Deciphering the role of radical precursors during the Second Texas Air Quality Study.

PubMed

Olaguer, Eduardo P; Rappenglück, Bernhard; Lefer, Barry; Stutz, Jochen; Dibb, Jack; Griffin, Robert; Brune, William H; Shauck, Maxwell; Buhr, Martin; Jeffries, Harvey; Vizuete, William; Pinto, Joseph P

2009-11-01

The Texas Environmental Research Consortium (TERC) funded significant components of the Second Texas Air Quality Study (TexAQS II), including the TexAQS II Radical and Aerosol Measurement Project (TRAMP) and instrumented flights by a Piper Aztec aircraft. These experiments called attention to the role of short-lived radical sources such as formaldehyde (HCHO) and nitrous acid (HONO) in increasing ozone productivity. TRAMP instruments recorded daytime HCHO pulses as large as 32 parts per billion (ppb) originating from upwind industrial activities in the Houston Ship Channel, where in situ surface monitors detected HCHO peaks as large as 52 ppb. Moreover, Ship Channel petrochemical flares were observed to produce plumes of apparent primary HCHO. In one such combustion plume that was depleted of ozone by large emissions of oxides of nitrogen (NOx), the Piper Aztec measured a ratio of HCHO to carbon monoxide (CO) 3 times that of mobile sources. HCHO from uncounted primary sources or ozonolysis of underestimated olefin emissions could significantly increase ozone productivity in Houston beyond previous expectations. Simulations with the CAMx model show that additional emissions of HCHO from industrial flares or mobile sources can increase peak ozone in Houston by up to 30 ppb. Other findings from TexAQS II include significant concentrations of HONO throughout the day, well in excess of current air quality model predictions, with large nocturnal vertical gradients indicating a surface or near-surface source of HONO, and large concentrations of nighttime radicals (approximately30 parts per trillion [ppt] HO2). HONO may be formed heterogeneously on urban canopy or particulate matter surfaces and may be enhanced by organic aerosol of industrial or motor vehicular origin, such as through conversion of nitric acid (HNO3). Additional HONO sources may increase daytime ozone by more than 10 ppb. Improving the representation of primary and secondary HCHO and HONO in air quality

Investigation of a potential HCHO measurement artifact from ISOPOOH

PubMed Central

St. Clair, Jason M.; Rivera-Rios, Jean C.; Crounse, John D.; Praske, Eric; Kim, Michelle J.; Wolfe, Glenn M.; Keutsch, Frank N.; Wennberg, Paul O.; Hanisco, Thomas F.

2018-01-01

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. PMID:29636831

Investigation of a Potential HCHO Measurement Artifact from ISOPOOH

NASA Technical Reports Server (NTRS)

St Clair, Jason M.; Rivera-Rios, Jean C.; Crounse, John D.; Praske, Eric; Kim, Michelle J.; Wolfe, Glenn M.; Keutche, Frank N.; Wennberg, Paul O.; Hanisco, Thomas F.

2016-01-01

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.

Ambient formaldehyde and its contributing factor to ozone and OH radical in a rural area

NASA Astrophysics Data System (ADS)

Xiaoyan, Wang; Huixiang, Wang; Shaoli, Wang

2010-06-01

Formaldehyde (HCHO), as well as correlative pollutants was measured from 1 to 31 July in 2007 at Mazhuang, a rural site located in the east of China. Gaseous HCHO was scrubbed from the air with an acidic 2,4-dinitrophenylhydrazine (DNPH) solution, which leaded to the reaction of HCHO with DNPH and produced a stable product, 2,4-dinitrophenylhydrazone, followed by online analysis by high-performance liquid chromatography (HPLC) coupled with Ultraviolet detector. During the observation period, mixing ratios of HCHO ranged from 0.2 ppbv to 6.2 ppbv, with an average of 1.5 ± 0.67 ppbv. HCHO shows an evident diurnal variation, the maximum appeared during 12:00-14:00. The average concentration diurnal variations of measured HCHO, ozone (O 3), Methylhydroperoxides (MHP, CH 3OOH), hydrogen peroxide (H 2O 2), nitrogen oxides (NO x) and meteorological parameters were compared. The similar variations of HCHO, O 3 and radiation imply that photo-oxidation of hydrocarbons might be the major source for HCHO. Based on the maximum incremental reactivity (MIR) coefficient of HCHO, the calculation shows that HCHO contributes about 20% to total observed O 3 during the study period. In order to compare the contributions of O 3, HCHO and HONO to OH radical, photolysis rate parameters ( J-values) of the three compounds were calculated by the Tropospheric Ultraviolet and Visible (TUV) Radiation Model (4.4 version). Based on the comparison, this study reaches the conclusion that O 3 is the dominant source of OH radical at Mazhuang. This study also uses P(HCHO)/P(O 3) which represents the ratio of contrbutions of HCHO and O 3 to OH radical, to discuss the action of HCHO in OH radical soucers. The result shows that P(HCHO)/P(O 3) is 12.5% on average, with the maximum of 21.0% at 13:00 P.M. and minimum of 7.5% before 9:00 A.M. and after 17:00 P.M..Therefore HCHO is also an important source of OH radical and cannot be ignored.

Equilibrium of particle nitrite with gas phase HONO: Tropospheric measurements in the high Arctic during polar sunrise

NASA Astrophysics Data System (ADS)

Li, Shao-Meng

1994-12-01

Gas phase HONO(g) and nitrite in particles of <5-μm size were measured in the troposphere during the Polar Sunrise Experiment at Alert, Northwest Territories, Canada, during January 19 to April 20, 1992, using denuder-filter pack sampling and IC-UV detection. The measurements indicated that HONO(g) existed at concentrations of up to 70 ppt before polar sunrise but gradually decreased to 5-10 ppt after sunrise. The calculated OH formation rate from HONO(g) photolysis was greater than from the photolysis of both O3 and CH2O by more than one order of magnitude during the sunlit period and led to moderately high levels of OH, e.g., 3×105 molecules cm-3 OH at noontime on April 5. Particle nitrite measurements showed a gradual increase in concentrations with increasing solar insolation, but the concentrations were generally less than 10 ppt. The pH and the sulfate molar concentrations of the particles and the water vapor mixing ratio indicate that the particles were highly acidic being approximately 70% (W/W) H2SO4 solution. In such highly concentrated H2SO4 solution, most particle nitrite should exist as hydrated nitrosonium ion H2ONO+. Taking this into consideration, the particle nitrite was in an approximate equilibrium with the measured HONO(g). This equilibrium, with HONO(g) rapidly photolyzed, was a good indication that the particles were effective sources of HONO(g) and implied rapid production of particle N(+III) during this period. Two possible pathways leading to the formation of particle N(+III) species are suggested, i.e., reduction of HNO3(aq) by SO2(g) and reduction of NO3-; (aq) by Br- (aq). However, N2O5 reaction with NaBr cannot be ruled out as the alternative HONO(g) formation mechanism which bypasses the equilibrium.

Evidence of Aerosols as a Media for Rapid Daytime HONO Production over China

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zhen; Wang, Yuhang; Costabile, Francesa

Current knowledge of daytime HONO sources remains incomplete. A large missing daytime HONO source has been found in many places around the world, including polluted regions in China. Conventional understanding and recent studies attributed this missing source mainly to ground surface processes or gas-phase chemistry, while assuming aerosols to be an insignificant media for HONO production. We analyze in situ observations of HONO and its precursors at an urban site in Beijing, China, and report an apparent dependence of the missing HONO source strength on aerosol surface area and solar ultraviolet radiation. Based on extensive correlation analysis and process-modeling, wemore » propose that the rapid daytime HONO production in Beijing can be explained by enhanced hydrolytic disproportionation of NO2 on aqueous aerosol surfaces due to catalysis by dicarboxylic acid anions. The combination of high abundance of NO2, aromatic hydrocarbons, and aerosols over broad regions in China likely leads to elevated HONO levels, rapid OH production, and enhanced oxidizing capacity on a regional basis. Our findings call for attention to aerosols as a media for daytime heterogeneous HONO production in polluted regions like Beijing. This study also highlights the complex and uncertain heterogeneous chemistry in China, which merits future efforts of reconciling regional modeling and laboratory experiments, in order to understand and mitigate the regional particulate and O3 pollutions over China.« less

The relationship between nighttime formation of gaseous HONO and nocturnal stability in an urban environment

NASA Astrophysics Data System (ADS)

McLaren, Robert; Wojtal, Patryk; Taylor, Peter

2014-05-01

Nitrous acid (HONO) is an important radical precursor in the troposphere that accumulates overnight giving rise to a significant photolytic production of the hydroxyl radical, OH, in the boundary layer during early morning hours the next day. It is understood that HONO is formed in the dark through the heterogeneous hydrolysis of NO2 on surfaces (2 NO2+ H2O -> HONO + HNO3) in a first order process, largely dominated by hydrolysis on ground surfaces and a smaller contribution from aerosol surfaces. Despite progress, the dark heterogeneous mechanism of HONO formation is still not well understood, mirroring our lack of consensus on the daytime production of HONO. We have measured HONO at night in an urban area (York University, Toronto, Canada) by DOAS for over one year. This rich dataset was analyzed with a view to understanding the nocturnal formation mechanism, and possible links to the daytime HONO formation mechanism. Frequently, "steady-states" of HONO are observed at night; d[HONO]/dt ~ 0, which follow after a rapid buildup of HONO during sunset at rates of several ppb hr-1. These steady-state levels of HONO are found to be independent of the mixing ratio of NO2 throughout the night. On other occasions, steady-states are not observed and HONO continues to increase throughout the night, highly correlated with the levels of NO2 d([HONO]/[NO2])/dt ~ 0). We have found that a very significant predictor of the type of behavior is the nocturnal stability of the atmosphere, measured by the thermal gradient, ΔT=T9.5m-T1.0m, and wind speed. The steady-state behavior is found to occur almost exclusively on unstable nights with higher wind speeds and ΔT ~ 0, when mixing of air in the lower atmosphere is more efficient. The non steady-state behavior of HONO is observed on stable nights with low wind speeds and large thermal gradients, ΔT > 2oC indicating limited vertical mixing. The observation of NO2 independent steady-states of HONO under conditions of efficient

The Reduction of HNO3 to HONO by Volatile Organic Compounds Associated with Rush Hour Traffic

NASA Astrophysics Data System (ADS)

Rutter, A. P.; Malloy, Q.; Scheuer, E.; Gutierrez, C.; Calzada, M.; Dibb, J. E.; Griffin, R. J.

2012-12-01

Nitrous acid (HONO) is an important source of OH radicals in urban environments. However, the sources of HONO are not completely understood, which makes modeling urban atmospheric chemistry difficult. During a previous field study in Houston, TX a correlation was observed between increases in HONO and organic aerosol freshly emitted by motor vehicle traffic during morning rush hours (Ziemba et al., 2010). This source of HONO could not be explained by primary HONO emissions, and the hypothesis was drawn that the HONO was being formed from the reduction of HNO3 by the organic aerosols emitted by motor vehicles. To test this hypothesis, nitric acid (HNO3) was combined in a flow tube with aerosols made from automobile engine oil, which were used as a model for the organic aerosols emitted by rush hour traffic. Reduction of the HNO3 to HONO was observed, although the reaction was found to occur with the volatile organic carbon compounds (VOCs) found in the aerosol vapor, and not the particle surfaces. To explore this further Teflon raschig rings were added to the flow tube to increase surface area but the reaction was not enhanced, confirming the reaction to be homogeneous. The HONO formation observed ranged between 0.1 and 0.5 ppb hr-1 with a mean of 0.3±0.1 ppb hr-1, for typical nitric acid concentrations of 4-5 ppb and estimated concentrations of the reactive components in the engine oil vapor of between 200 and 300 ppt. The observations in this study compared well to the cited field study which observed formation rates between 0.05 and 0.5 ppb hr-1 with an average of 0.3±0.15 ppb hr-1. Water vapor was found to decrease the HONO formation rate by 0.1 ppb hr-1 for every1% of increase in the water mixing ratio. Reference Ziemba L.D., Dibb J.E., Griffin R.J., Anderson C.H., Whitlow S.I., Lefer B.L., Rappenglueck B., and Flynn J. (2010) Heterogeneous conversion of nitric acid to nitrous acid on the surface of primary organic aerosol in an urban atmosphere. Atmospheric

Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

NASA Technical Reports Server (NTRS)

Elshorbany, Y. F.; Crutzen, P. J.; Steil, B.; Pozzer, A.; Tost, H.; Lelieveld, J.

2014-01-01

Recently, realistic simulation of nitrous acid (HONO) based on the HONO / NOx ratio of 0.02 was found to have a significant impact on the global budgets of HOx (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation

Tropospheric HONO Distribution and Chemistry in the Southeastern U.S.

NASA Astrophysics Data System (ADS)

Zhou, X.; Ye, C.; Pu, D.; Stutz, J.; Festa, J.; Spolaor, M.; Weinheimer, A. J.; Campos, T. L.; Haggerty, J. A.; Cantrell, C. A.; Mauldin, L.; Guenther, A. B.; Hornbrook, R. S.; Apel, E. C.; Jensen, J. B.

2014-12-01

During the NOMADSS field campaign, nitrous acid (HONO) and particulate nitrate (pNO3) was measured on NCAR C-130 research aircraft during five research flights over the Southeast U.S. Aerosol samples were also collected on Teflon filters for the determination of pNO3 photolysis rate constants in the laboratory. Daytime HONO concentrations range from low ppt in free troposphere to 10-20 ppt in the boundary layer in the background air masses, to up to 40 ppt in the industrial and urban plumes. While daytime HONO sink is well defined, dominated by its photolysis, daytime sources vary in different types of air masses: pNO3 photolysis appears to be the major HONO source in the background terrestrial air masses in both the boundary layer and the free troposphere. With an average pNO3 photolysis rate constant of (2.8±1.7)×10-4 s-1, p-NO3 photolysis becomes to be an effective pathway to recycle HNO3 to NOx in the troposphere, with HONO as a dominant intermediate product. Within the high-NOx industrial plumes encountered, HONO is predominantly produced by secondary formation processes involving NOx as the precursor. Away from ground surface, no significant nighttime HONO accumulation exists in the background terrestrial air mass.

Gradient Measurements of Nitrous Acid (hono)

NASA Astrophysics Data System (ADS)

Kleffmann, J.; Kurtenbach, R.; Lörzer, J.; Wiesen, P.; Kalthoff, N.; Vogel, B.; Vogel, H.

Nitrous acid (HONO) plays an important role in photochemical air pollution due to its photodissociation by solar UV radiation into hydroxyl radicals and thus significantly enhances photooxidation processes. Furthermore, HONO is an important indoor pol- lutant, which can react with amines leading to nitrosamines, which are known to be carcinogenic. Despite its importance in atmospheric chemistry the mechanisms lead- ing to HONO formation are still not completely understood at present. Although it is commonly proposed that HONO is formed by heterogeneous processes, i.e. by the conversion of NO2 on wet surfaces, it is still under discussion whether HONO produc- tion is dominated by the surface of particles or by the ground surface. Simultaneous vertical profile measurements of HONO, the precursor NO2 and the aerosol surface area, which could answer this question are not available at present. Accordingly, in the present study night-time HONO, NO2 and particle surface area gradients in the altitude range 10-190 m were measured on the meteorological tower at the Forschungszentrum Karlsruhe/Germany using a new, very sensitive HONO in- strument (LOPAP), a commercial NOx monitor and a SMPS system. For all gradient measurements during the campaign it was observed that the [HONO]/[NO2] ratio decreased with increasing altitude. In contrast, the particle sur- face area was found to be more or less constant. Accordingly, no correlation between the [HONO]/[NO2] ratio and the particle surface area was observed showing that HONO formation was dominated by processes on ground surfaces and that signifi- cant HONO formation on particle surfaces could be excluded for the measurement site.

Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

NASA Technical Reports Server (NTRS)

Elshorbany, Y. F.; Crutzen, P. J.; Steil, B.; Pozzer, A.; Tost, H.; Lelieveld, J.

2014-01-01

Recently, realistic simulation of nitrous acid (HONO) based on the HONO/NO(sub x) ratio of 0.02 was found to have a significant impact on the global budgets of HO(sub x) (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation.

HONO fluxes from soil surfaces: an overview

NASA Astrophysics Data System (ADS)

Wu, Dianming; Sörgel, Matthias; Tamm, Alexandra; Ruckteschler, Nina; Rodriguez-Caballero, Emilio; Cheng, Yafang; Pöschl, Ulrich; Weber, Bettina

2016-04-01

Gaseous nitrous acid (HONO) contributes up to 80% of atmospheric hydroxyl (OH) radicals and is also linked to health risks through reactions with tobacco smoke forming carcinogens. Field and modeling results suggested a large unknown HONO source in the troposphere during daytime. By measuring near ground HONO mixing ratio, up to 30% of HONO can be released from forest, rural and urban ground as well as snow surfaces. This source has been proposed to heterogeneous reactions of nitrogen dioxide (NO2) on humic acid surfaces or nitric acid photolysis. Laboratory studies showed that HONO emissions from bulk soil samples can reach 258 ng m-2 s-1 (in term of nitrogen), which corresponding to 1.1 × 1012 molecules cm-2 s-1and ˜ 100 times higher than most of the field studies, as measured by a dynamic chamber system. The potential mechanisms for soil HONO emissions include chemical equilibrium of acid-base reaction and gas-liquid partitioning between soil nitrite and HONO, but the positive correlation of HONO fluxes with pH (largest at neutral and slightly alkaline) points to the dominance of the formation process by ammonia-oxidizing bacteria (AOB). In general soil surface acidity, nitrite concentration and abundance of ammonia-oxidizing bacteria mainly regulate the HONO release from soil. A recent study showed that biological soil crusts in drylands can also emit large quantities of HONO and NO, corresponding to ˜20% of global nitrogen oxide emissions from soils under natural vegetation. Due to large concentrations of microorganisms in biological soil crusts, particularly high HONO and NO emissions were measured after wetting events. Considering large areas of arid and arable lands as well as peatlands, up to 70% of global soils are able to emitting HONO. However, the discrepancy between large soil HONO emissions measured in lab and low contributions of HONO flux from ground surfaces in field as well as the role of microorganisms should be further investigated.

Is Forest Ground and Soil a Net Source or Sink for HONO?

NASA Astrophysics Data System (ADS)

Kim, T.; Kim, K.; Zhou, X.

2017-12-01

Ambient measurements and chamber experiments were conducted at the PROPHET site during the PROPHET-AMOS 2016 field campaign, to investigate the exchange of nitrous acid (HONO) between the forest ground and the atmosphere. HONO concentrations measured at 1.3 m and 10 cm above the ground surface consistently showed positive gradients with height, suggesting that the ground surface was a net sink for HONO. The HONO concentration gradients were significantly more pronounced during rainy and foggy periods than during dry periods, indicating an enhancement of HONO deposition onto the wet ground surface. Significant loss of HONO from the gas phase to the ground surface in an open-bottom chamber supports the argument that forest ground is a net HONO sink via deposition. Despite the ground surface was not a net HONO source, HONO was found to accumulate in the atmosphere within the forest canopy during the first half of the night. Heterogeneous reactions of NO2 on the surfaces of tree trunks and branches is proposed to be responsible for the observed nighttime HONO production.

Detailed budget analysis of HONO in central London reveals a missing daytime source

NASA Astrophysics Data System (ADS)

Lee, J. D.; Whalley, L. K.; Heard, D. E.; Stone, D.; Dunmore, R. E.; Hamilton, J. F.; Young, D. E.; Allan, J. D.; Laufs, S.; Kleffmann, J.

2016-03-01

Measurements of HONO were carried out at an urban background site near central London as part of the Clean air for London (ClearfLo) project in summer 2012. Data were collected from 22 July to 18 August 2014, with peak values of up to 1.8 ppbV at night and non-zero values of between 0.2 and 0.6 ppbV seen during the day. A wide range of other gas phase, aerosol, radiation, and meteorological measurements were made concurrently at the same site, allowing a detailed analysis of the chemistry to be carried out. The peak HONO/NOx ratio of 0.04 is seen at ˜ 02:00 UTC, with the presence of a second, daytime, peak in HONO/NOx of similar magnitude to the night-time peak, suggesting a significant secondary daytime HONO source. A photostationary state calculation of HONO involving formation from the reaction of OH and NO and loss from photolysis, reaction with OH, and dry deposition shows a significant underestimation during the day, with calculated values being close to 0, compared to the measurement average of 0.4 ppbV at midday. The addition of further HONO sources from the literature, including dark conversion of NO2 on surfaces, direct emission, photolysis of ortho-substituted nitrophenols, the postulated formation from the reaction of HO2 × H2O with NO2, photolysis of adsorbed HNO3 on ground and aerosols, and HONO produced by photosensitized conversion of NO2 on the surface increases the daytime modelled HONO to 0.1 ppbV, still leaving a significant missing daytime source. The missing HONO is plotted against a series of parameters including NO2 and OH reactivity (used as a proxy for organic material), with little correlation seen. Much better correlation is observed with the product of these species with j(NO2), in particular NO2 and the product of NO2 with OH reactivity. This suggests the missing HONO source is in some way related to NO2 and also requires sunlight. Increasing the photosensitized surface conversion rate of NO2 by a factor of 10 to a mean daytime first

Resolving the HONO formation mechanism in the ionosphere via ab initio molecular dynamic simulations

PubMed Central

He, Rongxing; Li, Lei; Zhong, Jie; Zhu, Chongqin; Francisco, Joseph S.; Zeng, Xiao Cheng

2016-01-01

Solar emission produces copious nitrosonium ions (NO+) in the D layer of the ionosphere, 60 to 90 km above the Earth’s surface. NO+ is believed to transfer its charge to water clusters in that region, leading to the formation of gaseous nitrous acid (HONO) and protonated water cluster. The dynamics of this reaction at the ionospheric temperature (200–220 K) and the associated mechanistic details are largely unknown. Using ab initio molecular dynamics (AIMD) simulations and transition-state search, key structures of the water hydrates—tetrahydrate NO+(H2O)4 and pentahydrate NO+(H2O)5—are identified and shown to be responsible for HONO formation in the ionosphere. The critical tetrahydrate NO+(H2O)4 exhibits a chain-like structure through which all of the lowest-energy isomers must go. However, most lowest-energy isomers of pentahydrate NO+(H2O)5 can be converted to the HONO-containing product, encountering very low barriers, via a chain-like or a three-armed, star-like structure. Although these structures are not the global minima, at 220 K, most lowest-energy NO+(H2O)4 and NO+(H2O)5 isomers tend to channel through these highly populated isomers toward HONO formation. PMID:27071120

Resolving the HONO formation mechanism in the ionosphere via ab initio molecular dynamic simulations.

PubMed

He, Rongxing; Li, Lei; Zhong, Jie; Zhu, Chongqin; Francisco, Joseph S; Zeng, Xiao Cheng

2016-04-26

Solar emission produces copious nitrosonium ions (NO(+)) in the D layer of the ionosphere, 60 to 90 km above the Earth's surface. NO(+) is believed to transfer its charge to water clusters in that region, leading to the formation of gaseous nitrous acid (HONO) and protonated water cluster. The dynamics of this reaction at the ionospheric temperature (200-220 K) and the associated mechanistic details are largely unknown. Using ab initio molecular dynamics (AIMD) simulations and transition-state search, key structures of the water hydrates-tetrahydrate NO(+)(H2O)4 and pentahydrate NO(+)(H2O)5-are identified and shown to be responsible for HONO formation in the ionosphere. The critical tetrahydrate NO(+)(H2O)4 exhibits a chain-like structure through which all of the lowest-energy isomers must go. However, most lowest-energy isomers of pentahydrate NO(+)(H2O)5 can be converted to the HONO-containing product, encountering very low barriers, via a chain-like or a three-armed, star-like structure. Although these structures are not the global minima, at 220 K, most lowest-energy NO(+)(H2O)4 and NO(+)(H2O)5 isomers tend to channel through these highly populated isomers toward HONO formation.

Infrared Spectrum of N-Oxidohydroxylamine [ONH(OH)] Produced in Reaction H + Hono in Solid Para-Hydrogen

NASA Astrophysics Data System (ADS)

Haupa, Karolina Anna; Lee, Yuan-Pern

2017-06-01

Hydrogenation reactions in the N/O chemical network are important for an understanding of the mechanism of formation of organic molecules in dark interstellar clouds, but many reactions remain unknown. We present the results of the reaction H + HONO in solid {para}-hydrogen ({p}-H_{2}) at 3.3 K investigated with infrared spectra. Two methods that produced hydrogen atoms were the irradiation of HONO molecules in {p}-H_{2} at 365 nm to produce OH radicals that reacted readily with nearby H_{2} to produce mobile H atoms, and irradiation of Cl_{2} molecules (co-deposited with HONO) in {p}-H_{2} at 405 nm to produce Cl atoms that reacted readily with nearby H_{2} to produce mobile H atoms. In both experiments, we assigned IR lines at 3549.6 (νb{1}), 1465.0 (νb{3}), 1372.2 (νb{4}), 895.6/898.5 (νb{6}), and 630.9 (νb{7}) \\wn to N-oxidohydroxylamine [ONH(OH)], the primary product of HONO hydrogenation. The assignments were derived according to the consideration of possible reactions and comparison of observed vibrational wavenumbers and their IR intensities with values predicted with the B3LYP/aug-cc-pVTZ method of quantum-chemical calculations. The agreement between observed and calculated D/H- and ^{15}N/^{14}N-isotopic ratios further supports these assignments. The role of this reaction in the N/O chemical network in dark interstellar clouds is discussed.

Nitrous acid in a street canyon environment: Sources and contributions to local oxidation capacity

NASA Astrophysics Data System (ADS)

Yun, Hui; Wang, Zhe; Zha, Qiaozhi; Wang, Weihao; Xue, Likun; Zhang, Li; Li, Qinyi; Cui, Long; Lee, Shuncheng; Poon, Steven C. N.; Wang, Tao

2017-10-01

Nitrous acid (HONO) plays an important role in radical formation and photochemical oxidation processes in the boundary layer. However, its impact on the chemistry in a street canyon microenvironment has not been thoroughly investigated. In this study, we measured HONO in a street canyon in urban Hong Kong and used an observation-based box model (OBM) with the Master Chemical Mechanism (MCM v3.3.1) to investigate the contribution of HONO to local oxidation chemistry. The observed HONO mixing ratios were in the range of 0.4-13.9 ppbv, with an average of 3.91 ppbv in the daytime and 2.86 ppbv at night. A mean HONO/NOx emission ratio of 1.0% (±0.5%) from vehicle traffic was derived. OBM simulations constrained by the observed HONO showed that the maximum concentrations of OH, HO2, and RO2 reached 4.65 × 106, 4.40 × 106, and 1.83 × 106 molecules cm-3, which were 7.9, 5.0, and 7.5 times, respectively, the results in the case without HONO constrained. Photolysis of HONO contributed to 86.5% of the total primary radical production rates and led to efficient NO2 and O3 production under the condition of weak regional transport of O3. The formation of HNO3 contributed to 98.4% of the total radical termination rates. Our results suggest that HONO could significantly increase the atmospheric oxidation capacity in a street canyon and enhance the secondary formation of HNO3 and HCHO, which can damage outdoor building materials and pose health risks to pedestrians.

Development of an activated carbon filter to remove NO2 and HONO in indoor air.

PubMed

Yoo, Jun Young; Park, Chan Jung; Kim, Ki Yeong; Son, Youn-Suk; Kang, Choong-Min; Wolfson, Jack M; Jung, In-Ha; Lee, Sung-Joo; Koutrakis, Petros

2015-05-30

To obtain the optimum removal efficiency of NO2 and HONO by coated activated carbon (ACs), the influencing factors, including the loading rate, metal and non-metal precursors, and mixture ratios, were investigated. The NOx removal efficiency (RE) for K, with the same loading (1.0 wt.%), was generally higher than for those loaded with Cu or Mn. The RE of NO2 was also higher when KOH was used as the K precursor, compared to other K precursors (KI, KNO3, and KMnO4). In addition, the REs by the ACs loaded with K were approximately 38-55% higher than those by uncoated ACs. Overall, the REs (above 95%) of HONO and NOx with 3% KOH were the highest of the coated AC filters that were tested. Additionally, the REs of NOx and HONO using a mixing ratio of 6 (2.5% PABA (p-aminobenzoic acid)+6% H3PO4):4 (3% KOH) were the highest of all the coatings tested (both metal and non-metal). The results of this study show that AC loaded with various coatings has the potential to effectively reduce NO2 and HONO levels in indoor air. Copyright © 2015 Elsevier B.V. All rights reserved.

Reaction of H + HONO in solid para-hydrogen: infrared spectrum of ˙ONH(OH).

PubMed

Haupa, Karolina Anna; Tielens, Alexander Godfried Gerardus Maria; Lee, Yuan-Pern

2017-06-21

Hydrogenation reactions in the N/O chemical network are important for an understanding of the mechanism of formation of organic molecules in dark interstellar clouds, but many reactions remain unknown. We present the results of the reaction H + HONO in solid para-hydrogen (p-H 2 ) at 3.3 K investigated with infrared spectra. Two methods that produced hydrogen atoms were the irradiation of HONO molecules in p-H 2 at 365 nm to produce OH radicals that reacted readily with nearby H 2 to produce mobile H atoms, and irradiation of Cl 2 molecules (co-deposited with HONO) in p-H 2 at 405 nm to produce Cl atoms that reacted, upon IR irradiation of the p-H 2 matrix, readily with nearby H 2 to produce mobile H atoms. In both experiments, we assigned IR lines at 3549.6 (ν 1 ), 1465.0 (ν 3 ), 1372.2 (ν 4 ), 898.5/895.6 (ν 6 ), and 630.9 (ν 7 ) cm -1 to hydroxy(oxido)-λ 5 -azanyl radical [˙ONH(OH)], the primary product of HONO hydrogenation. Two weak lines at 3603.4 and 991.0 cm -1 are tentatively assigned to the dihydroxy-λ 5 -azanyl radical, ˙N(OH) 2 . The assignments were derived according to the consideration of possible reactions and comparison of observed vibrational wavenumbers and their IR intensities with values predicted quantum-chemically with the B3LYP/aug-cc-pVTZ method. The agreement between observed and calculated D/H- and 15 N/ 14 N-isotopic ratios further supports these assignments. The role of this reaction in the N/O chemical network in dark interstellar clouds is discussed.

Significant HONO concentration at a semi-rural site in the Pearl River Delta during a severe pollution period and its impact on atmospheric oxidation capacity

NASA Astrophysics Data System (ADS)

Yun, H.; Wang, T.; Wang, W.; Yu, C.; Xia, M.; Xue, L.; Wang, Z.; Zhang, N.; Poon, S.; Zhou, Y.; Yue, D.; Zhai, Y.

