to 7.7 × 1015 molecules/cm2. Monthly HCHO showed a strong seasonal pattern with annual peaks on March, July (small peak) and October, which well matched with the rainy seasons in Ethiopia and Kenya. Natural sources contributed 36% to the total HCHO in the study area. Grassland and savannas showed high column densities in the long rainy season starting from March, with the monthly average emission value of 5.6 × 1015 molecules/cm2. Multiple regression result showed that vegetation contributed 3.5 × 1013 molecules/cm2 to monthly HCHO, with grassland and forest in eastern Kenya and the boundary of Ethiopia and Kenya were the main contributors in these regions. Biomass burning and methane contributed to HCHO emission in the western and northern Ethiopia with a magnitude of 1.4 × 1014 molecules/cm2 and 6.2 × 1016 molecules/cm2 per month, respectively. Economic activities showed negative response to HCHO columns, except over the two small-scale regions of Addis Ababa City and Nairobi City. This study quantified the HCHO from various sources and suggested that natural sources produce more HCHO than anthropogenic sources over Ethiopia and Kenya.

Photochemistry of Methane and Ethane in the Martian Atmosphere

AbstractWe develop an existing 1‐D photochemistry model to include a comprehensive description of organic chemistry on Mars that includes the oxidation products of methane (CH4) and ethane (C2H6),a longer‐chain hydrocarbon that can be used to differentiate between abiotic and biotic surface releases of CH4. We find that CH4 is most volatile between 20 and 50 km during Mars' northern summer, where the local atmospheric CH4 lifetime lowers to 25–60 years. We study atmospheric formaldehyde (HCHO) and formic acid (HCOOH), as the two common oxidation products of CH4 and C2H6, and acetaldehyde (CH3CHO) and acetic acid (CH3COOH) as unique products of C2H6. We focus our analysis of these gases at Mars' aphelion and perihelion at latitudes between ‐30° and 30°, altitudes from the surface to 70 km, and from a homogeonous initial condition of 50 pptv of CH4 and C2H6. From this initial condition, CH4 produces HCHO in a latitude‐independent layered structure centered at 20–30 km at aphelion with column‐averaged mixing ratios of 10−4 pptv, and oxidation of C2H6 produces HCHO at 10−2 pptv. Formic acid has an atmospheric lifetime spanning 1–10 sols below 10 km that shows little temporal or zonal variability and is produced in comparable abundances (10−5 pptv) by the oxidation of C2H6 and CH4. We also find that oxidation of 50 pptv of C2H6 results in 10−3 pptv of CH3CHO and 10−4 pptv of CH3COOH. Subsequent UV photolysis of this CH3CHO results in 10−4 pptv of atmospheric CH4, potentially representing a new atmospheric source of Martian CH4.

Analysis of Volatile Organic Compounds during the OCTAVE Campaign: Sources and Distributions of Formaldehyde on Reunion Island

