Статті в журналах: "HOx and RO2 radicals"

1

Liao, J., L. G. Huey, D. J. Tanner, N. Brough, S. Brooks, J. E. Dibb, J. Stutz, et al. "Observations of hydroxyl and peroxy radicals and the impact of BrO at Summit, Greenland in 2007 and 2008." Atmospheric Chemistry and Physics 11, no. 16 (August 23, 2011): 8577–91. http://dx.doi.org/10.5194/acp-11-8577-2011.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The Greenland Summit Halogen-HOx (GSHOX) Campaign was performed in spring 2007 and summer 2008 to investigate the impact of halogens on HOx (= OH + HO2) cycling above the Greenland Ice Sheet. Chemical species including hydroxyl and peroxy radicals (OH and HO2 + RO2), ozone (O3), nitrogen oxide (NO), nitric acid (HNO3), nitrous acid (HONO), reactive gaseous mercury (RGM), and bromine oxide (BrO) were measured during the campaign. The median midday values of HO2 + RO2 and OH concentrations observed by chemical ionization mass spectrometry (CIMS) were 2.7 × 108 molec cm−3 and 3.0 × 106 molec cm−3 in spring 2007, and 4.2 × 108 molec cm−3 and 4.1 × 106 molec cm−3 in summer 2008. A basic photochemical 0-D box model highly constrained by observations of H2O, O3, CO, CH4, NO, and J values predicted HO2 + RO2 (R = 0.90, slope = 0.87 in 2007; R = 0.79, slope = 0.96 in 2008) reasonably well and under predicted OH (R = 0.83, slope = 0.72 in 2007; R = 0.76, slope = 0.54 in 2008). Constraining the model to HONO observations did not significantly improve the ratio of OH to HO2 + RO2 and the correlation between predictions and observations. Including bromine chemistry in the model constrained by observations of BrO improved the correlation between observed and predicted HO2 + RO2 and OH, and brought the average hourly OH and HO2 + RO2 predictions closer to the observations. These model comparisons confirmed our understanding of the dominant HOx sources and sinks in this environment and indicated that BrO impacted the OH levels at Summit. Although, significant discrepancies between observed and predicted OH could not be explained by the measured BrO. Finally, observations of enhanced RGM were found to be coincident with under prediction of OH.

2

Whalley, L. K., M. A. Blitz, M. Desservettaz, P. W. Seakins, and D. E. Heard. "Reporting the sensitivity of Laser Induced Fluorescence instruments used for HO2 detection to an interference from RO2 radicals and introducing a novel approach that enables HO2 and certain RO2 types to be selectively measured." Atmospheric Measurement Techniques Discussions 6, no. 4 (July 9, 2013): 6249–92. http://dx.doi.org/10.5194/amtd-6-6249-2013.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Laboratory studies have revealed that alkene-derived RO2 and longer-chain alkane-derived RO2 (>C3) radicals rapidly convert to HO2 and then to OH in the presence of NO in a Fluorescence Assay by Gas Expansion (FAGE) detection cell (Fuchs et al., 2011). Three different FAGE cells that have been used to make ambient measurements of OH and HO2 in the University of Leeds ground-based instrument have been assessed to determine the sensitivity of each cell, when operating in HO2 detection mode, to RO2 radicals. The sensitivity to this interference was found to be highly dependent on cell design and operating parameters. Under the operating conditions employed during fieldwork undertaken in the Borneo rainforest in 2008, an OH yield of 17% was experimentally determined for both ethene- and isoprene-derived RO2 radicals. The high pumping capacity of this system, resulting in a short residence time, coupled with poor mixing of NO into the ambient air-stream for the titration of HO2 to OH effectively minimised this potential interference. An OH yield of 46% was observed for ethene-derived RO2 radicals when a smaller detection cell was used, in which the mixing of NO into the ambient air was improved and the cell residence times were longer. For a newly developed ROx LIF cell, used for detection of HO2 and RO2 radicals, when running in HOx mode an OH yield of 95% was observed for ethene-derived RO2 radicals. In experiments in which conditions ensured the conversion of RO2 to OH was complete, the yields of OH from a range of different RO2 species agreed well with model predictions based on the Master Chemical Mechanism version 3.2. For ethene and isoprene derived RO2 species, the relative sensitivity of FAGE was found to be close to that for HO2 with an OH yield of 100% and 92% respectively. For the longer-chain alkane-derived RO2 radicals, model predicted OH yields were highly dependent upon temperature. A model predicted OH yield of 74% at 298 K and 36% at 255 K were calculated for cyclohexane derived RO2 radicals and an experimental yield of 38% was observed indicating that the temperature within the cell was below ambient owing to the supersonic expansion of the airstream in the low pressure cell. These findings suggest that observations of HO2 by some LIF instruments worldwide may be higher than the true value if the instruments were sensitive to these RO2 species. If this is the case, it becomes necessary to compare atmospheric chemistry model simulations to HO2* observations, where HO2&ast; = [HO2] + α [RO2] and α is the mean fractional contribution of the RO2 species that interfere RO2i). This methodology, however, relies on model simulations of speciated RO2 radicals, as instrumentation to make speciated RO2 measurements does not currently exist. Here we present an approach that enables the concentration of HO2 and RO2i to be selectively determined by varying the concentration of NO injected into a FAGE cell. Measurements of [HO2] and [RO2i] taken in London are presented.