2017-12-01

Nitrous acid (HONO) is an important source of hydroxyl radical (OH) in the boundary layer, and has considerable impact on atmospheric oxidation capacity and ozone formation. However, the abundance of HONO and subsequent effects under severe pollution conditions, especially in winter, has not been thoroughly investigated. We conducted an intensive observation at a semi-rural site (Heshan) in the center of the Pearl River Delta (PRD) in January 2017. Extremely high HONO concentrations (up to 9.0 ppbv) were observed with a LOng-Path Absorption Photometer (LOPAP) in a severe pollution episode with especially high PM2.5 ( 400 μg m-3) and O3 ( 160 ppbv). HONO sustained at a relatively high level in the morning and had peaks even in the afternoon. An observation-based box model (OBM) built on Master Chemical Mechanism (MCM v3.3.1) was used to simulate the formation of HONO and its contribution to the radical concentrations. The results showed that HONO was the dominant source of primary radicals (= OH+HO2+RO2) and governed the in-situ production of ozone. Currently-identified HONO sources were added into the model to reveal the formation process of HONO during both the nighttime and daytime, and the relative importance of these sources will be discussed.

Wavelength-Resolved Photon Fluxes of Indoor Light Sources: Implications for HOx Production

NASA Astrophysics Data System (ADS)

Kowal, S.; Kahan, T.

2017-12-01

Only a handful of studies have considered photolytic reactions indoors because photon fluxes at short wavelengths are generally considered to be negligible. We have measured wavelength resolved photon fluxes from indoor light sources including incandescent, halogen, compact fluorescent (CFL), and light emitting diodes (LED). In addition, fluorescent tubes, used in many offices and industrial buildings, and sunlight through windows were measured. The measured photon fluxes were used to calculate photolysis rate constants for potential indoor hydroxyl and peroxy radical (OH and HO2, "HOx") precursors: acetaldehyde (CH3CHO), formaldehyde (HCHO), hydrogen peroxide (H2O2), nitrous acid (HONO) and ozone (O3). Rate constants in conjunction with typical indoor concentrations were used to predict HOx production rates under various lighting conditions. Our results illustrate that all light sources except LEDs emit light at high enough energy to photolyze HOx precursors. Under typical lighting conditions only fluorescent tubes and sunlight will initiate significant photochemical HOx formation, and HONO and HCHO will be the only molecules that will have a strong influence on HOx levels indoors. Data from our experiments can be used in indoor air models to better predict HOx levels indoors.

Investigation of effective line intensities of trans-HONO near 1255 cm-1 using continuous-wave quantum cascade laser spectrometers

NASA Astrophysics Data System (ADS)

Cui, Xiaojuan; Dong, Fengzhong; Sigrist, Markus W.; Zhang, Zhirong; Wu, Bian; Xia, Hua; Pang, Tao; Sun, Pengshuai; Fertein, Eric; Chen, Weidong

2016-10-01

Effective line intensities of P branch transitions of trans-nitrous acid (HONO) in the ν3 H-O-N bending mode near 1255 cm-1 have been determined by scaling measured HONO absorption intensities by continuous-wave quantum cascade laser absorption spectroscopy to reference values. Gaseous HONO samples were synthetized in the laboratory using the reaction of H2SO4 and NaNO2 solutions and the heterogeneous formation on surfaces in the presence of ambient water vapor and NO2 gas in a sealed gas sampling bag. The quantification of HONO was performed using a denuder associated with a NOx analyzer. Observed absorption line strengths for the trans conformer are found to be by a factor of approximately 1.17 higher than previously reported line strengths.

Observations of Radical Precursors during TexAQS II: Findings and Implications

NASA Astrophysics Data System (ADS)

Olaguer, E. P.; Lefer, B. L.; Rappenglueck, B.; Pinto, J. P.

2009-12-01

The Texas Environmental Research Consortium (TERC) sponsored and helped organize significant components of the Second Texas Air Quality Study (TexAQS II). Some of the TERC-sponsored experiments, most notably those associated with the TexAQS II Radical and Aerosol Measurement Project (TRAMP) sited on top of the Moody Tower at the University of Houston, found evidence for the importance of short-lived radical sources such as formaldehyde (HCHO) and nitrous acid (HONO) in increasing ozone productivity. During TRAMP, daytime HCHO pulses as large as 32 ppb were observed and attributed to industrial activities upwind in the Houston Ship Channel (HSC), and HCHO peaks as large as 52 ppb were detected by in-situ surface monitors in the HSC. In addition, an instrumented Piper Aztec aircraft observed plumes of apparent primary formaldehyde in flares from petrochemical facilities in the HSC. In one such combustion plume, depleted of ozone by large NOx emissions, the Piper Aztec measured an HCHO-to-CO ratio three times that of mobile sources. HCHO from uncounted primary sources or ozonolysis of underestimated olefin emissions could significantly increase ozone productivity in Houston beyond previous expectations. Simulations with the CAMx model show that additional emissions of HCHO from industrial flares can increase peak ozone in Houston by up to 30 ppb, depending on conditions in the planetary boundary layer. Other findings from TexAQS II include significant concentrations of HONO throughout the day, well in excess of current air quality model predictions, with large nocturnal vertical gradients indicating a surface or near-surface source of HONO, and large concentrations of night-time radicals (~30 ppt HO2). Additional HONO sources could increase daytime ozone by more than 10 ppb. Improving the representation of primary and secondary HCHO and HONO in air quality models could enhance the effectiveness of simulated control strategies, and thus make ozone attainment

Inter-comparison of HONO field measurements and its summertime variation in Seoul, Korea

NASA Astrophysics Data System (ADS)

Kim, J.; Lee, G.; Lee, D.; Cho, S.

2017-12-01

HONO is a key source of OH radical responsible for atmospheric oxidative capacity and plays an important role in heterogeneous oxidation of some species. To understand the oxidative mechanisms that lead to urban ozone and aerosol formation we need to know the sources and behavior of this trace gas. Despite its importance, HONO budgets, especially in the urban conditions in Korea are not well understood. In this study, HONO measurement was conducted in Olympic Park located in Seoul, Korea from May 19 to June 15 of 2016 using Quantum Cascade-Tunable Infrared Laser Differential Absorption Spectrometer (QC-TILDAS), High Efficiency Diffusion Scrubber-Ion Chromatography (HEDS-IC) and Monitor for AeRosols & Gases in ambient Air (MARGA). Overall, the measurements obtained with the three instruments agreed within analysis uncertainty. The resulting detection limits of all instruments were close to 0.10 ppbv for HONO. HONO concentrations over the measurement period varied from the detection limit to 3.46 ppbv (QC-TILDAS), 3.03 ppbv (HEDS-IC) and 4.81 ppbv (MARGA), respectively. Using a chemical box model including varying PBL heights and emissions, major paths of HONO production and its contributions to ozone was identified. The model showed significant underestimation compared to observations, which suggests additional unknown HONO production or direct HONO emission.

Oxidative capacity of the Mexico City atmosphere - Part 1: A radical source perspective

NASA Astrophysics Data System (ADS)

Volkamer, R.; Sheehy, P. M.; Molina, L. T.; Molina, M. J.

2007-04-01

A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10-25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: HCHO and O3 photolysis, each about 20%; O3/alkene reactions and HONO photolysis, each about 15%; unmeasured sources about 30%. While the direct contribution of O3/alkene reactions appears to be moderately small, source-apportionment of ambient HCHO and HONO identifies O3/alkene reactions as being largely responsible for jump-starting photochemistry about one hour after sunrise. The peak radical production is found to be higher than in any other urban influenced environment studied to date; further, differences exist in the timing of radical production. Our measurements and analysis comprise a database

BrO, OClO and HCHO Observations from the EOS-Aura Ozone Monitoring Instrument

NASA Astrophysics Data System (ADS)

Kurosu, T. P.; Chance, K.; Sioris, C. E.

2004-12-01

The Ozone Monitoring Instrument (OMI) was launched on 15 July 2004 on the EOS-Aura platform into a sun-synchronous, polar orbit with an equator crossing time of 13:45h (ascending node). OMI is a nadir-viewing near-UV/Visible spectrometer, covering the spectral region of 270 nm to 500 nm with a resolution between 0.45 nm and 1.0 nm and a nominal ground footprint of 13 km×24 km. Global coverage is achieved in one day. The very high spatial resolution of OMI measurements sets a new standard for trace gas and air quality monitoring from space. Combined with daily global coverage, this significantly advances our ability to answer outstanding questions on air pollution, including the determination of BrO sources in mid and low latitudes, BrO--O3 anti-correlations as a function of latitude, and the production of formaldehyde in cities of the developing world. We introduce the design of the OMI operational retrieval algorithm for BrO, OClO and HCHO. Based on a direct (non-DOAS) non-linear fitting approach, it includes wavelength calibration for radiances and irradiances, an undersampling correction, and the characterization of the instrument slit function. We will present results of BrO (global distribution, and tropospheric contributions from the break-up ice shelves and volcanic emissions), formaldehyde (over regions of isoprene emissions, forest fires, and heavy urban pollution), and, contingent upon the availability of suitable OMI observations, OClO (under ozone hole conditions). Where available, trace gas retrievals from OMI will be compared to results from the SCIAMACHY and GOME instruments.

The Oxidant Production over Antarctic Land and its Export (OPALE) project: An overview of data collected in summer 2011-2012 at Concordia

NASA Astrophysics Data System (ADS)

Kukui, Alexandre; Legrand, Michel; Frey, Markus; Preunkert, Susanne; Savarino, Joel; Gallée, Hubert; Vicars, William; Gil Roca, Jaime; Jourdain, Bruno

2015-04-01

The need to characterize the oxidative capacity of the atmosphere of East Antarctica motivated the OPALE investigations at the top of the high plateau (Concordia) where processes are suspected to differ from those already identified at South Pole. For instance, in contrast to South Pole experiencing 24-hour sunlight, the solar irradiance at Concordia has a strong diurnal cycle. This has consequences on intensity of snow emissions as well as on the dynamic of the boundary layer. Concordia is also the inland site where the longest chemical ice core records have been extracted. Investigations made at Concordia in December 2011-January 2012 included OH and RO2 together with concurrent measurements of NO, NO2, HONO, O3, H2O2, HCHO, photolysis rates as well as meteorological parameters and physics of the boundary layer. HONO was investigated by deploying for the first time in Antarctica an absorption photometer (LOPAP), an analyser supposed to be free of interferences with numerous chemical species. Also investigated for the first time is the excess of 17O of ozone with a newly developed fast sampling method. The diurnal cycle of snow emissions was also documented for NOx and HCHO that strongly influence the level of radicals. The concentrations of OH and RO2 radicals (median values of 3x106 and 1x108 in molecule cm-3, respectively) were found to be comparable to those observed at South Pole confirming that the elevated oxidative capacity is a common characteristic of near-surface atmospheric layer for most of the Antarctic plateau. Similar to the SP findings the major factor explaining to high radical levels at Concordia was the high levels of NO leading to fast recycling of RO2 to OH. At the same time, in contrast to the SP where the radical levels are controlled by NO levels mostly via changing boundary layer properties, OH and RO2 at Concordia show strong diurnal variability. The variability of NOx at Concordia is also determined by the solar diurnal cycle via an

Retrieval of tropospheric HCHO in El Salvador using ground based DOAS

NASA Astrophysics Data System (ADS)

Abarca, W.; Gamez, K.; Rudamas, C.

2017-12-01

Formaldehyde (HCHO) is the most abundant carbonyl in the atmosphere, being an intermediate product in the oxidation of most volatile organic compounds (VOCs). HCHO is carcinogenic, and highly water soluble [1]. HCHO can originate from biomass burning and fossil fuel combustion and has been observed from satellite and ground-based sensors by using the Differential Optical Absorption Spectroscopy (DOAS) technique [2].DOAS products can be used for air quality monitoring, validation of chemical transport models, validation of satellite tropospheric column density retrievals, among others [3]. In this study, we report on column density levels of HCHO measured by ground based Multi-Axis -DOAS in different locations of El Salvador in March, 2015. We have not observed large differences of the HCHO column density values at different viewing directions. This result points out a reasonably polluted and hazy atmosphere in the measuring sites, as reported by other authors [4]. Average values ranging from 1016 to 1017 molecules / cm2 has been obtained. The contribution of vehicular traffic and biomass burning to the column density levels in these sites of El Salvador will be discussed. [1] A. R. Garcia et al., Atmos. Chem. Phys. 6, 4545 (2006) [2] E. Peters et al., Atmos. Chem. Phys. 12, 11179 (2012) [3] T. Vlemmix, et al. Atmos. Meas. Tech., 8, 941-963, 2015 [4] A. Heckel et al., Atmos. Chem. Phys. 5, (2005)

Nitrous acid (HONO) measurements during winter haze events in Beijing

NASA Astrophysics Data System (ADS)

Bloss, W.; Kramer, L. J.; Crilley, L.; Lee, J. D.; Squires, F. A.; Tong, S.

2017-12-01

Daytime HONO levels can reach several parts per billion in megacities during winter haze events and hence act as the dominant (primary) precursor to OH radicals in the urban boundary layer, and affect NOx abundance. Understanding the sources of HONO is therefore important to quantify atmospheric oxidative capacity and secondary pollutant formation during such haze events. Despite decades of research, there are still large uncertainties in HONO formation mechanisms, and as a result models often substantially underestimate peak HONO levels. In this study, measurements of HONO were performed at the Institute of Atmospheric Physics (IAP) site located in central Beijing during Nov/Dec 2016, across both haze and non-haze events. Using a commercial long-path absorption photometer (LOPAP), vertical profiles of HONO concentrations up to a height of 260 m on the IAP Meteorological Tower were performed, as well as continuous near-surface measurements. Preliminary results showed that HONO levels near the ground were very high during the winter haze events with concentrations over 10 ppbV observed. Typically, during the vertical profiles a negative gradient was observed, indicating a large HONO source close to the surface. However, during some of the profiles elevated HONO concentrations were also observed at higher altitudes pointing to a strong source within the boundary layer. Co-located NOx and SO2 measurements are used to elucidate potential HONO sources from direct emissions, homogeneous gas phase reactions and heterogeneous conversion of NO2 on surfaces. Results from ground level HONO/NOx ratios show a midday peak during clean periods indicating a photo-enhanced process, which was not apparent during hazy days. The potential impact of these findings on the OH radical budget in wintertime Beijing will be discussed.

Sensitivities of winter ozone pollution events in oil and gas producing regions to VOCs, NOx and radicals (Invited)

NASA Astrophysics Data System (ADS)

Edwards, P. M.; Aikin, K.; De Gouw, J. A.; Dube, W. P.; Geiger, F.; Gilman, J.; Helmig, D.; Holloway, J.; Kercher, J. P.; Koss, A.; Lerner, B. M.; Martin, R. S.; McLaren, R.; Min, K.; Parrish, D. D.; Peischl, J.; Roberts, J. M.; Ryerson, T. B.; Thornton, J. A.; Veres, P. R.; Warneke, C.; Wild, R. J.; Williams, E. J.; Young, C.; Yuan, B.; Brown, S. S.