The Oxygenated Compounds in the Tropical Atmosphere: Variability and Exchanges (OCTAVE) campaign aimed to improve the assessment of the budget and role of oxygenated volatile organic compounds (OVOCs) in tropical regions, and especially over oceans, relying on an integrated approach combining in situ measurements, satellite retrievals, and modeling. As part of OCTAVE, volatile organic compounds (VOCs) were measured using a comprehensive suite of instruments on Reunion Island (21.07° S, 55.38° E) from 7 March to 2 May 2018. VOCs were measured at a receptor site at the Maïdo observatory during the entire campaign and at two source sites: Le Port from 19 to 24 April 2018 (source of anthropogenic emissions) and Bélouve from 25 April to 2 May 2018 (source of biogenic emissions) within a mobile lab. The Maïdo observatory is a remote background site located at an altitude of 2200 m, whereas Bélouve is located in a tropical forest to the east of Maïdo and Le Port is an urban area located northwest of Maïdo. The major objective of this study was to understand the sources and distributions of atmospheric formaldehyde (HCHO) in the Maïdo observatory on Reunion Island. To address this objective, two different approaches were used to quantify and determine the main drivers of HCHO at Maïdo. First, a chemical-kinetics-based (CKB) calculation method was used to determine the sources and sinks (biogenic, anthropogenic/primary, or secondary) of HCHO at the Maïdo site. The CKB method shows that 9% of the formaldehyde formed from biogenic emissions and 89% of HCHO had an unknown source; that is, the sources cannot be explicitly described by this method. Next, a positive matrix factorization (PMF) model was applied to characterize the VOC source contributions at Maïdo. The PMF analysis including VOCs measured at the Maïdo observatory shows that the most robust solution was obtained with five factors: secondary biogenic accounting for 17%, primary anthropogenic/solvents (24%), primary biogenic (14%), primary anthropogenic/combustion (22%), and background (23%). The main contributions to formaldehyde sources as described by the PMF model are secondary biogenic (oxidation of biogenic VOCs with 37%) and background (32%). Some assumptions were necessary concerning the high percentage of unknown HCHO sources of the CKB calculation method such as the biogenic emission factor resulting in large discrepancies between the two methods.

Improved spherical mirror multipass-cell-based interband cascade laser spectrometer for detecting ambient formaldehyde at parts per trillion by volume levels.

We report the development of an improved spherical mirror multipass-cell-based interband cascade laser (ICL) spectrometer for ambient formaldehyde (HCHO) detection. The multipass cell consists of two easily manufactured spherical mirrors that are low cost, and have a simple structure, large mirror area utilization, and dense spot pattern. Optical interference caused by the multipath cell was largely reduced, resulting in good sensitivity. Using wavelength modulation spectroscopy (WMS), a detection precision (${1} \sigma $1σ) of 51 pptv in 10 s was achieved with an absorption pathlength of 96 m, which compared favorably with the performance of other state-of-the-art instruments. The precision can be further improved by using a long absorption pathlength configuration and by removing fringe-like optical noise caused by the collimation lens. Ambient application of the developed spectrometer was demonstrated.

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.

Contributions to local- and regional-scale formaldehyde concentrations

Abstract. Reducing ambient formaldehyde concentrations is a complex task because formaldehyde is both a primary and a secondary air pollutant, with significant anthropogenic and biogenic sources of volatile organic compound (VOC) precursor emissions. This work uses adjoint sensitivity analysis in a chemical transport model to identify emission sources and chemical reactions that influence formaldehyde mixing ratios in the San Francisco Bay Area and within three urbanized sub-areas. For each of these receptors, the use of the adjoint technique allows for efficient calculation of the sensitivity of formaldehyde to emissions of NOx, formaldehyde, and VOC precursors occurring at any location and time. Formaldehyde mixing ratios are found to be generally higher in summer than in winter. The opposite seasonal trend is observed for the sensitivities of these mixing ratios to formaldehyde emissions. In other words, even though formaldehyde is higher in summer, reducing formaldehyde emissions has a greater impact in winter. In winter, 85 %–90 % of the sensitivity to emissions is attributed to direct formaldehyde emissions. In summer, this contribution is smaller and more variable, ranging from 27 % to 75 % among the receptor areas investigated in this study. Higher relative contributions of secondary formation versus direct emissions are associated with receptors located farther away from heavily urbanized and emission-rich areas. In particular, the relative contribution of biogenic VOC emissions (15 %–43 % in summer) is largest for these receptors. Ethene and other alkenes are the most influential anthropogenic precursors to secondary formaldehyde. Isoprene is the most influential biogenic precursor. Sensitivities of formaldehyde to NOx emissions are generally negative but relatively small in magnitude compared to sensitivities to VOC emissions. The magnitude of anthropogenic emissions of organic compounds other than formaldehyde is found to correlate reasonably well with their influence on population-weighted formaldehyde mixing ratios at the air-basin scale. This correlation does not hold for ambient formaldehyde in smaller urbanized sub-areas. The magnitude of biogenic emissions does not correlate with their influence in either case.