3

Liao, J., L. G. Huey, D. J. Tanner, S. Brooks, J. E. Dibb, J. Stutz, J. L. Thomas, B. Lefer, C. Haman, and K. Gorham. "Observations of hydroxyl and peroxy radicals and the impact of BrO at Summit, Greenland in 2007 and 2008." Atmospheric Chemistry and Physics Discussions 11, no. 4 (April 26, 2011): 12725–62. http://dx.doi.org/10.5194/acpd-11-12725-2011.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The Greenland Summit Halogen-HOx (GSHOX) Campaign was performed in spring~2007 and summer~2008 to investigate the impact of halogens on HOx (=OH + HO2) cycling above the Greenland Ice Sheet. Chemical species including hydroxyl and peroxy radicals (OH and HO2 + ROx), ozone (O3), nitrogen oxide (NO), nitric acid (HNO2), nitrous acid (HONO), reactive gaseous mercury (RGM), and bromine oxide (BrO) were measured during the campaign. The median midday values of HO2 + RO2 and OH concentrations observed by chemical ionization mass spectrometry (CIMS) were 2.7 × 108 molec cm−3 and 3.0 × 106 molec cm−3 in spring 2007, and 4.2 × 108 molec cm−3 and 4.1 × 106 molec cm−3 in summer~2008. A basic photochemical 0-D box model highly constrained by observations of H2O, O3, CO, CH4, NO, and J values predicted HO2 + RO2 (R = 0.90, slope = 0.87 in 2007; R = 0.79, slope = 0.96 in 2008) reasonably well and under predicted OH (R = 0.83, slope = 0.72 in 2007; R = 0.76, slope = 0.54 in 2008). Constraining the model to HONO observations did not significantly change the predictions. Including bromine chemistry in the model constrained by observations of BrO improved the correlation between observed and predicted HO2 + RO2 and OH, and brought the average hourly OH and HO2+RO2 predictions closer to the observations. These model comparisons confirmed our understanding of the dominant HOx sources and sinks in this environment and indicated that BrO impacted the OH levels at Summit. Although, significant discrepancies between observed and predicted OH could not be explained by the measured BrO. Finally, observations of enhanced RGM were found to be coincident with under prediction of OH.

4

Bottorff, Brandon, Michelle M. Lew, Youngjun Woo, Pamela Rickly, Matthew D. Rollings, Benjamin Deming, Daniel C. Anderson, et al. "OH, HO₂, and RO₂ radical chemistry in a rural forest environment: measurements, model comparisons, and evidence of a missing radical sink." Atmospheric Chemistry and Physics 23, no. 18 (September 15, 2023): 10287–311. http://dx.doi.org/10.5194/acp-23-10287-2023.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The hydroxyl (OH), hydroperoxy (HO2), and organic peroxy (RO2) radicals play important roles in atmospheric chemistry. In the presence of nitrogen oxides (NOx), reactions between OH and volatile organic compounds (VOCs) can initiate a radical propagation cycle that leads to the production of ozone and secondary organic aerosols. Previous measurements of these radicals under low-NOx conditions in forested environments characterized by emissions of biogenic VOCs, including isoprene and monoterpenes, have shown discrepancies with modeled concentrations. During the summer of 2016, OH, HO2, and RO2 radical concentrations were measured as part of the Program for Research on Oxidants: Photochemistry, Emissions, and Transport – Atmospheric Measurements of Oxidants in Summer (PROPHET-AMOS) campaign in a midlatitude deciduous broadleaf forest. Measurements of OH and HO2 were made by laser-induced fluorescence–fluorescence assay by gas expansion (LIF-FAGE) techniques, and total peroxy radical (XO2) mixing ratios were measured by the Ethane CHemical AMPlifier (ECHAMP) instrument. Supporting measurements of photolysis frequencies, VOCs, NOx, O3, and meteorological data were used to constrain a zero-dimensional box model utilizing either the Regional Atmospheric Chemical Mechanism (RACM2) or the Master Chemical Mechanism (MCM). Model simulations tested the influence of HOx regeneration reactions within the isoprene oxidation scheme from the Leuven Isoprene Mechanism (LIM1). On average, the LIM1 models overestimated daytime maximum measurements by approximately 40 % for OH, 65 % for HO2, and more than a factor of 2 for XO2. Modeled XO2 mixing ratios were also significantly higher than measured at night. Addition of RO2 + RO2 accretion reactions for terpene-derived RO2 radicals to the model can partially explain the discrepancy between measurements and modeled peroxy radical concentrations at night but cannot explain the daytime discrepancies when OH reactivity is dominated by isoprene. The models also overestimated measured concentrations of isoprene-derived hydroxyhydroperoxides (ISOPOOH) by a factor of 10 during the daytime, consistent with the model overestimation of peroxy radical concentrations. Constraining the model to the measured concentration of peroxy radicals improves the agreement with the measured ISOPOOH concentrations, suggesting that the measured radical concentrations are more consistent with the measured ISOPOOH concentrations. These results suggest that the models may be missing an important daytime radical sink and could be overestimating the rate of ozone and secondary product formation in this forest.