2013-12-01

The Uintah Basin in northeastern Utah, a region of intense oil and gas extraction, experienced ozone (O3) mixing ratios well above limits set by air quality standards for multiple days during three of the last four winters. The Uintah Basin Winter Ozone Study (UBWOS) consisted of two field intensives, in early 2012 and 2013, with the goal of addressing current uncertainties in the chemical and physical processes that drive wintertime O3 production in regions of oil and gas development. The data from these two study periods provide an excellent comparison of high and low O3 production years, as meteorological conditions during the winter of 2011-2012 resulted in no elevated O3 mixing ratios, in contrast to the winter of 2012-2013 when observed O3 mixing ratios were the highest yet recorded in the Uintah Basin. Box modeling studies, using the Master Chemical Mechanism (MCM v3.2) chemistry scheme, have been used to investigate our understanding of O3 photochemistry in this unusual emissions environment. Simulations identify O3 production in 2012 to be highly radical limited, with less conventional radical sources, such as HCHO, HONO, and ClNO2 photolysis, playing a central role. Consequently, O3 production during 2012 was highly VOC sensitive, despite the much larger mixing ratio of total non-methane hydrocarbons relative to NO¬x. Conditions during UBWOS 2013 resulted in significantly higher O3 precursor species concentrations than during 2012, including the concentrations of the radical precursors HCHO and HONO. Simulations constrained to the 2013 data show the effects of these changes in pre-cursor concentrations on the radical budget, and thus on local O3 photochemistry and its sensitivities during a wintertime O3 pollution episode.

Photoenhanced uptakes of NO2 by indoor surfaces: A new HONO source

NASA Astrophysics Data System (ADS)

Gligorovski, S.; Bartolomei, V.; Soergel, M.; Gomez Alvarez, E.; Zetzsch, C.; Wortham, H.

2012-12-01

Nitrous acid (HONO) is a known household pollutant that can lead to human respiratory tract irritation. HONO acts as the nitrosating agent, e.g. by the formation of the so-called third-hand smoke after wall reactions of HONO with nicotine (1). HONO can be generated indoors directly during combustion processes or indirectly via heterogeneous NO2 reactions with adsorbed water on diverse surfaces (2). Recently a new source was identified as another path of HONO formation in the troposphere (3). Namely, the light-induced heterogeneous reaction of NO2 with adsorbed organics (known as photosensitizers) on various surfaces such as roads, buildings, rocks or plants leads to enhanced HONO production. The detected values of HONO indoors vary in the range between 2 and 25 parts per billion (ppb). However, like outdoors, the processes leading to HONO formation indoors are not completely understood (4). Indoor photolysis radiation sources include exterior sunlight (λ>350 nm) that enters typically through the windows and indoor illumination sources, i.e., rare gas/mercury fluorescent light bulbs and tungsten and tungsten/halogen light bulbs among others. The present work is showing the importance of indoor sources of HONO recently identified or postulated. We have tested a number of common household chemical agents commonly used for cleaning purposes or coatings of domestic surfaces to better identify different indoor HONO sources. We used a heterogeneous flow tube technique to test the HONO production potentials of these household chemical agents under different experimental conditions, namely with and without light and at different relative humidity levels and different NO2 concentrations. We report uptake kinetics measurements of the heterogeneous reaction of gas phase NO2 with lacquer and paint coated on the walls of the reactor. The flow tube was irradiated with four near-ultraviolet (UV) emitting lamps (range of wavelengths 300-420nm). We observed that the heterogeneous

Characterizing agricultural soil nitrous acid (HONO) and nitric oxide (NO) emissions with their nitrogen isotopic composition

NASA Astrophysics Data System (ADS)

Chai, J.; Miller, D. J.; Guo, F.; Dell, C. J.; Karsten, H.; Hastings, M. G.

2017-12-01

Nitrous acid (HONO) is a major source of atmospheric hydroxyl radical (OH), which greatly impacts air quality and climate. Fertilized soils may be important sources of HONO in addition to nitric oxide (NO). However, soil HONO emissions are especially challenging to quantify due to huge spatial and temporal variation as well as unknown HONO chemistry. With no in-situ measurements available, soil HONO emissions are highly uncertain. Isotopic analysis of HONO may provide a tool for tracking these sources. We characterize in situ soil HONO and NO fluxes and their nitrogen isotopic composition (δ15N) across manure management and meteorological conditions during a sustainable dairy cropping study in State College, Pennsylvania. HONO and NO were simultaneously collected at hourly resolution from a custom-coated dynamic soil flux chamber ( 3 LPM) using annular denuder system (ADS) coupled with an alkaline-permanganate NOx collection system for offline isotopic analysis of δ15N with ±0.6 ‰ (HONO) and ±1.5 ‰ (NO) precision. The ADS method was tested using laboratory generated HONO flowing through the chamber to verify near 100% collection (with no isotopic fractionation) and suitability for soil HONO collection. Corn-soybean rotation plots (rain-fed) were sampled following dairy manure application with no-till shallow-disk injection (112 kg N ha-1) and broadcast with tillage incorporation (129 kg N ha-1) during spring 2017. Soil HONO fluxes (n=10) ranged from 0.1-0.6 ng N-HONO m-2 s-1, 4-28% of total HONO+NO mass fluxes. HONO and NO fluxes were correlated, with both declining during the measurement period. The soil δ15N-HONO flux weighted mean ±1σ of -15 ± 6‰ was less negative than δ15N of simultaneously collected NO (-29 ± 8‰). This can potentially be explained by fractionations associated with microbial conversion of nitrite, abiotic production of HONO from soil nitrite, and uptake and release with changing soil moisture. Our results have implications for

Detailed budget analysis of HONO in central London reveals a missing daytime source

NASA Astrophysics Data System (ADS)

Lee, J. D.; Whalley, L. K.; Heard, D. E.; Stone, D.; Dunmore, R. E.; Hamilton, J. F.; Young, D. E.; Allan, J. D.; Laufs, S.; Kleffmann, J.

2015-08-01

Measurements of HONO were carried out at an urban background site near central London as part of the Clean air for London (ClearfLo) project in summer 2012. Data was collected from 22 July-18 August 2014, with peak values of up to 1.8 ppbV at night and non-zero values of between 0.2 and 0.6 ppbV seen during the day. A wide range of other gas phase, aerosol, radiation and meteorological measurements were made concurrently at the same site, allowing a detailed analysis of the chemistry to be carried out. The peak HONO/NOx ratio of 0.04 is seen at ~ 02:00 UTC, with the presence of a second, daytime peak in HONO/NOx of similar magnitude to the night-time peak suggesting a significant secondary daytime HONO source. A photostationary state calculation of HONO involving formation from the reaction of OH and NO and loss from photolysis, reaction with OH and dry deposition shows a significant underestimation during the day, with calculated values being close to zero, compared to the measurement average of 0.4 ppbV at midday. The addition of further HONO sources, including postulated formation from the reaction of HO2 with NO2 and photolysis of HNO3, increases the daytime modelled HONO to 0.1 ppbV, still leaving a significant extra daytime source. The missing HONO is plotted against a series of parameters including NO2 and OH reactivity, with little correlation seen. Much better correlation is observed with the product of these species with j(NO2), in particular NO2 and the product of NO2 with OH reactivity. This suggests the missing HONO source is in some way related to NO2 and also requires sunlight. The effect of the missing HONO to OH radical production is also investigated and it is shown that the model needs to be constrained to measured HONO in order to accurately reproduce the OH radical measurements.

NO2 and HCHO variability in Mexico City from MAX-DOAS measurements

NASA Astrophysics Data System (ADS)

Grutter, M.; Friedrich, M. M.; Rivera, C. I.; Arellano, E. J.; Stremme, W.

2015-12-01

Atmospheric studies in large cities are of great relevance since pollution affects air quality and human health. A network of Multi Axis Differential Optical Absorption Spectrometers (MAX-DOAS) has been established in strategic sites within the Mexico City metropolitan area. Four instruments are now in operation with the aim to study the variability and spatial distribution of key pollutants, providing results of O4, NO2 and HCHO slant column densities (SCD). A numerical code has been written to retrieve gas profiles of NO2 and HCHO using radiative transfer simulations. We present the first results of the variability of these trace gases which will bring new insight in the current knowledge of transport patterns, emissions as well as frequency and origin of extraordinary events. Results of the vertical column densities (VCD) valiability of NO2 and HCHO in Mexico City are presented. These studies are useful to validate current and future satellite observatopns such as OMI, TROPOMI and TEMPO.

Investigation of the 3D distribution of tropospheric formaldehyde (HCHO) at the city of Mainz (Germany) using measurements of a 4 azimuth MAX-DOAS instrument

NASA Astrophysics Data System (ADS)

Donner, Sebastian; Gu, Myojeong; Remmers, Julia; Wang, Yang; Wagner, Thomas

2017-04-01

The Differential Optical Absorption Spectroscopy (DOAS)-method allows to investigate the distribution of different atmospheric trace gases (e.g. NO2, SO2, HCHO...) simultaneously. This is done by analysing the absorptions of these species in spectra of scattered sunlight. Multi-AXis (MAX)-DOAS measurements observe scattered sun light under different elevation angles. From such measurements tropospheric vertical column densities (VCDs) and vertical profiles of the measured trace gases and aerosols can be determined. We performed measurements using a 4 azimuth MAX-DOAS system on the roof of the Max Planck Institute for Chemistry in Mainz/Germany since 2013. This instrument observes scattered sunlight in 4 separate orthogonal azimuth directions. We derive vertical profiles of trace gases in these 4 different azimuth directions. From these results we can investigate the 3D distribution of the trace gases. Mainz is located at the edge of the Rhine-Main area which is one of the densest populated areas in Germany. Therefore it experiences episodes of high and low pollution depending on the meteorological conditions. In this study we focus on formaldehyde (HCHO). It is either emitted directly by industries and other anthropogenic and biogenic activities. Usually higher amounts are produced by photochemical reactions from precursor substances (secondary production), where it plays an important role in photochemical smog chemistry and O3 chemistry. As it is an intermediate product of basic oxidation cycles of other hydrocarbons (also referred to as volatile organic compounds (VOCs)) especially in summer its concentrations are determined by the abundances of VOCs. Therefore HCHO observations can be used as an indicator for VOCs. Up to now we have nearly 4 years (starting from May 2013) of almost continuous data which provides already a quite large dataset. In this work we present a first overview of our HCHO results including time series of HCHO columns, a first comparison of

Measurement of HONO Production From Traffic in a UK Road Tunnel

NASA Astrophysics Data System (ADS)

Kramer, L. J.; Crilley, L.; Adams, T. J.; Ball, S. M.; Pope, F.; Bloss, W.

2016-12-01

Nitrous Acid (HONO) has an important role in the boundary layer as a source of hydroxyl radicals (OH) which can oxidize VOCs and, in the presence of NOx, lead to the formation of ozone. In urban areas with high traffic density, vehicular emissions can be an important source of HONO, however, there are limited real-world studies on HONO emissions from vehicles and large uncertainties on emission values from different traffic fleets (e.g. diesel, gasoline cars, and light- and heavy-duty vehicles). Here, we will present preliminary results from measurements of HONO, nitrogen oxides, CO2 and particulate matter performed over the summer in a road tunnel in Birmingham, UK. A broadband cavity enhanced absorption spectroscopy system (BBCEAS) was deployed to perform high temporal resolution measurements (20 s) of HONO and NO2, alongside commercial analysers for NO, NOy, CO2 and PM. Using information on vehicle density and traffic fleet, emissions ratios of HONO/NOx and estimates of direct HONO emissions will be presented.

Laser-Based and Ultra-Portable Gas Sensor for Indoor and Outdoor Formaldehyde (HCHO) Monitoring

NASA Astrophysics Data System (ADS)

Shutter, J. D.; Allen, N.; Paul, J.; Thiebaud, J.; So, S.; Scherer, J. J.; Keutsch, F. N.

2017-12-01

While used as a key tracer of oxidative chemistry in the atmosphere, formaldehyde (HCHO) is also a known human carcinogen and is listed and regulated by the United States EPA as a hazardous air pollutant. Combustion processes and photochemical oxidation of volatile organic compounds (VOCs) are the major outdoor sources of HCHO, and building materials and household products are ubiquitous sources of indoor HCHO. Due to the ease with which humans can be exposed to HCHO, it is imperative to monitor levels of both indoor and outdoor HCHO exposure in both short and long-term studies.High-quality direct and indirect methods of quantifying HCHO mixing ratios exist, but instrument size and user-friendliness can make them cumbersome or impractical for certain types of indoor and long-term outdoor measurements. In this study, we present urban HCHO measurements by using a new, commercially-available, ppbv-level accurate HCHO gas sensor (Aeris Technologies' MIRA Pico VOC Laser-Based Gas Analyzer) that is highly portable (29 cm x 20 cm x 10 cm), lightweight (3 kg), easy-to-use, and has low power (15 W) consumption. Using an ultra-compact multipass cell, an absorption path length of 13 m is achieved, resulting in a sensor capable of achieving ppbv/s sensitivity levels with no significant spectral interferences.To demonstrate the utility of the gas sensor for emissions measurements, a GPS was attached to the sensor's housing in order to map mobile HCHO measurements in real-time around the Boston, Massachusetts, metro area. Furthermore, the sensor was placed in residential and industrial environments to show its usefulness for indoor and outdoor pollution measurements. Lastly, we show the feasibility of using the HCHO sensor (or a network of them) in long-term monitoring stations for hazardous air pollutants.

CARIBIC DOAS observations of nitrous acid and formaldehyde in a large convective cloud

NASA Astrophysics Data System (ADS)

Heue, K.-P.; Riede, H.; Walter, D.; Brenninkmeijer, C. A. M.; Wagner, T.; Frieß, U.; Platt, U.; Zahn, A.; Stratmann, G.; Ziereis, H.

2014-07-01

The chemistry in large thunderstorm clouds is influenced by local lightning-NOx production and uplift of boundary layer air. Under these circumstances trace gases like nitrous acid (HONO) or formaldehyde (HCHO) are expected to be formed or to reach the tropopause region. However, up to now only few observations of HONO at this altitude have been reported. Here we report on a case study where enhancements in HONO, HCHO and nitrogen oxides (NOx) were observed by the CARIBIC flying laboratory (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container). The event took place in a convective system over the Caribbean Sea in August 2011. Inside the cloud the light path reaches up to 100 km. Therefore the DOAS instrument on CARIBIC was very sensitive to the tracers inside the cloud. Based on the enhanced slant column densities of HONO, HCHO and NO2, average mixing ratios of 37, 468 and 210 ppt, respectively, were calculated. These data represent averages for constant mixing ratios inside the cloud. However, a large dependency on the assumed profile is found; for HONO a mixing ratio of 160 ppt is retrieved if the total amount is assumed to be situated in the uppermost 2 km of the cloud. The NO in situ instrument measured peaks up to 5 ppb NO inside the cloud; the background in the cloud was about 1.3 ppb, and hence clearly above the average outside the cloud (≈ 150 ppt). The high variability and the fact that the enhancements were observed over a pristine marine area led to the conclusion that, in all likelihood, the high NO concentrations were caused by lighting. This assumption is supported by the number of flashes that the World Wide Lightning Location Network (WWLLN) counted in this area before and during the overpass. The chemical box model CAABA is used to estimate the NO and HCHO source strengths which are necessary to explain our measurements. For NO a source strength of 10 × 109 molec cm-2 s-1 km-1 is found, which

Light-induced nitrous acid (HONO) production from NO2 heterogeneous reactions on household chemicals

NASA Astrophysics Data System (ADS)

Gómez Alvarez, Elena; Sörgel, Matthias; Gligorovski, Sasho; Bassil, Sabina; Bartolomei, Vincent; Coulomb, Bruno; Zetzsch, Cornelius; Wortham, Henri

2014-10-01

Nitrous acid (HONO) can be generated in various indoor environments directly during combustion processes or indirectly via heterogeneous NO2 reactions with water adsorbed layers on diverse surfaces. Indoors not only the concentrations of NO2 are higher but the surface to volume (S/V) ratios are larger and therefore the potential of HONO production is significantly elevated compared to outdoors. It has been claimed that the UV solar light is largely attenuated indoors. Here, we show that solar light (λ > 340 nm) penetrates indoors and can influence the heterogeneous reactions of gas-phase NO2 with various household surfaces. The NO2 to HONO conversion mediated by light on surfaces covered with domestic chemicals has been determined at atmospherically relevant conditions i.e. 50 ppb NO2 and 50% RH. The formation rates of HONO were enhanced in presence of light for all the studied surfaces and are determined in the following order: 1.3·109 molecules cm-2 s-1 for borosilicate glass, 1.7·109 molecules cm-2 s-1 for bathroom cleaner, 1.0·1010 molecules cm-2 s-1 on alkaline detergent (floor cleaner), 1.3·1010 molecules cm-2 s-1 for white wall paint and 2.7·1010 molecules cm-2 s-1 for lacquer. These results highlight the potential of household chemicals, used for cleaning purposes to generate HONO indoors through light-enhanced NO2 heterogeneous reactions. The results obtained have been applied to predict the timely evolution of HONO in a real indoor environment using a dynamic mass balance model. A steady state mixing ratio of HONO has been estimated at 1.6 ppb assuming a contribution from glass, paint and lacquer and considering the photolysis of HONO as the most important loss process.