The Controlling Factors of Atmospheric Formaldehyde (HCHO) in Amazon as Seen From Satellite

AbstractTo understand the relative importance of biogenic emission, biomass burning emission on volatile organic compounds in Amazon, the spatial and temporal correlations between atmospheric column‐integrated formaldehyde (HCHO) and fire count, vegetation hydrological states index, surface solar radiation flux, near‐surface air temperature are studied using synergized satellite products and reanalysis data. A recently developed microwave‐based vegetation index (emissivity difference vegetation index, EDVI) with high temporal resolution is used for the linkages between vegetation and HCHO at daily scale with and without fire contaminations. At large regional scale, EDVI shows highest spatial correlation with HCHO indicating the important controlling effect of biogenic emission. In given subregions with frequent fires, the temporal variations of monthly HCHO show much stronger correlations with fire count. The temporal correlations between monthly HCHO and EDVI are vague and even negative in some subregions. Radiation and temperature show stable positive temporal correlations with HCHO, particularly in areas with few fires. After excluding the samples contaminated by fires, the daily temporal correlation between vegetation (EDVI) and HCHO becomes significant and positive in most areas except the northern rainforest with weak temporal variations of EDVI. We proposed a bilinear model of biogenic‐emission‐induced HCHO (B‐HCHO) using radiation and EDVI as inputs. The bias between modeled long‐term mean B‐HCHO and satellite observation is less than 20%. And the daily time series of modeled B‐HCHO matches observations as well. It is the first time to provide satellite observational evidences of the relative importance of biogenic emission and biomass burning emission on HCHO, the proxy of atmospheric volatile organic compounds concentration.

Primary and secondary sources of ambient formaldehyde in the Yangtze River Delta based on Ozone Mapping and Profiler Suite (OMPS) observations

Abstract. Formaldehyde (HCHO) in the ambient air not only causes cancer but is also an ideal indicator of volatile organic compounds (VOCs), which are major precursors of ozone (O3) and secondary organic aerosol (SOA) near the surface. It is meaningful to differentiate between the direct emission and the secondary formation of HCHO for HCHO pollution control and sensitivity studies of O3 production. However, understanding of the sources of HCHO is still poor in China, due to the scarcity of field measurements (both spatially and temporally). In this study, tropospheric HCHO vertical column densities (VCDs) in the Yangtze River Delta (YRD), East China, where HCHO pollution is serious, were retrieved from the Ozone Mapping and Profiler Suite (OMPS) onboard the Suomi National Polar-orbiting Partnership (Suomi-NPP) satellite from 2014 to 2017; these retrievals showed good agreement with the tropospheric HCHO columns measured using ground-based high-resolution Fourier transform infrared spectrometry (FTS) with a correlation coefficient (R) of 0.78. Based on these results, the cancer risk was estimated both nationwide and in the YRD region. It was calculated that at least 7840 people in the YRD region would develop cancer in their lives due to outdoor HCHO exposure, which comprised 23.4 % of total national cancer risk. Furthermore, the contributions of primary and secondary sources were apportioned, in addition to primary and secondary tracers from surface observations. Overall, the HCHO from secondary formation contributed most to ambient HCHO and can be regarded as the indicator of VOC reactivity in Hangzhou and in urban areas of Nanjing and Shanghai from 2015 to 2017, due to the strong correlation between total HCHO and secondary HCHO. At industrial sites in Nanjing, primary emissions more strongly influenced ambient HCHO concentrations in 2015 and showed an obvious decreasing trend. Seasonally, HCHO from secondary formation reached a maximum in summer and a minimum in winter. In the spring, summer, and autumn, secondary formation had a significant effect on the variation of ambient HCHO in urban regions of Nanjing, Hangzhou, and Shanghai, whereas in the winter the contribution from secondary formation became less significant. A more thorough understanding of the variation of the primary and secondary contributions of ambient HCHO is needed to develop a better knowledge regarding the role of HCHO in atmospheric chemistry and to formulate effective control measures to decrease HCHO pollution and the associated cancer risk.