5

Lew, Michelle M., Sebastien Dusanter, and Philip S. Stevens. "Measurement of interferences associated with the detection of the hydroperoxy radical in the atmosphere using laser-induced fluorescence." Atmospheric Measurement Techniques 11, no. 1 (January 10, 2018): 95–109. http://dx.doi.org/10.5194/amt-11-95-2018.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. One technique used to measure concentrations of the hydroperoxy radical (HO2) in the atmosphere involves chemically converting it to OH by addition of NO and subsequent detection of OH. However, some organic peroxy radicals (RO2) can also be rapidly converted to HO2 (and subsequently OH) in the presence of NO, interfering with measurements of ambient HO2 radical concentrations. This interference must be characterized for each instrument to determine to what extent various RO2 radicals interfere with measurements of HO2 and to assess the impact of this interference on past measurements. The efficiency of RO2-to-HO2 conversion for the Indiana University laser-induced fluorescence–fluorescence assay by gas expansion (IU-FAGE) instrument was measured for a variety of RO2 radicals. Known quantities of OH and HO2 radicals were produced from the photolysis of water vapor at 184.9 nm, and RO2 radicals were produced by the reaction of several volatile organic compounds (VOCs) with OH. The conversion efficiency of RO2 radicals to HO2 was measured when NO was added to the sampling cell for conditions employed during several previous field campaigns. For these conditions, approximately 80 % of alkene-derived RO2 radicals and 20 % of alkane-derived RO2 radicals were converted to HO2. Based on these measurements, interferences from various RO2 radicals contributed to approximately 35 % of the measured HO2 signal during the Mexico City Metropolitan Area (MCMA) 2006 campaign (MCMA-2006), where the measured VOCs consisted of a mixture of saturated and unsaturated species. However, this interference can contribute more significantly to the measured HO2 signal in forested environments dominated by unsaturated biogenic emissions such as isoprene.

6

Hornbrook, R. S., J. H. Crawford, G. D. Edwards, O. Goyea, R. L. Mauldin III, J. S. Olson, and C. A. Cantrell. "Measurements of tropospheric HO2 and RO2 by oxygen dilution modulation and chemical ionization mass spectrometry." Atmospheric Chemistry and Physics Discussions 10, no. 9 (September 28, 2010): 22219–77. http://dx.doi.org/10.5194/acpd-10-22219-2010.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. An improved method for the measurement of hydroperoxy radicals (HO2) and organic peroxy radicals (RO2, where R is any organic group) has been developed that combines two previous chemical conversion/chemical ionization mass spectrometry (CIMS) peroxy radical measurement techniques. Applicable to both ground-based and aircraft platforms, the method provides good separation between HO2 and RO2 and frequent measurement capability with observations of both HO2 and HO2 + RO2 amounts each minute. This allows for analyses of measured [HO2]/[HO2 + RO2] ratios on timescales relevant to tropospheric photochemistry. By varying both [NO] and [O2] simultaneously in the chemical conversion region of the PeRCIMS (Peroxy Radical CIMS) inlet, the method exploits the changing conversion efficiency of RO2 to HO2 under different inlet [NO]/[O2] to selectively observe either primarily HO2 or the sum of HO2 and RO2. Two modes of operation have been established for ambient measurements: in the first half of the minute, RO2 radicals are measured at close to 100% efficiency along with HO2 radicals (low [NO]/[O2] = 2.53 × 10−5) and in the second half of the minute, HO2 is detected while the majority of ambient RO2 radicals are measured with approximately 15% efficiency (high [NO]/[O2] = 6.80 × 10−4). The method has been tested extensively in the laboratory under various conditions and for a variety of organic peroxy radicals relevant to the atmosphere and the results of these tests are presented. The modified PeRCIMS instrument has been deployed successfully using the current measurement technique on a number of aircraft campaigns, including on the NSF/NCAR C-130 during the MIRAGE-Mex and NASA INTEX-B field campaigns in the spring of 2006. A brief comparison of the peroxy radical measurements during these campaigns to a photochemical box model confirms that the PeRCIMS is able to successfully separate and measure HO2 and RO2 under the majority of tropospheric conditions.