A comparison of measured HONO uptake and release with calculated source strengths in a heterogeneous forest environment

NASA Astrophysics Data System (ADS)

Sörgel, Matthias; Trebs, Ivonne; Wu, Dianming; Held, Andreas

2015-04-01

Vertical mixing ratio profiles of nitrous acid (HONO) were measured in a clearing and on the forest floor in a rural forest environment (in the south-east of Germany) by applying a lift system to move the sampling unit of the LOng Path Absorption Photometer (LOPAP) up and down. For the forest floor, HONO was found to be predominantly deposited, whereas net deposition was dominating in the clearing only during nighttime and net emissions were observed during daytime. For selected days, net fluxes of HONO were calculated from the measured profiles using the aerodynamic gradient method. The emission fluxes were in the range of 0.02 to 0.07 nmol m-2 s-1, and, thus were in the lower range of previous observations. These fluxes were compared to the strengths of postulated HONO sources and to the amount of HONO needed to sustain photolysis in the boundary layer. Laboratory measurements of different soil samples from both sites revealed an upper limit for soil biogenic HONO emission fluxes of 0.025 nmol m-2 s-1. HONO formation by light induced NO2 conversion was calculated to be below 0.03 nmol m-2 s-1 for the investigated days, which is comparable to the potential soil fluxes. Due to light saturation at low irradiance, this reaction pathway was largely found to be independent of light intensity, i.e. it was only dependent on ambient NO2. We used three different approaches based on measured leaf nitrate loadings for calculating HONO formation from HNO3 photolysis. While the first two approaches based on empirical HONO formation rates yielded values in the same order of magnitude as the estimated fluxes, the third approach based on available kinetic data of the postulated pathway failed to produce noticeable amounts of HONO. Estimates based on reported cross sections of adsorbed HNO3 indicate that the lifetime of adsorbed HNO3 was only about 15 min, which would imply a substantial renoxification. Although the photolysis of HNO3 was significantly enhanced at the surface, the

Which processes drive observed variations of HCHO columns over India?

NASA Astrophysics Data System (ADS)

Surl, Luke; Palmer, Paul I.; González Abad, Gonzalo

2018-04-01

We interpret HCHO column variations observed by the Ozone Monitoring Instrument (OMI), aboard the NASA Aura satellite, over India during 2014 using the GEOS-Chem atmospheric chemistry and transport model. We use a nested version of the model with a horizontal resolution of approximately 25 km. HCHO columns are related to local emissions of volatile organic compounds (VOCs) with a spatial smearing that increases with the VOC lifetime. Over India, HCHO has biogenic, pyrogenic, and anthropogenic VOC sources. Using a 0-D photochemistry model, we find that isoprene has the largest molar yield of HCHO which is typically realized within a few hours. We also find that forested regions that neighbour major urban conurbations are exposed to high levels of nitrogen oxides. This results in depleted hydroxyl radical concentrations and a delay in the production of HCHO from isoprene oxidation. We find that propene is the only anthropogenic VOC emitted in major Indian cities that produces HCHO at a comparable (but slower) rate to isoprene. The GEOS-Chem model reproduces the broad-scale annual mean HCHO column distribution observed by OMI (r = 0.6), which is dominated by a distinctive meridional gradient in the northern half of the country, and by localized regions of high columns that coincide with forests. Major discrepancies are noted over the Indo-Gangetic Plain (IGP) and Delhi. We find that the model has more skill at reproducing observations during winter (JF) and pre-monsoon (MAM) months with Pearson correlations r > 0.5 but with a positive model bias of x≃1×1015 molec cm-2. During the monsoon season (JJAS) we reproduce only a diffuse version of the observed meridional gradient (r = 0.4). We find that on a continental scale most of the HCHO column seasonal cycle is explained by monthly variations in surface temperature (r = 0.9), suggesting a role for biogenic VOCs, in agreement with the 0-D and GEOS-Chem model calculations. We also find that the seasonal cycle during

Photo-induced formation of nitrous acid (HONO) on protein surfaces

NASA Astrophysics Data System (ADS)

Meusel, Hannah; Elshorbany, Yasin; Bartels-Rausch, Thorsten; Selzle, Kathrin; Lelieveld, Jos; Ammann, Markus; Pöschl, Ulrich; Su, Hang; Cheng, Yafang

2014-05-01

The study of nitrous acid (HONO) is of great interest, as the photolysis of HONO leads to the OH radical, which is the most important oxidant in the troposphere. HONO is directly emitted by combustion of fossil fuel and from soil biogenic nitrite (Su et al., 2011), and can also be formed by gas phase reactions of NO and OH and heterogeneous reactions of NO2. Previous atmospheric measurements have shown unexpectedly high HONO concentrations during daytime. Measured mixing ratios were about one order of magnitude higher than model simulations (Kleffmann et al. 2005, Vogel et al. 2003). The additional daytime source of HONO might be attributed to the photolysis of adsorbed nitric acid or heterogeneous photochemistry of NO2 on organic substrates, such as humic acids or polyphenolic compounds (Stemmler et al., 2006), or indirectly through nitration of phenols and subsequent photolysis of nitrophenols (Sosedova et al., 2011, Bejan et al., 2006). An important reactive surface for the heterogeneous formation of HONO could involve proteins, which are ubiquitous in the environment. They are part of coarse biological aerosol particles like pollen grains, fine particles (fragments of pollen, microorganism, plant debris) and dissolved in rainwater, soil and road dust (Miguel et al. 1999). In this project a thin film of bovine serum albumin (BSA), a model protein with 67 kDa and 21 tyrosine residues per molecule, is irradiated and exposed to nitrogen dioxide in humidified nitrogen. The formation of HONO is measured with long path absorption photometry (LOPAP). The generated HONO is in the range of 100 to 1100 ppt depending on light intensity, NO2 concentration and film thickness. Light induced HONO formation on protein surfaces is stable over the 20-hours experiment of irradiation and exposure. On the other hand, light activated proteins reacting with NO2 form nitrated proteins, as detected by liquid chromatography (LC-DAD). Our experiments on tetranitromethane (TNM) nitrated

Light-induced protein nitration and degradation with HONO emission

NASA Astrophysics Data System (ADS)

Meusel, Hannah; Elshorbany, Yasin; Kuhn, Uwe; Bartels-Rausch, Thorsten; Reinmuth-Selzle, Kathrin; Kampf, Christopher J.; Li, Guo; Wang, Xiaoxiang; Lelieveld, Jos; Pöschl, Ulrich; Hoffmann, Thorsten; Su, Hang; Ammann, Markus; Cheng, Yafang

2017-10-01

Proteins can be nitrated by air pollutants (NO2), enhancing their allergenic potential. This work provides insight into protein nitration and subsequent decomposition in the presence of solar radiation. We also investigated light-induced formation of nitrous acid (HONO) from protein surfaces that were nitrated either online with instantaneous gas-phase exposure to NO2 or offline by an efficient nitration agent (tetranitromethane, TNM). Bovine serum albumin (BSA) and ovalbumin (OVA) were used as model substances for proteins. Nitration degrees of about 1 % were derived applying NO2 concentrations of 100 ppb under VIS/UV illuminated conditions, while simultaneous decomposition of (nitrated) proteins was also found during long-term (20 h) irradiation exposure. Measurements of gas exchange on TNM-nitrated proteins revealed that HONO can be formed and released even without contribution of instantaneous heterogeneous NO2 conversion. NO2 exposure was found to increase HONO emissions substantially. In particular, a strong dependence of HONO emissions on light intensity, relative humidity, NO2 concentrations and the applied coating thickness was found. The 20 h long-term studies revealed sustained HONO formation, even when concentrations of the intact (nitrated) proteins were too low to be detected after the gas exchange measurements. A reaction mechanism for the NO2 conversion based on the Langmuir-Hinshelwood kinetics is proposed.

Potential sources of nitrous acid (HONO) and their impacts on ozone: A WRF-Chem study in a polluted subtropical region

NASA Astrophysics Data System (ADS)

Zhang, Li; Wang, Tao; Zhang, Qiang; Zheng, Junyu; Xu, Zheng; Lv, Mengyao

2016-04-01

Current chemical transport models commonly undersimulate the atmospheric concentration of nitrous acid (HONO), which plays an important role in atmospheric chemistry, due to the lack or inappropriate representations of some sources in the models. In the present study, we parameterized up-to-date HONO sources into a state-of-the-art three-dimensional chemical transport model (Weather Research and Forecasting model coupled with Chemistry: WRF-Chem). These sources included (1) heterogeneous reactions on ground surfaces with the photoenhanced effect on HONO production, (2) photoenhanced reactions on aerosol surfaces, (3) direct vehicle and vessel emissions, (4) potential conversion of NO2 at the ocean surface, and (5) emissions from soil bacteria. The revised WRF-Chem was applied to explore the sources of the high HONO concentrations (0.45-2.71 ppb) observed at a suburban site located within complex land types (with artificial land covers, ocean, and forests) in Hong Kong. With the addition of these sources, the revised model substantially reproduced the observed HONO levels. The heterogeneous conversions of NO2 on ground surfaces dominated HONO sources contributing about 42% to the observed HONO mixing ratios, with emissions from soil bacterial contributing around 29%, followed by the oceanic source (~9%), photochemical formation via NO and OH (~6%), conversion on aerosol surfaces (~3%), and traffic emissions (~2%). The results suggest that HONO sources in suburban areas could be more complex and diverse than those in urban or rural areas and that the bacterial and/or ocean processes need to be considered in HONO production in forested and/or coastal areas. Sensitivity tests showed that the simulated HONO was sensitive to the uptake coefficient of NO2 on the surfaces. Incorporation of the aforementioned HONO sources significantly improved the simulations of ozone, resulting in increases of ground-level ozone concentrations by 6-12% over urban areas in Hong Kong and

Soil HONO Emissions and Its Potential Impact on the Atmospheric Chemistry and Nitrogen Cycle

NASA Astrophysics Data System (ADS)

Su, H.; Chen, C.; Zhang, Q.; Poeschl, U.; Cheng, Y.

2014-12-01

Hydroxyl radicals (OH) are a key species in atmospheric photochemistry. In the lower atmosphere, up to ~30% of the primary OH radical production is attributed to the photolysis of nitrous acid (HONO), and field observations suggest a large missing source of HONO. The dominant sources of N(III) in soil, however, are biological nitrification and denitrification processes, which produce nitrite ions from ammonium (by nitrifying microbes) as well as from nitrate (by denitrifying microbes). We show that soil nitrite can release HONO and explain the reported strength and diurnal variation of the missing source. The HONO emissions rates are estimated to be comparable to that of nitric oxide (NO) and could be an important source of atmospheric reactive nitrogen. Fertilized soils appear to be particularly strong sources of HONO. Thus, agricultural activities and land-use changes may strongly influence the oxidizing capacity of the atmosphere. A new HONO-DNDC model was developed to simulate the evolution of HONO emissions in agriculture ecosystems. Because of the widespread occurrence of nitrite-producing microbes and increasing N and acid deposition, the release of HONO from soil may also be important in natural environments, including forests and boreal regions. Reference: Su, H. et al., Soil Nitrite as a Source of Atmospheric HONO and OH Radicals, Science, 333, 1616-1618, 10.1126/science.1207687, 2011.

3 dimensional distributions of NO2, CHOCHO, and HCHO measured by the University of Colorado 2D-MAX-DOAS during MAD-CAT

NASA Astrophysics Data System (ADS)

Ortega, Ivan; Sinreich, Roman; Volkamer, Rainer

2014-05-01

We present results of 2 dimensional Multi Axis-DOAS (2D-MAX-DOAS) measurements to infer 3-dimensional measurements of trace gases by characterizing boundary layer vertical profiles and near surface azimuth horizontal distribution of NO2 (14 angles covering 360°). We combine the established optimal estimation inversion with a new parameterization approach; the first method to derive NO2 tropospheric vertical profiles and boundary layer height and the second one to retrieve the azimuth horizontal distribution of near surface NO2 mixing ratios, both at multiple wavelengths (350 nm, 450 nm, and 560 nm). This was conducted for three cloud-free days in the framework of the intensive Multi Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) in Mainz, Germany 2013. By retrieving NO2 at multiple wavelengths range-resolved distributions of NO2 are derived using an 'Onion-peeling' approach, i.e., exploiting the fact that the optical path lengths at different wavelengths probe different horizontal air masses. We also measure glyoxal (CHOCHO) and formaldehyde (HCHO) distributions, and present to our knowledge the first 3-dimesional trace-gas distribution measurements of CHOCHO by a ground-based instrument. We expand the 2D-MAX-DOAS capabilities to calculate azimuth ratios of HCHO-to-NO2 (RFN) and CHOCHO-to-NO2 (RGN) to pinpoint volatile organic compound (VOC) oxidation chemistry and CHOCHO-to-HCHO (RGF) ratios as an indicator of biogenic and/or anthropogenic VOC emissions. The results of RFN correlate well with RGN and we identify azimuth variations that indicate gradients in the VOC/NOx chemistry that leads to O3 and secondary aerosol production. While there is a clear diurnal pattern in the RFN and RGN, no such variations are observed in the RGF, which shows rather constant values below 0.04 throughout the day, consistent with previous measurements, and indicative of urban air masses.