MAX-DOAS measurements and vertical profiles of glyoxal and formaldehyde in Madrid, Spain

Glyoxal (CHOCHO) and formaldehyde (HCHO) are organic trace gases that play an important role in tropospheric chemistry as oxidation products of a number of volatile organic compounds (VOCs). In this study, we report year-round daytime measurements of glyoxal and formaldehyde in the urban atmosphere of Madrid, Spain. Their vertical concentration profiles were retrieved using the Multi AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) technique and a Radiative Transfer Model (RTM) that simulates solar photon paths through the atmosphere. The diurnal variations of HCHO show two distinct peaks during the day, in the early morning and late afternoon in spring and summer, while the second peak is shifted towards noon in autumn and winter, due to lower photolysis rates and more effective boundary layer accumulation of HCHO in those seasons. The HCHO surface mixing ratios range from 6 ppbv to 27 ppbv in spring-summer and from 10 ppbv to 30 ppbv in autumn-winter. Monthly hourly-averaged glyoxal surface mixing ratios in the early morning show higher values during winter, 2 ppbv, than in summer, 0.7 ppbv. We also evaluated the ratio between glyoxal and formaldehyde (RGF) surface mixing ratios, as an indicator of the nature of VOCs precursors. The RGF was also correlated with the measured NO2, which represents a direct signal of anthropogenic emissions, along with the VOCs emission inventories in Madrid. The RGF results yielded higher ratios in spring, 0.1–0.13, than in winter and autumn (in the range of 0.02–0.07) when NO2 levels were higher.

Sodium Enhances Ir/TiO2 Activity for Catalytic Oxidation of Formaldehyde at Ambient Temperature

The development of highly efficient catalysts for ambient formaldehyde (HCHO) destruction is of great interest for indoor air purification. Here, we show that a sodium (Na)-doped iridium (Ir) catal...

The IVAIRE Study: Inter- and Intra-Seasonal Variations in VOC's Measured in Canadian Homes with Asthmatic Children during a Intervention Field Study

A randomized intervention study was done to measure the impact of improved ventilation on indoor air quality (IAQ) and the respiratory health of asthmatic children in Qu&amp;#233;bec City. The intervention involved the installation of a Heat or Energy Recovery Ventilator while a comprehensive suite of environmental parameters were used to characterize the IAQ. The IAQ measurements were taken during three separate periods both before and after the intervention. The winter measurements, used to correlate ventilation rates with IAQ and respiratory health, were taken twice to account for intra-seasonal variations in IAQ while the single summer measurement was taken to determine the inter-seasonal variations. A cohort of 111 asthmatic children were enrolled for the pre-intervention phase of which 83 were selected to participate in the subsequent intervention phase because their homes were found to be under-ventilated (air exchange rate &amp;lt;0.30 h-1). The children were then randomized into an intervention (n&amp;#61;43) and control (n&amp;#61;40) group for the second year (post-intervention phase) of the study. This paper presents the variations in the VOC&amp;#8217;s measured within the same season, between seasons (winter, summer), along with the year-over-year variations within the same season. A statistically significant seasonal variability was observed for relative humidity, NO2, VOC&amp;#8217;s and aldehydes. The aromatic and aliphatic hydrocarbons were most elevated in winter, up to 2x higher, and were the most strongly impacted by the ventilation intervention. The aldehydes, oxygenated VOC&amp;#8217;s, and NO2, all had higher summertime concentrations despite the median air exchange rate being almost twice as high during summer. A possible explanation could be that the increased temperature and humidity encountered in summer would promote the release of aldehydes from hydrolysis reactions and off-gassing from construction and consumer products and that ambient formaldehyde is generally higher in summer.

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.