7

Andrés-Hernández, M. D., D. Kartal, J. N. Growley, V. Sinha, E. Regelin, M. Martínez-Harder, V. Nenakhov, et al. "Diel peroxy radicals in a semi industrial coastal area: nighttime formation of free radicals." Atmospheric Chemistry and Physics Discussions 12, no. 8 (August 7, 2012): 19529–70. http://dx.doi.org/10.5194/acpd-12-19529-2012.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Peroxy radicals were measured by a PeRCA (Peroxy Radical Chemical Amplifier) instrument in the boundary layer during the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) campaign at a coastal, forested site influenced by urban-industrial emissions in Southern Spain in late autumn. Total peroxy radicals (RO2* = HO2 + ΣRO2) generally showed a daylight maximum between 10 and 50 pptv at 13:00 UTC, with an average of 18 pptv over the 15 days of measurements. Emissions from the industrial area of Huelva often impacted the measurement site at night during the campaign. The processing of significant levels of anthropogenic organics leads to an intense nocturnal radical chemistry accompanied by formation of organic peroxy radicals at comparable levels to those of summer photochemical conditions with peak events up to 60–80 pptv. The RO2 production initiated by reactions of NO3 with organic trace gases was estimated to be significant but not sufficient to account for the concentrations of RO2* observed in air masses carrying high pollutant loading. The nocturnal production of peroxy radicals seems therefore to be dominated by ozonolysis of volatile organic compounds. RO2* diurnal variations were consistent with other HO2 measurements available at the site. HO2/RO2* ratios generally varied between 0.3 and 0.4 in all wind directions. Occasional HO2/RO2* ≥ 1 seemed to be associated with periods of high RO2* variability and with RO2 interferences in the HO2 measurement in air masses with high RO2 load.

8

Ma, Xuefei, Zhaofeng Tan, Keding Lu, Xinping Yang, Xiaorui Chen, Haichao Wang, Shiyi Chen, et al. "OH and HO2 radical chemistry at a suburban site during the EXPLORE-YRD campaign in 2018." Atmospheric Chemistry and Physics 22, no. 10 (May 31, 2022): 7005–28. http://dx.doi.org/10.5194/acp-22-7005-2022.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The first OH and HO2 radical observation in Yangtze River Delta, one of the four major urban agglomerations in China, was carried out at a suburban site (Taizhou) in summer 2018 from May to June, aiming to elucidate the atmospheric oxidation capacity in this region. The maximum diurnal averaged OH and HO2 concentrations were 1.0×107 and 1.1×109 cm−3, respectively, which were the second highest HOx (sum of OH and HO2) radical concentrations observed in China. HONO photolysis was the dominant radical primary source, accounting for 42 % of the total radical initiation rate. Other contributions were from carbonyl photolysis (including HCHO, 24 %), O3 photolysis (17 %), alkene ozonolysis (14 %), and NO3 oxidation (3 %). A chemical box model based on the RACM2-LIM1 mechanism could generally reproduce the observed HOx radicals, but systematic discrepancy remained in the afternoon for the OH radical, when the NO mixing ratio was less than 0.3 ppb. An additional recycling mechanism equivalent to 100 ppt NO was capable to fill the gap. The sum of monoterpenes was on average up to 0.4 ppb during daytime, which was all allocated to α-pinene in the base model. A sensitivity test without monoterpene input showed the modeled OH and HO2 concentrations would increase by 7 % and 4 %, respectively, but modeled RO2 concentration would significantly decrease by 23 %, indicating that monoterpene was an important precursor of RO2 radicals in this study. Consequently, the daily integrated net ozone production would reduce by 6.3 ppb without monoterpene input, proving the significant role of monoterpene in the photochemical O3 production in this study. In addition, the generally good agreement between observed and modeled HOx concentrations suggested no significant HO2 heterogeneous uptake process during this campaign. Incorporation of HO2 heterogeneous uptake process would worsen the agreement between HOx radical observation and simulation, and the discrepancy would be beyond the combined measurement–model uncertainties using an effective uptake coefficient of 0.2. Finally, the ozone production efficiency (OPE) was only 1.7 in this study, a few folds lower than other studies in (sub)urban environments. The low OPE indicated a slow radical propagation rate and short chain length. As a consequence, ozone formation was suppressed by the low NO concentration in this study.