Ag-Modified In2O3/ZnO Nanobundles with High Formaldehyde Gas-Sensing Performance

PubMed Central

Fang, Fang; Bai, Lu; Song, Dongsheng; Yang, Hongping; Sun, Xiaoming; Sun, Hongyu; Zhu, Jing

2015-01-01

Ag-modified In2O3/ZnO bundles with micro/nano porous structures have been designed and synthesized with by hydrothermal method continuing with dehydration process. Each bundle consists of nanoparticles, where nanogaps of 10–30 nm are present between the nanoparticles, leading to a porous structure. This porous structure brings high surface area and fast gas diffusion, enhancing the gas sensitivity. Consequently, the HCHO gas-sensing performance of the Ag-modified In2O3/ZnO bundles have been tested, with the formaldehyde-detection limit of 100 ppb (parts per billion) and the response and recover times as short as 6 s and 3 s, respectively, at 300 °C and the detection limit of 100 ppb, response time of 12 s and recover times of 6 s at 100 °C. The HCHO sensing detect limitation matches the health standard limitation on the concentration of formaldehyde for indoor air. Moreover, the strategy to synthesize the nanobundles is just two-step heating and easy to scale up. Therefore, the Ag-modified In2O3/ZnO bundles are ready for industrialization and practical applications. PMID:26287205

Summertime photochemistry during CAREBeijing-2007: ROx budgets and O3 formation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Zhen; Wang, Y.; Gu, Dasa

2012-08-28

We analyze summertime photochemistry near the surface in Beijing, China, using a 1-D photochemical model (Regional chEmical and trAnsport Model, REAM-1D) constrained by in situ observations, focusing on the budgets of ROx (OH + HO2 + RO2) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O3 in the planetary boundary layer are also discussed. In terms of daytime average, the total ROx primary production rate near the surface in Beijing is 6.6 ppbv per hour (ppbv h{sup 1}, among the highest found in urban atmospheres. The largest primary ROxmore » source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO2 and RO2 at 2.5 ppbv h{sup 1}1 and 1.7 ppbv h{sup 1}, respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2 ppbv h{sup 1}, much larger than that of O1D+H2O (0.4 ppbv h{sup 1}). The largest ROx sink is via OH + NO2 reaction (1.6 ppbv h{sup 1}), followed by formation of RO2NO2 (1.0 ppbv h{sup 1}) and RONO2 (0.7 ppbv h{sup 1}). Due to the large aerosol surface area, aerosol uptake of HO2 appears to be another important radical sink, although the estimate of its magnitude is highly variable depending on the uptake coefficient value used. The daytime average O3 production and loss rates near the surface are 32 ppbv h{sup 1} and 6.2 ppbv h{sup 1}, respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO transformation leads to considerable O3 loss and reduction of its lifetime. Our observation-constrained modeling analysis suggests that oxidation of VOCs (especially aromatics) and heterogeneous reactions (e.g. HONO formation and aerosol uptake HO2) play potentially critical roles in the primary radical budget and O3 formation in Beijing. One important ramification is that O3 production is neither NOx nor VOC limited, but in a transition regime where reduction

The Unique OMI HCHO/NO2 Feature During the 2008 Beijing Summer Olympics: Implications for Ozone Production Sensitivity

NASA Technical Reports Server (NTRS)

Witte, J. C.; Duncan, B. N.; Douglass, A. R.; Kurosu, T. P.; Chance, K.; Retscher, C.

2010-01-01

In preparation of the Beijing Summer Olympic and Paralympics Games, strict controls were imposed between July and September 2008 on motor vehicle traffic and industrial emissions to improve air quality for the competitors. We assessed chemical sensitivity of ozone production to these controls using Ozone Monitoring Instrument (OMI) column measurements of formaldehyde (HCHO) and nitrogen dioxide (NO2), where their ratio serves as a proxy for the sensitivity. During the emission controls, HCHO/NO2 increased and indicated a NOx-limited regime, in contrast to the same period in the preceding three years when the ratio indicates volatile organic carbon (VOC)-limited and mixed NOx-VOC-limited regimes. After the emission controls were lifted, observed NO2 and HCHO/NO2 returned to their previous values. The 2005-2008 OMI record shows that this transition in regimes was unique as ozone production in Beijing was rarely NOx-limited. OMI measured summertime increases in HCHO of around 13% in 2008 compared to prior years, the same time period during which MODIS vegetation indices increased. The OMI HCHO increase may be due to higher biogenic emissions of HCHO precursors, associated with Beijing's greening initiative for the Olympics. However, NO2 and HCHO were also found to be well-correlated during the summer months. This indicates an anthropogenic VOC contribution from vehicle emissions to OMI HCHO and is a plausible explanation for the relative HCHO minimum observed in August 2008, concurrent with a minimum in traffic emissions. We calculated positive trends in 2005-2008 OMI HCHO and NO2 of about +1 x 10(exp 14) Molec/ square M-2 and +3 x 10(exp 13) molec CM-2 per month, respectively. The positive trend in NO2 may be an indicator of increasing vehicular traffic since 2005, while the positive trend in HCHO may be due to a combined increase in anthropogenic and biogenic emissions since 2005.

Measurements of HONO, NO, NOy and SO2 in aircraft exhaust plumes at cruise

NASA Astrophysics Data System (ADS)

Jurkat, T.; Voigt, C.; Arnold, F.; Schlager, H.; Kleffmann, J.; Aufmhoff, H.; Schäuble, D.; Schaefer, M.; Schumann, U.

2011-05-01

Measurements of gaseous nitrogen and sulfur oxide emissions in young aircraft exhaust plumes give insight into chemical oxidation processes inside aircraft engines. Particularly, the OH-induced formation of nitrous acid (HONO) from nitrogen oxide (NO) and sulfuric acid (H2SO4) from sulfur dioxide (SO2) inside the turbine which is highly uncertain, need detailed analysis to address the climate impact of aviation. We report on airborne in situ measurements at cruise altitudes of HONO, NO, NOy, and SO2 in 9 wakes of 8 different types of modern jet airliners, including for the first time also an A380. Measurements of HONO and SO2 were made with an ITCIMS (Ion Trap Chemical Ionization Mass Spectrometer) using a new ion-reaction scheme involving SF5- reagent ions. The measured molar ratios HONO/NO and HONO/NOy with averages of 0.038 ± 0.010 and 0.027 ± 0.005 were found to decrease systematically with increasing NOx emission-index (EI NOx). We calculate an average EI HONO of 0.31 ± 0.12 g NO2 kg-1. Using reliable measurements of HONO and NOy, which are less adhesive than H2SO4 to the inlet walls, we derive the OH-induced conversion fraction of fuel sulfur to sulfuric acid $\\varepsilon$ with an average of 2.2 ± 0.5 %. $\\varepsilon$ also tends to decrease with increasing EI NOx, consistent with earlier model simulations. The lowest HONO/NO, HONO/NOy and $\\varepsilon$ was observed for the largest passenger aircraft A380.

Potential role of the nitroacidium ion on HONO emissions from the snowpack.

PubMed

Hellebust, Stig; Roddis, Tristan; Sodeau, John R

2007-02-22

The effects of photolysis on frozen, thin films of water-ice containing nitrogen dioxide (as its dimer dinitrogen tetroxide) have been investigated using a combination of Fourier transform reflection-absorption infrared (FT-RAIR) spectroscopy and mass spectrometry. The release of HONO is ascribed to a mechanism in which nitrosonium nitrate (NO+NO3-) is formed. Subsequent solvation of the cation leads to the nitroacidium ion, H2ONO+, i.e., protonated nitrous acid. The pathway proposed explains why the field measurement of HONO at different polar sites is often contradictory.

Investigation of the role of the calvin cycle and C1 metabolism during HCHO metabolism in gaseous HCHO-treated petunia under light and dark conditions using 13C-NMR.

PubMed

Sun, Huiqun; Zhang, Wei; Tang, Lijuan; Han, Shuang; Wang, Xinjia; Zhou, Shengen; Li, Kunzhi; Chen, Limei

2015-01-01

It has been shown that formaldehyde (HCHO) absorbed by plants can be assimilated through the Calvin cycle or C1 metabolism. Our previous study indicated that Petunia hybrida could effectively eliminate HCHO from HCHO-polluted air. To understand the roles of C1 metabolism and the Calvin cycle during HCHO metabolism and detoxification in petunia plants treated with gaseous H(13)CHO under light and dark conditions. Aseptically grown petunia plants were treated with gaseous H(13)CHO under dark and light conditions. The metabolites generated from HCHO detoxification in petunia were investigated using (13)C-NMR. [2-(13)C]glycine (Gly) was generated via C1 metabolism and [U-(13)C]glucose (Gluc) was produced through the Calvin cycle simultaneously in petunia treated with low-level gaseous H(13)CHO under light conditions. Generation of [2-(13)C]Gly decreased whereas [U-(13) C]Gluc and [U-(13)C]fructose (Fruc) production increased greatly under high-level gaseous H(13)CHO stress in the light. In contrast, [U-(13)C]Gluc and [U-(13)C] Fruc production decreased greatly and [2-(13)C]Gly generation increased significantly under low-level and high-level gaseous H(13)CHO stress in the dark. C1 metabolism and the Calvin cycle contributed differently to HCHO metabolism and detoxification in gaseous H(13CHO-treated petunia plants. As the level of gaseous HCHO increased, the role of C1 metabolism decreased and the role of the Calvin cycle increased under light conditions. However, opposite changes were observed in petunia plants under dark conditions. Copyright © 2015 John Wiley & Sons, Ltd.

The Role of Iron-Bearing Minerals in NO2 to HONO Conversion on Soil Surfaces.

PubMed

Kebede, Mulu A; Bish, David L; Losovyj, Yaroslav; Engelhard, Mark H; Raff, Jonathan D

2016-08-16

Nitrous acid (HONO) accumulates in the nocturnal boundary layer where it is an important source of daytime hydroxyl radicals. Although there is clear evidence for the involvement of heterogeneous reactions of NO2 on surfaces as a source of HONO, mechanisms remain poorly understood. We used coated-wall flow tube measurements of NO2 reactivity on environmentally relevant surfaces (Fe (hydr)oxides, clay minerals, and soil from Arizona and the Saharan Desert) and detailed mineralogical characterization of substrates to show that reduction of NO2 by Fe-bearing minerals in soil can be a more important source of HONO than the putative NO2 hydrolysis mechanism. The magnitude of NO2-to-HONO conversion depends on the amount of Fe(2+) present in substrates and soil surface acidity. Studies examining the dependence of HONO flux on substrate pH revealed that HONO is formed at soil pH < 5 from the reaction between NO2 and Fe(2+)(aq) present in thin films of water coating the surface, whereas in the range of pH 5-8 HONO stems from reaction of NO2 with structural iron or surface complexed Fe(2+) followed by protonation of nitrite via surface Fe-OH2(+) groups. Reduction of NO2 on ubiquitous Fe-bearing minerals in soil may explain HONO accumulation in the nocturnal boundary layer and the enhanced [HONO]/[NO2] ratios observed during dust storms in urban areas.

An Atmospheric Constraint on the NO2 Dependence of Daytime Near-Surface Nitrous Acid (HONO).

PubMed

Pusede, Sally E; VandenBoer, Trevor C; Murphy, Jennifer G; Markovic, Milos Z; Young, Cora J; Veres, Patrick R; Roberts, James M; Washenfelder, Rebecca A; Brown, Steven S; Ren, Xinrong; Tsai, Catalina; Stutz, Jochen; Brune, William H; Browne, Eleanor C; Wooldridge, Paul J; Graham, Ashley R; Weber, Robin; Goldstein, Allen H; Dusanter, Sebastien; Griffith, Stephen M; Stevens, Philip S; Lefer, Barry L; Cohen, Ronald C

2015-11-03

Recent observations suggest a large and unknown daytime source of nitrous acid (HONO) to the atmosphere. Multiple mechanisms have been proposed, many of which involve chemistry that reduces nitrogen dioxide (NO2) on some time scale. To examine the NO2 dependence of the daytime HONO source, we compare weekday and weekend measurements of NO2 and HONO in two U.S. cities. We find that daytime HONO does not increase proportionally to increases in same-day NO2, i.e., the local NO2 concentration at that time and several hours earlier. We discuss various published HONO formation pathways in the context of this constraint.

Consistency of the Health of the Nation Outcome Scales (HoNOS) at inpatient-to-community transition.

PubMed

Luo, Wei; Harvey, Richard; Tran, Truyen; Phung, Dinh; Venkatesh, Svetha; Connor, Jason P

2016-04-27

The Health of the Nation Outcome Scales (HoNOS) are mandated outcome-measures in many mental-health jurisdictions. When HoNOS are used in different care settings, it is important to assess if setting specific bias exists. This article examines the consistency of HoNOS in a sample of psychiatric patients transitioned from acute inpatient care and community centres. A regional mental health service with both acute and community facilities. 111 psychiatric patients were transferred from inpatient care to community care from 2012 to 2014. Their HoNOS scores were extracted from a clinical database; Each inpatient-discharge assessment was followed by a community-intake assessment, with the median period between assessments being 4 days (range 0-14). Assessor experience and professional background were recorded. The difference of HoNOS at inpatient-discharge and community-intake were assessed with Pearson correlation, Cohen's κ and effect size. Inpatient-discharge HoNOS was on average lower than community-intake HoNOS. The average HoNOS was 8.05 at discharge (median 7, range 1-22), and 12.16 at intake (median 12, range 1-25), an average increase of 4.11 (SD 6.97). Pearson correlation between two total scores was 0.073 (95% CI -0.095 to 0.238) and Cohen's κ was 0.02 (95% CI -0.02 to 0.06). Differences did not appear to depend on assessor experience or professional background. Systematic change in the HoNOS occurs at inpatient-to-community transition. Some caution should be exercised in making direct comparisons between inpatient HoNOS and community HoNOS scores. Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://www.bmj.com/company/products-services/rights-and-licensing/

Measurement of nitrous acid (HONO) by external-cavity quantum cascade laser based quartz-enhanced photoacoustic absorption spectroscopy

NASA Astrophysics Data System (ADS)

Yi, Hongming; Maamary, Rabih; Gao, Xiaoming; Sigrist, Markus W.; Fertein, Eric; Chen, Weidong

2016-04-01

Spectroscopic detection of short-lived gaseous nitrous acid (HONO) at 1254.85 cm-1 was realized by off-beam coupled quartz-enhanced photoacoustic spectroscopy (QEPAS) in conjunction with an external cavity quantum cascade lasers (EC-QCL). High sensitivity monitoring of HONO was performed within a very small gas-sample volume (of ~40 mm3) allowing a significant reduction (of about 4 orders of magnitude) of air sampling residence time which is highly desired for accurate quantification of chemically reactive short-lived species. Calibration of the developed QEPAS-based HONO sensor was carried out by means of lab-generated HONO samples whose concentrations were determined by simultaneous measurements of direct HONO absorption spectra in a 109.5 m multipass cell using a distributed feedback (DBF) QCL. A minimum detection limit (MDL @ SNR=1) of 66 ppbv HONO was achieved at 70 mbar using a laser output power of 50 mW and 1 s integration time, which corresponded to a normalized noise equivalent absorption coefficient of 3.6×10-8 cm-1.W/Hz1/2. This MDL was down to 7 ppbv at the optimal integration time of 150 s. The corresponding minimum detected absorption coefficient (SNR=1) is ~1.1×10-7 cm-1 (MDL: ~3 ppbv) in 1 s and ~1.1×10-8 cm-1 (MDL~330 pptv) in 150 s, respectively, with 1 W laser power. Acknowledgements The authors acknowledge financial supports from the CaPPA project (ANR-10-LABX-005) and the CPER CLIMIBIO program. References H. Yi, R. Maamary, X. Gao, M. W. Sigrist, E. Fertein, W. Chen, "Short-lived species detection of nitrous acid by external-cavity quantum cascade laser based quartz-enhanced photoacoustic absorption spectroscopy", Appl. Phys. Lett. 106 (2015) 101109

Enhanced photochemical conversion of NO2 to HONO on humic acids in the presence of benzophenone.