High-resolution inversion of OMI formaldehyde columns to quantify isoprene emission on ecosystem-relevant scales: application to the southeast US

Abstract. Isoprene emissions from vegetation have a large effect on atmospheric chemistry and air quality. “Bottom-up” isoprene emission inventories used in atmospheric models are based on limited vegetation information and uncertain land cover data, leading to potentially large errors. Satellite observations of atmospheric formaldehyde (HCHO), a high-yield isoprene oxidation product, provide “top-down” information to evaluate isoprene emission inventories through inverse analyses. Past inverse analyses have however been hampered by uncertainty in the HCHO satellite data, uncertainty in the time- and NOx-dependent yield of HCHO from isoprene oxidation, and coarse resolution of the atmospheric models used for the inversion. Here we demonstrate the ability to use HCHO satellite data from OMI in a high-resolution inversion to constrain isoprene emissions on ecosystem-relevant scales. The inversion uses the adjoint of the GEOS-Chem chemical transport model at 0.25∘ × 0.3125∘ horizontal resolution to interpret observations over the southeast US in August–September 2013. It takes advantage of concurrent NASA SEAC4RS aircraft observations of isoprene and its oxidation products including HCHO to validate the OMI HCHO data over the region, test the GEOS-Chem isoprene oxidation mechanism and NOx environment, and independently evaluate the inversion. This evaluation shows in particular that local model errors in NOx concentrations propagate to biases in inferring isoprene emissions from HCHO data. It is thus essential to correct model NOx biases, which was done here using SEAC4RS observations but can be done more generally using satellite NO2 data concurrently with HCHO. We find in our inversion that isoprene emissions from the widely used MEGAN v2.1 inventory are biased high over the southeast US by 40 % on average, although the broad-scale distributions are correct including maximum emissions in Arkansas/Louisiana and high base emission factors in the oak-covered Ozarks of southeast Missouri. A particularly large discrepancy is in the Edwards Plateau of central Texas where MEGAN v2.1 is too high by a factor of 3, possibly reflecting errors in land cover. The lower isoprene emissions inferred from our inversion, when implemented into GEOS-Chem, decrease surface ozone over the southeast US by 1–3 ppb and decrease the isoprene contribution to organic aerosol from 40 to 20 %.

Characterizing CO and NOy Sources and Relative Ambient Ratios in the Baltimore Area Using Ambient Measurements and Source Attribution Modeling

Modeled source attribution information from the Community Multiscale Air Quality model was coupled with ambient data from the 2011 Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality Baltimore field study. We assess source contributions and evaluate the utility of using aircraft measured CO and NOy relationships to constrain emission inventories. We derive ambient and modeled ΔCO:ΔNOy ratios that have previously been interpreted to represent CO:NOy ratios in emissions from local sources. Modeled and measured ΔCO:ΔNOy are similar; however, measured ΔCO:ΔNOy has much more daily variability than modeled values. Sector-based tagging shows that regional transport, on-road gasoline vehicles, and nonroad equipment are the major contributors to modeled CO mixing ratios in the Baltimore area. In addition to those sources, on-road diesel vehicles, soil emissions, and power plants also contribute substantially to modeled NOy in the area. The sector mix is important because emitted CO:NOx ratios vary by several orders of magnitude among the emission sources. The model-predicted gasoline/diesel split remains constant across all measurement locations in this study. Comparison of ΔCO:ΔNOy to emitted CO:NOy is challenged by ambient and modeled evidence that free tropospheric entrainment, and atmospheric processing elevates ambient ΔCO:ΔNOy above emitted ratios. Specifically, modeled ΔCO:ΔNOy from tagged mobile source emissions is enhanced 5–50% above the emitted ratios at times and locations of aircraft measurements. We also find a correlation between ambient formaldehyde concentrations and measured ΔCO:ΔNOy suggesting that secondary CO formation plays a role in these elevated ratios. This analysis suggests that ambient urban daytime ΔCO:ΔNOy values are not reflective of emitted ratios from individual sources.