9

Xue, L. K., T. Wang, H. Guo, D. R. Blake, J. Tang, X. C. Zhang, S. M. Saunders, and W. X. Wang. "Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory." Atmospheric Chemistry and Physics 13, no. 17 (September 2, 2013): 8551–67. http://dx.doi.org/10.5194/acp-13-8551-2013.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The chemistry of the natural atmosphere and the influence by long-range transport of air pollution are key issues in the atmospheric sciences. Here we present two intensive field measurements of volatile organic compounds (VOCs) in late spring and summer of 2003 at Mt. Waliguan (WLG, 36.28° N, 100.90° E, 3816 m a.s.l.), a baseline station in the northeast part of the Qinghai-Tibetan Plateau. Most VOC species exhibited higher concentrations in late spring than in summer. A typical diurnal variation was observed with higher nighttime levels, in contrast to results from other mountainous sites. Five different air masses were identified from backward trajectory analysis showing distinct VOC speciation. Air masses originating from the central Eurasian continent contained the lowest VOC levels compared to the others that were impacted by anthropogenic emissions from China and the Indian subcontinent. A photochemical box model based on the Master Chemical Mechanism (version 3.2) and constrained by a full suite of measurements was developed to probe the photochemistry of atmosphere at WLG. Our results show net ozone production from in situ photochemistry during both late spring and summer. Oxidation of nitric oxide (NO) by the hydroperoxyl radical (HO2) dominates the ozone production relative to the oxidation by the organic peroxy radicals (RO2), and the ozone is primarily destroyed by photolysis and reactions with the HOx (HOx = OH + HO2) radicals. Ozone photolysis is the predominant primary source of radicals (ROx = OH + HO2 + RO2), followed by the photolysis of secondary oxygenated VOCs and hydrogen peroxides. The radical losses are governed by the self and cross reactions among the radicals. Overall, the findings of the present study provide insights into the background chemistry and the impacts of pollution transport on the pristine atmosphere over the Eurasian continent.

10

Liu, Y. J., I. Herdlinger-Blatt, K. A. McKinney, and S. T. Martin. "Production of methyl vinyl ketone and methacrolein via the hydroperoxyl pathway of isoprene oxidation." Atmospheric Chemistry and Physics Discussions 12, no. 12 (December 21, 2012): 33323–58. http://dx.doi.org/10.5194/acpd-12-33323-2012.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The photo-oxidation chemistry of isoprene (C5H8) was studied in a continuous-flow chamber under conditions such that the reactions of isoprene-derived peroxyl radicals (RO2) were dominated by hydroperoxyl (HO2) pathway. A proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) with switchable H3O+ and NO+ reagent ions was used for product analysis. The products methyl vinyl ketone (MVK; C4H6O) and methacrolein (MACR; C4H6O) were differentiated using NO+ reagent ions. The MVK and MACR yields were 4.3 ± 0.4% and 3.2 ± 0.3%, respectively, for HO2-dominant conditions at +25 °C and < 2% relative humidity. The respective yields were 41.1 ± 2.2% and 28.8 ± 1.2% for NO-dominant conditions. The yields for HO2-dominant conditions imply a concomitant yield (i.e., recycling factor) of hydrogen oxide radicals (HOx) of 15 ± 0.7% from the reaction of isoprene-derived RO2 with HO2. Other isoprene oxidation products, believed to be organic hydroperoxides, also contributed to the ion intensity at the same mass-to-charge (m/z) ratios as the MVK and MACR product ions, and these products were selectively removed from the gas phase using a variable temperature cold trap (−40 °C) in front of the PTR-TOF-MS. These hydroperoxide products were absent for NO-dominant conditions. When incorporated into regional and global chemical transport models, the yields of MVK and MACR and concomitant HOx yields reported in this study will improve the accuracy of simulations of the HO2 reaction pathway of isoprene, which has been shown to make a significant contribution to the total reactivity of isoprene-derived RO2 radicals on a global scale.