PubMed

Han, Chong; Yang, Wangjin; Yang, He; Xue, Xiangxin

2017-12-01

The photochemical conversion of NO 2 to HONO on humic acids (HA) in the presence of benzophenone (BP) was investigated using a flow tube reactor coupled to a NO x analyzer at ambient pressure. BP significantly enhanced the reduction of NO 2 to HONO on HA under simulated sunlight, as shown by the increase of NO 2 uptake coefficient (γ) and HONO yield with the mass ratio of BP to HA. The γ and HONO yield on the mixtures of HA and BP obviously depended on the environmental conditions. Both γ and HONO yield increased with the increase of irradiation intensity and temperature, whereas they decreased with pH. The γ exhibited a negative dependence on the NO 2 concentration, which had slight influences on the HONO yield. There were maximum values for the γ and HONO yield at relative humidity (RH) of 22%. Finally, atmospheric implications about the photochemical reaction of NO 2 and HA in the presence of photosensitive species were discussed. Copyright © 2017 Elsevier Ltd. All rights reserved.

Intercomparison of field measurements of nitrous acid (HONO) during the SHARP Campaign

EPA Science Inventory

Because of the importance of HONO as a radical reservoir, consistent and accurate measurements of its concentration are needed. As part of the SHARP (Study of Houston Atmospheric Radical Precursors), time series of HONO were obtained by five different measurement techniques on th...

Gaseous nitrous acid (HONO) and nitrogen oxides (NOx) emission from gasoline and diesel vehicles under real-world driving test cycles.

PubMed

Trinh, Ha T; Imanishi, Katsuma; Morikawa, Tazuko; Hagino, Hiroyuki; Takenaka, Norimichi

2017-04-01

Reactive nitrogen species emission from the exhausts of gasoline and diesel vehicles, including nitrogen oxides (NO x ) and nitrous acid (HONO), contributes as a significant source of photochemical oxidant precursors in the ambient air. Multiple laboratory and on-road exhaust measurements have been performed to estimate the NO x emission factors from various vehicles and their contribution to atmospheric pollution. Meanwhile, HONO emission from vehicle exhaust has been under-measured despite the fact that HONO can contribute up to 60% of the total hydroxyl budget during daytime and its formation pathway is not fully understood. A profound traffic-induced HONO to NO x ratio of 0.8%, established by Kurtenbach et al. since 2001, has been widely applied in various simulation studies and possibly linked to under-estimation of HONO mixing ratios and OH radical budget in the morning. The HONO/NO x ratios from direct traffic emission have become debatable when it lacks measurements for direct HONO emission from vehicles upon the fast-changing emission reduction technology. Several recent studies have reported updated values for this ratio. This study has reported the measurement of HONO and NO x emission as well as the estimation of exhaust-induced HONO/NO x ratios from gasoline and diesel vehicles using different chassis dynamometer tests under various real-world driving cycles. For the tested gasoline vehicle, which was equipped with three-way catalyst after-treatment device, HONO/NO x ratios ranged from 0 to 0.95 % with very low average HONO concentrations. For the tested diesel vehicle equipped with diesel particulate active reduction device, HONO/NO x ratios varied from 0.16 to 1.00 %. The HONO/NO x ratios in diesel exhaust were inversely proportional to the average speeds of the tested vehicles. Photolysis of HONO is a dominant source of morning OH radicals. Conventional traffic-induced HONO/NO x ratio of 0.8% has possibly linked to underestimation of the total HONO

A review and update of the Health of the Nation Outcome Scales (HoNOS).

PubMed

James, Mick; Painter, Jon; Buckingham, Bill; Stewart, Malcolm W

2018-04-01

Aims and method The Health of the Nation Outcome Scales (HoNOS) and its older adults' version (HoNOS 65+) have been used widely for 20 years, but their glossaries have not been revised to reflect clinicians' experiences or changes in service delivery. The Royal College of Psychiatrists convened an international advisory board, with UK, Australian and New Zealand expertise, to identify desirable amendments. The aim was to improve rater experience by removing ambiguity and inconsistency in the glossary rather than more radical revision. Changes proposed to the HoNOS are reported. HoNOS 65+ changes will be reported separately. Based on the views and experience of the countries involved, a series of amendments were identified. Clinical implications While effective clinician training remains critically important, these revisions aim to improve intra- and interrater reliability and improve validity. Next steps will depend on feedback from HoNOS users. Reliability and validity testing will depend on funding. Declaration of interest None.

Key role of pH in the photochemical conversion of NO2 to HONO on humic acid

NASA Astrophysics Data System (ADS)

Han, Chong; Yang, Wangjin; Wu, Qianqian; Yang, He; Xue, Xiangxin

2016-10-01

The heterogeneous photochemical reactions of NO2 with humic acid (HA) were performed using a flow tube reactor coupled to a NOx analyzer. The effects of the pH on the uptake coefficient (γ) of NO2 and HONO and NO yields were investigated in detail. With increasing the pH in the range of 2-12, γ was almost constant with an average value of (4.21 ± 0.46) × 10-6, whereas the HONO yield and NO yield linearly decreased from (81.07 ± 4.07)% and (10.35 ± 3.86)% to (13.87 ± 9.15)% and (1.51 ± 0.94)%, respectively. According to the characterization of HA compositions and possible reaction paths, it can be concluded that the pH may influence the transfer of protons and the equilibrium of HONO with NO2- by varying the contents of carboxyl and phenol groups in HA, which should primarily contribute to the change in the HONO yield with the pH.

Anthropogenic Emissions of Highly Reactive Volatile Organic Compounds (HRVOCs) Inferred from Oversampling of OMI HCHO Columns

NASA Technical Reports Server (NTRS)

Zhu, Lei; Jacob, Daniel; Mickley, Loretta; Marais, Eloise; Zhang, Aoxing; Cohan, Daniel; Yoshida, Yasuko; Duncan, Bryan; Abad, Gonzalo Gonzalez; Chance, Kelly;

Car MAX-DOAS measurements of the tropospheric Formaldehyde (HCHO) column around Bucharest (Romania) and in the Rhein-Main area (Germany)

NASA Astrophysics Data System (ADS)

Donner, Sebastian; Shaiganfar, Reza; Riffel, Katharina; Dörner, Steffen; Lampel, Johannes; Remmers, Julia; Wagner, Thomas

2016-04-01

The DOAS (differential optical absorption spectroscopy)-method analyses the absorptions of atmospheric trace gases in spectra of scattered sun light. It is an excellent way to determine the concentrations of different trace gases (e.g. NO2, SO2, HCHO…) simultaneously. MAX (Multi-AXis)-DOAS measurements observe scattered sun light under different elevation angles. From such measurements tropospheric vertical column densities (VCDs) or even vertical profiles of the measured trace gases and aerosols can be determined. We performed mobile MAX-DOAS measurements using two instruments on the roof of a car in summer 2015 in Romania during the AROMAT2 campaign and in the Winter/Spring 2016 in the Rhein-Main area (Germany). The latter is one of the densest populated areas in Germany. One instrument is a commercial Mini-MAX-DOAS instrument from the Hoffmann company, the other a self-built instrument using an AVANTES spectrometer with better optical characteristics. The instruments were looking in two different directions (one forward and one backward). Mobile MAX-DOAS measurements cover a quite large area in a short period of time. This enables to map existing gradients of concentrations of tropospheric trace gases, e.g. NO2 and HCHO. The results of those measurements then can be used to validate satellite measurements or can be compared to model results. In this study we focus on formaldehyde (HCHO). In small amounts it is emitted directly by industries and other anthropogenic and biogenic activities. Large amounts are mostly secondary produced. As it is an intermediate product of basic oxidation cycles of other hydrocarbons its concentrations are determined by the abundances of other hydrocarbons. Therefore it can be used as an indicator for volatile organic compounds (VOCs). Furthermore HCHO plays an important role in photochemical smog chemistry and tropospheric O3 chemistry. In this work we present the measurement setup and preliminary HCHO results of the AROMAT2

Intercomparison of HONO Measurements Made Using Wet-Chemical (NITROMAC) and Spectroscopic (IBBCEAS & LP/FAGE) Techniques

NASA Astrophysics Data System (ADS)

Dusanter, S.; Lew, M.; Bottorff, B.; Bechara, J.; Mielke, L. H.; Berke, A.; Raff, J. D.; Stevens, P. S.; Afif, C.

2013-12-01

A good understanding of the oxidative capacity of the atmosphere is important to tackle fundamental issues related to climate change and air quality. The hydroxyl radical (OH) is the dominant oxidant in the daytime troposphere and an accurate description of its sources in atmospheric models is of utmost importance. Recent field studies indicate higher-than-expected concentrations of HONO during the daytime, suggesting that the photolysis of HONO may be an important underestimated source of OH. Understanding the tropospheric HONO budget requires confidence in analytical instrumentation capable of selectively measuring HONO. In this presentation, we discuss an intercomparison study of HONO measurements performed during summer 2013 at the edge of a hardwood forest in Southern Indiana. This exercise involved a wet chemical technique (NITROMAC), an Incoherent Broad-Band Cavity Enhanced Absorption Spectroscopy instrument (IBBCEAS), and a Laser-Photofragmentation/Fluorescence Assay by Gas Expansion instrument (LP/FAGE). The agreement observed between the three techniques will be discussed for both ambient measurements and cross calibration experiments.

Direct emission of nitrous acid (HONO) from gasoline cars in China determined by vehicle chassis dynamometer experiments

NASA Astrophysics Data System (ADS)

Liu, Yuhan; Lu, Keding; Ma, Yufang; Yang, Xinping; Zhang, Wenbin; Wu, Yusheng; Peng, Jianfei; Shuai, Shijin; Hu, Min; Zhang, Yuanhang

2017-11-01

HONO plays a key role in atmospheric chemistry, and while its importance is well-known, the sources of HONO are still not completely understood. As a component of ambient HONO sources, direct emission from vehicles is an area that should be extensively studied. In this study, we determined the HONO emission index for typical gasoline vehicles in the car population of China through a chassis dynamometer with different types of engines (PFI/GDI), starting conditions (cold/warm) and running styles (Beijing cycle). Emission ratios of HONO to nitrogen oxide (NOX) for the Chinese gasoline cars are determined to be in the range of (0.03-0.42) % and an averaged value is about 0.18%, which are comparable to those reported in the few studies available in Europe, the United States and Japan for gasoline cars while smaller for those of the diesel cars. The atmospheric impact of the direct HONO emission from gasoline cars was analyzed for a typical urban site in Beijing, significant contributions of the direct emission toward the HONO budget were found during morning rush hours or twilight conditions to be 8-12%.

Analysis of Strong Wintertime Ozone Events in an Area of Extensive Oil and Gas Extraction

NASA Astrophysics Data System (ADS)

Rappenglück, Bernhard; Ackermann, Luis; Alvarez, Sergio; Golovko, Julia; Buhr, Martin; Field, Robert; Soltis, Jeff; Montague, Derek C.; Hauze, Bill; Scott, Adamson; Risch, Dan; Wilkerson, George; Bush, David; Stoeckenius, Till; Keslar, Cara

2015-04-01

During recent years, elevated ozone (O3) values have been observed repeatedly in the Upper Green River Basin (UGRB), Wyoming during wintertime. This paper presents an analysis of high ozone days in late winter 2011 (1-hour average up to 166 ppbv). Intensive Observational Periods (IOPs) were performed which included comprehensive surface and boundary layer measurements. Low windspeeds in combination with low mixing layer heights (~50 m agl) are essential for accumulation of pollutants. Air masses contain substantial amounts of reactive nitrogen (NOx) and non-methane hydrocarbons (NMHC) emitted from fossil fuel exploration activities in the Pinedale Anticline. On IOP days in the morning hours reactive nitrogen (up to 69%), then aromatics and alkanes (each ~10-15%; mostly ethane and propane) are major contributors to the hydroxyl (OH) reactivity. This time frame largely coincides with lowest NMHC/NOx ratios (~50), reflecting a relatively low NMHC mixture, and a change from a NOx-limited regime towards a NMHC limited regime. OH production on IOP days is mainly due to nitrous acid (HONO). On a 24-hr basis and as determined for a measurement height of 1.80 m above the surface HONO photolysis on IOP days can contribute ~83% to OH production on average, followed by alkene ozonolysis (~9%). Photolysis by ozone and HCHO photolysis contributes about 4% each to hydroxyl formation. High HONO levels (maximum hourly median on IOP days: 1,096 pptv) are favored by a combination of shallow boundary layer conditions and enhanced photolysis rates due to the high albedo of the snow surface. HONO is most likely formed through (i) abundant nitric acid (HNO3) produced in atmospheric oxidation of NOx, deposited onto the snow surface and undergoing photo-enhanced heterogeneous conversion to HONO and (ii) combustion related emission of HONO. HONO production is confined to the lowermost 10 m of the boundary layer. HONO, serves as the most important precursor for OH, strongly enhanced due to

Nitrogen Oxides in the Nocturnal Boundary Layer: Chemistry of Nitrous Acid (HONO) and the Nitrate Radical (N03)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jochen Stutz

altitude dependent. Measurements at one altitude, for example at the ground, where most air quality monitoring stations are located, are not representative for the rest of the NBL. Our model also revealed that radical chemistry is, in general, altitude dependent at night. We distinguish three regions: an unreactive, NO rich, ground layer; an upper, O3 and NO3 dominated layer, and a reactive mixing layer, where RO2 radicals are mixed from aloft with NO from the ground. In this reactive layer an active radical chemistry and elevated OH radical levels can be found. The downward transport of N2O5 and HO2NO2, followed by their thermal decay, was also identified as a radical source in this layer. Our observations also gave insight into the formation of HONO in the NBL. Based on our field experiments we were able to show that the NO2 to HONO conversion was relative humidity dependent. While this fact was well known, we found that it is most likely the uptake of HONO onto surfaces which is R.H. dependent, rather than the NO2 to HONO conversion. This finding led to the proposal of a new NO2 to HONO conversion mechanism, which is based on solid physical chemical principles. Noteworthy is also the observation of enhanced NO2 to HONO conversion during a dust storm event in Phoenix. The final activity in our project investigated the influence of the urban canopy, i.e. building walls and surfaces, on nocturnal chemistry. For the first time the surface area of a city was determined based on a Geographical Information System database of the city of Santa Monica. The surface to volume areas found in this study showed that, in the 2 lower part of the NBL, buildings provide a much larger surface area than the aerosol. In addition, buildings take up a considerable amount of the volume near the ground. The expansion of our model and sensitivity studies based on the Santa Monica data revealed that the surface area of buildings considerably influences HONO levels in urban areas. The volume

The Enhanced Formaldehyde-Sensing Properties of P3HT-ZnO Hybrid Thin Film OTFT Sensor and Further Insight into Its Stability

PubMed Central

Tai, Huiling; Li, Xian; Jiang, Yadong; Xie, Guangzhong; Du, Xiaosong

2015-01-01

A thin-film transistor (TFT) having an organic–inorganic hybrid thin film combines the advantage of TFT sensors and the enhanced sensing performance of hybrid materials. In this work, poly(3-hexylthiophene) (P3HT)-zinc oxide (ZnO) nanoparticles' hybrid thin film was fabricated by a spraying process as the active layer of TFT for the employment of a room temperature operated formaldehyde (HCHO) gas sensor. The effects of ZnO nanoparticles on morphological and compositional features, electronic and HCHO-sensing properties of P3HT-ZnO thin film were systematically investigated. The results showed that P3HT-ZnO hybrid thin film sensor exhibited considerable improvement of sensing response (more than two times) and reversibility compared to the pristine P3HT film sensor. An accumulation p-n heterojunction mechanism model was developed to understand the mechanism of enhanced sensing properties by incorporation of ZnO nanoparticles. X-ray photoelectron spectroscope (XPS) and atomic force microscopy (AFM) characterizations were used to investigate the stability of the sensor in-depth, which reveals the performance deterioration was due to the changes of element composition and the chemical state of hybrid thin film surface induced by light and oxygen. Our study demonstrated that P3HT-ZnO hybrid thin film TFT sensor is beneficial in the advancement of novel room temperature HCHO sensing technology. PMID:25608214

The enhanced formaldehyde-sensing properties of P3HT-ZnO hybrid thin film OTFT sensor and further insight into its stability.