11

Hornbrook, R. S., J. H. Crawford, G. D. Edwards, O. Goyea, R. L. Mauldin III, J. S. Olson, and C. A. Cantrell. "Measurements of tropospheric HO2 and RO2 by oxygen dilution modulation and chemical ionization mass spectrometry." Atmospheric Measurement Techniques Discussions 4, no. 1 (January 18, 2011): 385–442. http://dx.doi.org/10.5194/amtd-4-385-2011.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. An improved method for the measurement of hydroperoxy radicals (HO2) and organic peroxy radicals (RO2, where R is any organic group) has been developed that combines two previous chemical conversion/chemical ionization mass spectrometry (CIMS) peroxy radical measurement techniques. Applicable to both ground-based and aircraft platforms, the method provides good separation between HO2 and RO2 and frequent measurement capability with observations of both HO2 and HO2+RO2 amounts each minute. This allows for analyses of measured [HO2]/[HO2+RO2] ratios on timescales relevant to tropospheric photochemistry. By varying both [NO] and [O2] simultaneously in the chemical conversion region of the PeRCIMS (Peroxy Radical CIMS) inlet, the method exploits the changing conversion efficiency of RO2 to HO2 under different inlet [NO]/[O2] to selectively observe either primarily HO2 or the sum of HO2 and RO2. Two modes of operation have been established for ambient measurements: in the first half of the minute, RO2 radicals are measured at close to 100% efficiency along with HO2 radicals (low [NO]/[O2] = 2.53×10−5) and in the second half of the minute, HO2 is detected while the majority of ambient RO2 radicals are measured with low efficiency, approximately 15% (high [NO]/[O2] = 6.80×10−4). The method has been tested extensively in the laboratory under various conditions and for a variety of organic peroxy radicals relevant to the atmosphere and the results of these tests are presented. The modified PeRCIMS instrument has been deployed successfully using the new measurement technique on a number of aircraft campaigns, including on the NSF/NCAR C-130 during the MIRAGE-Mex and NASA INTEX-B field campaigns in the spring of 2006. A brief comparison of the peroxy radical measurements during these campaigns to a photochemical box model indicates good agreement under tropospheric conditions where NOx (NO+NO2) concentrations are lower than 0.5 ppbV (parts per billion by volume).

12

Hornbrook, R. S., J. H. Crawford, G. D. Edwards, O. Goyea, R. L. Mauldin III, J. S. Olson, and C. A. Cantrell. "Measurements of tropospheric HO2 and RO2 by oxygen dilution modulation and chemical ionization mass spectrometry." Atmospheric Measurement Techniques 4, no. 4 (April 14, 2011): 735–56. http://dx.doi.org/10.5194/amt-4-735-2011.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. An improved method for the measurement of hydroperoxy radicals (HO2) and organic peroxy radicals (RO2, where R is any organic group) has been developed that combines two previous chemical conversion/chemical ionization mass spectrometry (CIMS) peroxy radical measurement techniques. Applicable to both ground-based and aircraft platforms, the method provides good separation between HO2 and RO2, and frequent measurement capability with observations of both HO2 and HO2 + RO2 amounts each minute. These improvements allow for analyses of measured [HO2]/[HO2 + RO2] ratios on timescales relevant to tropospheric photochemistry. By varying both [NO] and [O2] simultaneously in the chemical conversion region of the PeRCIMS (Peroxy Radical CIMS) inlet, the method exploits the changing conversion efficiency of RO2 to HO2 under different inlet [NO]/[O2] to selectively observe either primarily HO2 or the sum of HO2 and RO2. Two modes of operation have been established for ambient measurements: in the first half of the minute, RO2 radicals are measured at close to 100% efficiency along with HO2 radicals (low [NO]/[O2] = 2.53 × 10−5) and in the second half of the minute, HO2 is detected while the majority of ambient RO2 radicals are measured with low efficiency, approximately 15% (high [NO]/[O2] = 6.80 × 10−4). The method has been tested extensively in the laboratory under various conditions and for a variety of organic peroxy radicals relevant to the atmosphere and the results of these tests are presented. The modified PeRCIMS instrument has been deployed successfully using the new measurement technique on a number of aircraft campaigns, including on the NSF/NCAR C-130 during the MIRAGE-Mex and NASA INTEX-B field campaigns in the spring of 2006. A brief comparison of the peroxy radical measurements during these campaigns to a photochemical box model indicates good agreement under tropospheric conditions where NOx (NO + NO2) concentrations are lower than 0.5 ppbV (parts per billion by volume).

13

Fuchs, H., B. Bohn, A. Hofzumahaus, F. Holland, K. D. Lu, S. Nehr, F. Rohrer, and A. Wahner. "Detection of HO2 by laser-induced fluorescence: calibration and interferences from RO2 radicals." Atmospheric Measurement Techniques Discussions 4, no. 1 (February 25, 2011): 1255–302. http://dx.doi.org/10.5194/amtd-4-1255-2011.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. HO2 concentration measurements are widely accomplished by chemical conversion of HO2 to OH including reaction with NO and subsequent detection of OH by laser-induced fluorescence. RO2 radicals can be converted to OH via a similar radical reaction sequence including reaction with NO, so that they are potential interferences for HO2 measurements. Here, the conversion efficiency of various RO2 species to HO2 is investigated. Experiments were conducted with a radical source that produces OH and HO2 by water photolysis at 185 nm, which is frequently used for calibration of LIF instruments. The ratio of HO2 and the sum of OH and HO2 concentrations provided by the radical source was investigated and was found to be 0.50 ± 0.02. RO2 radicals are produced by the reaction of various organic compounds with OH in the radical source. Interferences via chemical conversion from RO2 radicals produced by the reaction of OH with alkanes (H-atom abstraction) are negligible consistent with measurements in the past. However, RO2 radicals from OH plus alkene- and aromatic-precursors including isoprene (mainly OH-addition) are detected with a relative sensitivity larger than 80% with respect to that for HO2 for the configuration of the instrument with which it was operated during field campaigns. Also RO2 from OH plus methyl vinyl ketone and methacrolein exhibit a relative detection sensitivity of 60%. Thus, previous measurements of HO2 radical concentrations with this instrument were biased in the presence of high RO2 radical concentrations from isoprene, alkenes or aromatics, but were not affected by interferences in clean air, when the OH reactivity was dominated by small alkanes. By reducing the NO concentration and/or the transport time between NO addition and OH detection, interference from these RO2 species are suppressed to values below 20% relative to the HO2 detection sensitivity. The HO2 conversion efficiency is also smaller by a factor of four, but this is still sufficient for atmospheric HO2 concentration measurements for a wide range of conditions.

14

Fuchs, H., B. Bohn, A. Hofzumahaus, F. Holland, K. D. Lu, S. Nehr, F. Rohrer, and A. Wahner. "Detection of HO2 by laser-induced fluorescence: calibration and interferences from RO2 radicals." Atmospheric Measurement Techniques 4, no. 6 (June 28, 2011): 1209–25. http://dx.doi.org/10.5194/amt-4-1209-2011.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. HO2 concentration measurements are widely accomplished by chemical conversion of HO2 to OH including reaction with NO and subsequent detection of OH by laser-induced fluorescence. RO2 radicals can be converted to OH via a similar radical reaction sequence including reaction with NO, so that they are potential interferences for HO2 measurements. Here, the conversion efficiency of various RO2 species to HO2 is investigated. Experiments were conducted with a radical source that produces OH and HO2 by water photolysis at 185 nm, which is frequently used for calibration of LIF instruments. The ratio of HO2 and the sum of OH and HO2 concentrations provided by the radical source was investigated and was found to be 0.50 ± 0.02. RO2 radicals are produced by the reaction of various organic compounds with OH in the radical source. Interferences via chemical conversion from RO2 radicals produced by the reaction of OH with methane and ethane (H-atom abstraction) are negligible consistent with measurements in the past. However, RO2 radicals from OH plus alkene- and aromatic-precursors including isoprene (mainly OH-addition) are detected with a relative sensitivity larger than 80 % with respect to that for HO2 for the configuration of the instrument with which it was operated during field campaigns. Also RO2 from OH plus methyl vinyl ketone and methacrolein exhibit a relative detection sensitivity of 60 %. Thus, previous measurements of HO2 radical concentrations with this instrument were biased in the presence of high RO2 radical concentrations from isoprene, alkenes or aromatics, but were not affected by interferences in remote clean environment with no significant emissions of biogenic VOCs, when the OH reactivity was dominated by small alkanes. By reducing the NO concentration and/or the transport time between NO addition and OH detection, interference from these RO2 species are suppressed to values below 20 % relative to the HO2 detection sensitivity. The HO2 conversion efficiency is also smaller by a factor of four, but this is still sufficient for atmospheric HO2 concentration measurements for a wide range of conditions.