PubMed

Tai, Huiling; Li, Xian; Jiang, Yadong; Xie, Guangzhong; Du, Xiaosong

2015-01-19

A thin-film transistor (TFT) having an organic-inorganic hybrid thin film combines the advantage of TFT sensors and the enhanced sensing performance of hybrid materials. In this work, poly(3-hexylthiophene) (P3HT)-zinc oxide (ZnO) nanoparticles' hybrid thin film was fabricated by a spraying process as the active layer of TFT for the employment of a room temperature operated formaldehyde (HCHO) gas sensor. The effects of ZnO nanoparticles on morphological and compositional features, electronic and HCHO-sensing properties of P3HT-ZnO thin film were systematically investigated. The results showed that P3HT-ZnO hybrid thin film sensor exhibited considerable improvement of sensing response (more than two times) and reversibility compared to the pristine P3HT film sensor. An accumulation p-n heterojunction mechanism model was developed to understand the mechanism of enhanced sensing properties by incorporation of ZnO nanoparticles. X-ray photoelectron spectroscope (XPS) and atomic force microscopy (AFM) characterizations were used to investigate the stability of the sensor in-depth, which reveals the performance deterioration was due to the changes of element composition and the chemical state of hybrid thin film surface induced by light and oxygen. Our study demonstrated that P3HT-ZnO hybrid thin film TFT sensor is beneficial in the advancement of novel room temperature HCHO sensing technology.

Observation and modeling of ambient nitrous acid (HONO) at a rural site (Wangdu) in the North China Plain in summer 2014

NASA Astrophysics Data System (ADS)

Liu, Y.; Lu, K.; Li, X.; Dong, H.; Tan, Z.; Wu, Y.; Zeng, L.; Bohn, B.; Broch, S.; Zou, Q.; Fuchs, H.; Hofzumahaus, A.; Holland, F.; Rohrer, F.; Min, K. E.; Brown, S. S.; Wahner, A.; Zhang, Y.

2017-12-01

The photolysis of HONO, was frequently determined to be the major OH primary production channels in the city clusters of China. However, the source of ambient HONO is still a mystery needs to be elucidated. In the framework of an integrated field experiment performed at a rural site in the North China Plain (NCP), HONO was measured by two LOPAP instruments and one CEAS instrument in order to obtain the best quality of the observations and comprehensive parameters that support the exploration of the HONO budget were completely available. In general, the observed HONO concentrations by these three different instruments showed reasonable good agreement as indicated by the high correlation efficiencies while the difference of the regression slopes showed the HONO measured uncertainty is about 15% which is twice about the known uncertainties from each instrument. The diurnal variation of the observed HONO concentrations showed high value (1 -5 ppb) at night and small values (100 - 500 ppt) around noon time which is similar to other reported campaigns. With the assumption of photo stationary state, the missing HONO source is determined experimentally constrained to the observed HONO, jHONO, OH, and NO. Possible HONO formation rates from the chemical reactions as proposed from literatures were calculated in the framework of an observational based box model. It is found that heteorogeneous uptake of NO2 on the ground and the photolysis of nitrate were the major HONO sources for this site when constrained with the recommended kinetc parameters. Uncertainty analysis showed that the uptake coefficient of NO2 and the photolysis frequency of nitrate are the important kinetc factors to be determined in the future studies. In addition, the direct emission of HONO from soil is found to be very important for a few days after fertilization.

MAX-DOAS measurements of HONO slant column densities during the MAD-CAT campaign: inter-comparison, sensitivity studies on spectral analysis settings, and error budget

NASA Astrophysics Data System (ADS)

Wang, Yang; Beirle, Steffen; Hendrick, Francois; Hilboll, Andreas; Jin, Junli; Kyuberis, Aleksandra A.; Lampel, Johannes; Li, Ang; Luo, Yuhan; Lodi, Lorenzo; Ma, Jianzhong; Navarro, Monica; Ortega, Ivan; Peters, Enno; Polyansky, Oleg L.; Remmers, Julia; Richter, Andreas; Puentedura, Olga; Van Roozendael, Michel; Seyler, André; Tennyson, Jonathan; Volkamer, Rainer; Xie, Pinhua; Zobov, Nikolai F.; Wagner, Thomas

2017-10-01

In order to promote the development of the passive DOAS technique the Multi Axis DOAS - Comparison campaign for Aerosols and Trace gases (MAD-CAT) was held at the Max Planck Institute for Chemistry in Mainz, Germany, from June to October 2013. Here, we systematically compare the differential slant column densities (dSCDs) of nitrous acid (HONO) derived from measurements of seven different instruments. We also compare the tropospheric difference of SCDs (delta SCD) of HONO, namely the difference of the SCDs for the non-zenith observations and the zenith observation of the same elevation sequence. Different research groups analysed the spectra from their own instruments using their individual fit software. All the fit errors of HONO dSCDs from the instruments with cooled large-size detectors are mostly in the range of 0.1 to 0.3 × 1015 molecules cm-2 for an integration time of 1 min. The fit error for the mini MAX-DOAS is around 0.7 × 1015 molecules cm-2. Although the HONO delta SCDs are normally smaller than 6 × 1015 molecules cm-2, consistent time series of HONO delta SCDs are retrieved from the measurements of different instruments. Both fits with a sequential Fraunhofer reference spectrum (FRS) and a daily noon FRS lead to similar consistency. Apart from the mini-MAX-DOAS, the systematic absolute differences of HONO delta SCDs between the instruments are smaller than 0.63 × 1015 molecules cm-2. The correlation coefficients are higher than 0.7 and the slopes of linear regressions deviate from unity by less than 16 % for the elevation angle of 1°. The correlations decrease with an increase in elevation angle. All the participants also analysed synthetic spectra using the same baseline DOAS settings to evaluate the systematic errors of HONO results from their respective fit programs. In general the errors are smaller than 0.3 × 1015 molecules cm-2, which is about half of the systematic difference between the real measurements.The differences of HONO delta SCDs

Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions

NASA Astrophysics Data System (ADS)

Roberts, J. M.; Veres, P.; Warneke, C.; Neuman, J. A.; Washenfelder, R. A.; Brown, S. S.; Baasandorj, M.; Burkholder, J. B.; Burling, I. R.; Johnson, T. J.; Yokelson, R. J.; de Gouw, J.

2010-07-01

A negative-ion proton-transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO), nitric (HNO3), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be intrinsically sensitive (6-16 cts/pptv), but prone to inlet effects for HNO3 and HCl. The ion chemistry was found to be insensitive to water vapor concentrations, in agreement with previous studies of carboxylic acids. The inlet equilibration times for HNCO and HONO were 2 to 4 s, allowing for measurement in biomass burning studies. Several potential interferences in HONO measurements were examined: decomposition of HNO3·NO3- clusters within the CIMS, and NO2-water production on inlet surfaces, and were quite minor (≤1%, 3.3%, respectively). The detection limits of the method were limited by the instrument backgrounds in the ion source and flow tube, and were estimated to range between 16 and 50 pptv (parts per trillion by volume) for a 1 min average. The comparison of HONO measured by CIMS and by in situ FTIR showed good correlation and agreement to within 17%. The method provided rapid and accurate measurements of HNCO and HONO in controlled biomass burning studies, in which both acids were seen to be important products.

Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions

NASA Astrophysics Data System (ADS)

Roberts, J. M.; Veres, P.; Warneke, C.; Neuman, J. A.; Washenfelder, R. A.; Brown, S. S.; Baasandorj, M.; Burkholder, J. B.; Burling, I. R.; Johnson, T. J.; Yokelson, R. J.; de Gouw, J.

2010-01-01

A negative-ion proton transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO), nitric (HNO3), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be intrinsically sensitive (6-16 cts/pptv), but prone to inlet effects for HNO3 and HCl. The ion chemistry was found to be insensitive to water vapor concentrations, in agreement with previous studies of carboxylic acids. The inlet equilibration times for HNCO and HONO were 2 to 4 s, allowing for measurement in biomass burning studies. Several potential interferences in HONO measurements were examined: decomposition of HNO3·NO3- clusters within the CIMS, and NO2-water production on inlet surfaces, and were quite minor (≤1%, 3.3%, respectively). The detection limits of the method were limited by the instrument backgrounds in the ion source and flow tube, and were estimated to range between 16 and 50 pptv (parts per trillion by volume) for a 1 min average. The comparison of HONO measured by CIMS and by in situ FTIR showed good correlation and agreement to within 17%. The method provided rapid and accurate measurements of HNCO and HONO in controlled biomass burning studies, in which both acids were seen to be important products.

Measurement of HONO, HNCO, and Other Inorganic Acids by Negative-ion Proton-Transfer Chemical-Ionization Mass Spectrometry (NI-PT-CIMS):Application to Biomass Burning Emissions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roberts, James M.; Veres, Patrick; Warneke, Carsten

2010-07-23

A negative-ion proton transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO) nitric (HNO3), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be intrinsically sensitive (6-16 cts/pptv), but prone to inlet effects for HNO3 and HCl. The ion chemistry was found to be insensitive to water vapor concentrations, in agreement with previous studies of carboxylic acids. The inlet equilibration times for HNCO and HONO were 2 to 4 seconds, allowing for measurement inmore » biomass burning studies. Several potential interferences in HONO measurements were examined: decomposition of HNO3•NO3- clusters within the CIMS, and NO2-water production on inlet surfaces, and were quite minor (>_1%, 3.3%, respectively). The detection limits of the method were limited by the instrument backgrounds in the ion source and flow tube, and were estimated to range between 16 and 50 pptv (parts per trillion by volume). The comparison of HONO measured by CIMS and by in situ FTIR showed good correlation and agreement to within 17%. The method provided rapid and accurate measurements of HNCO and HONO in controlled biomass burning studies, and suggest both as products of biomass burning.« less

Heterogeneous Reactivity of NO2 with Photocatalytic Paints: A Possible Source of Nitrous Acid (HONO) in the Indoor Environment

NASA Astrophysics Data System (ADS)

Gligorovski, S.; Bartolomei, V.; Gandolfo, A.; Gomez Alvarez, E.; Kleffmann, J.; Wortham, H.

2014-12-01

There is an increasing concern about the indoor air environment, where we spend most of our time. Common methods of improving indoor air quality include controlling pollution sources, increasing ventilation rates or using air purifiers. Photocatalytic remediation technology was suggested as a new possibility to eliminate indoor air pollutants instead of just diluting or disposing them. In the present study, heterogeneous reactions of NO2 were studied on photocatalytic paints containing different size and quantity of TiO2. The heterogeneous reactions were conducted in a photo reactor under simulated atmospheric conditions. The flat pyrex rectangular plates covered with the paint were inserted into the reactor. These plates have been sprayed with the photocatalytic paints at our industrial partner's (ALLIOS) facilities using a high precision procedure that allowed the application of a thin layer of a given thickness of the paint. This allows a homogeneous coverage of the surface with the paint and an accurate determination of the exact amount of paint exposed to gaseous NO2. We demonstrate that the indoor photocatalytic paints which contain TiO2 can substantially reduce the concentrations of nitrogen dioxide (NO2). We show that the efficiency of nitrogen dioxide (NO2) removal increase with the quantity of TiO2 in the range 0 - 7 %. The geometric uptake coefficients increase from 5 · 10-6 to 1.6 · 10-5 under light irradiation of the paints. On the other hand, during the reactions of NO2 with this paint (7 % of TiO2) nitric oxide (NO) and nitrous acid (HONO) are formed. Nitrous acid (HONO) is an important harmful indoor pollutant and its photolysis leads to the formation of highly reactive OH radicals (Gomez Alvarez et al., 2013). Maximum conversion efficiencies of NO2to HONO and NO of 15 % and 33 % were observed at 30 % RH, respectively. Thus, the quantity of TiO2 embedded in the paint is an important parameter regarding the nitrogen oxides (NOx = NO + NO2

The Primary and Recycling Sources of OH During the NACHTT-2011 Campaign: HONO as an Important OH Primary Source in the Wintertime

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, S.; VandenBoer, Trevor; Young, Cora

2014-06-10

We present OH observation results during the NACHTT-11 field campaign at the Boulder Atmospheric Observatory in Weld County, Colorado. The observed OH levels during the daytime (at noon) were ~ 2.7 × 106 molecules cm-3 at the ground level (2 m above ground level, AGL). HONO and ozone photolysis were the two dominant photochemical OH production pathways during the field campaign. However, alkene ozonolysis, found an important source for OH by two previous winter season OH observations, was a minor contribution to OH primary production (~5 %). To evaluate recycling sources of OH from HO2 and RO2, an observation constrainedmore » University of Washington Chemical Mechanism (UWCM) box model is employed to simulated ambient OH levels with different model scenarios. For the base run without constraining observed HONO, the model simulated OH significantly underestimates the observed OH level (20.8 times in the morning and 7.2 times in the daytime). This indicates that the known HONO sources incorporated in the UWCM model cannot explain the observed HONO level. Once HONO is constrained by the observation, the discrepancy between observation and model simulation improves (5.1 times in the morning and 2.1 times in the daytime) but still out of the measurement uncertainty range (35 %). We explore two possible reasons for the observed unexplainably high wintertime OH levels. First, potential roles of Cl atoms produce organic peroxy radicals from the reactions between Cl atmos and alkane compounds. However, the Cl levels during the observation period are estimated very low (~ 103 atoms cm-3) to explain the enhanced OH levels. Second, Impacts of higher HONO levels on the ground was evaluated. Strong HONO gradient towards ground was observed especially during the early morning (6 am to 8 am) was observed and the lowest level available for the HONO observation during the campaign is 5 m AGL. Once we assume the twice of the observed HONO levels averaged between 5 m to 15 m at 2

Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid: A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols

NASA Technical Reports Server (NTRS)

Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

1996-01-01

Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.

Long-term (2005-2014) trends in formaldehyde (HCHO) columns across North America as seen by the OMI satellite instrument: Evidence of changing emissions of volatile organic compounds

NASA Astrophysics Data System (ADS)

Zhu, Lei; Mickley, Loretta J.; Jacob, Daniel J.; Marais, Eloïse A.; Sheng, Jianxiong; Hu, Lu; Abad, Gonzalo González; Chance, Kelly

2017-07-01

Satellite observations of formaldehyde (HCHO) columns provide top-down information on emissions of highly reactive volatile organic compounds (VOCs). We examine the long-term trends in HCHO columns observed by the Ozone Monitoring Instrument from 2005 to 2014 across North America. Biogenic isoprene is the dominant source of HCHO, and its emission has a large temperature dependence. After correcting for this dependence, we find a general pattern of increases in much of North America but decreases in the southeastern U.S. Over the Houston-Galveston-Brazoria industrial area, HCHO columns decreased by 2.2% a-1 from 2005 to 2014, consistent with trends in emissions of anthropogenic VOCs. Over the Cold Lake Oil Sands in the southern Alberta in Canada, HCHO columns increased by 3.8% a-1, consistent with the increase in crude oil production there. HCHO variability in the northwestern U.S. and Midwest could be related to afforestation and corn silage production. Although NOx levels can affect the HCHO yield from isoprene oxidation, we find that decreases in anthropogenic NOx emissions made only a small contribution to the observed HCHO trends.