15

Jenkin, Michael E., Richard Valorso, Bernard Aumont, and Andrew R. Rickard. "Estimation of rate coefficients and branching ratios for reactions of organic peroxy radicals for use in automated mechanism construction." Atmospheric Chemistry and Physics 19, no. 11 (June 7, 2019): 7691–717. http://dx.doi.org/10.5194/acp-19-7691-2019.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Organic peroxy radicals (RO2), formed from the degradation of hydrocarbons and other volatile organic compounds (VOCs), play a key role in tropospheric oxidation mechanisms. Several competing reactions may be available for a given RO2 radical, the relative rates of which depend on both the structure of RO2 and the ambient conditions. Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO2 with NO, NO2, NO3, OH and HO2; and for their self-reactions and cross-reactions with other RO2 radicals. This information is used to define generic rate coefficients and structure–activity relationship (SAR) methods that can be applied to the bimolecular reactions of a series of important classes of hydrocarbon and oxygenated RO2 radicals. Information for selected unimolecular isomerization reactions (i.e. H-atom shift and ring-closure reactions) is also summarized and discussed. The methods presented here are intended to guide the representation of RO2 radical chemistry in the next generation of explicit detailed chemical mechanisms.

16

Andrés-Hernández, M. D., D. Kartal, J. N. Crowley, V. Sinha, E. Regelin, M. Martínez-Harder, V. Nenakhov, et al. "Diel peroxy radicals in a semi-industrial coastal area: nighttime formation of free radicals." Atmospheric Chemistry and Physics 13, no. 11 (June 14, 2013): 5731–49. http://dx.doi.org/10.5194/acp-13-5731-2013.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Peroxy radicals were measured by a PeRCA (Peroxy Radical Chemical Amplifier) instrument in the boundary layer during the DOMINO (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) campaign at a coastal, forested site influenced by urban-industrial emissions in southern Spain in late autumn. Total peroxy radicals (RO2* = HO2 + ΣRO2) generally showed a daylight maximum between 10 and 50 pptv at 13:00 UTC, with an average of 18 pptv over the 15 days of measurements. Emissions from the industrial area of Huelva often impacted the measurement site at night during the campaign. The processing of significant levels of anthropogenic organics leads to an intense nocturnal radical chemistry accompanied by formation of organic peroxy radicals at comparable levels to those of summer photochemical conditions with peak events up to 60–80 pptv. The RO2 production initiated by reactions of NO3 with organic trace gases was estimated to be significant, but not sufficient to account for the concentrations of RO2* observed in air masses carrying high pollutant loading. The nocturnal production of peroxy radicals in those periods seems therefore to be dominated by ozonolysis of volatile organic compounds, in particular alkenes of industrial petrochemical origin. RO2* diurnal variations were consistent with HO2 measurements available at the site. HO2/RO2* ratios generally varied between 0.3 and 0.6, though on some occasions this ratio was likely to have been affected by instrumental artifacts (overestimated HO2) associated with high RO2 loads.

17

Sheehy, P. M., R. Volkamer, L. T. Molina, and M. J. Molina. "Oxidative capacity of the Mexico City atmosphere – Part 2: A ROx radical cycling perspective." Atmospheric Chemistry and Physics 10, no. 14 (July 30, 2010): 6993–7008. http://dx.doi.org/10.5194/acp-10-6993-2010.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. A box model using measurements from the Mexico City Metropolitan Area study in the spring of 2003 (MCMA-2003) is presented to study oxidative capacity (our ability to predict OH radicals) and ROx (ROx=OH+HO2+RO2+RO) radical cycling in a polluted (i.e., very high NOx=NO+NO2) atmosphere. Model simulations were performed using the Master Chemical Mechanism (MCMv3.1) constrained with 10 min averaged measurements of major radical sources (i.e., HCHO, HONO, O3, CHOCHO, etc.), radical sink precursors (i.e., NO, NO2, SO2, CO, and 102 volatile organic compounds (VOC)), meteorological parameters (temperature, pressure, water vapor concentration, dilution), and photolysis frequencies. Modeled HOx (=OH+HO2) concentrations compare favorably with measured concentrations for most of the day; however, the model under-predicts the concentrations of radicals in the early morning. This "missing reactivity" is highest during peak photochemical activity, and is least visible in a direct comparison of HOx radical concentrations. We conclude that the most likely scenario to reconcile model predictions with observations is the existence of a currently unidentified additional source for RO2 radicals, in combination with an additional sink for HO2 radicals that does not form OH. The true uncertainty due to "missing reactivity" is apparent in parameters like chain length. We present a first attempt to calculate chain length rigorously i.e., we define two parameters that account for atmospheric complexity, and are based on (1) radical initiation, n(OH), and (2) radical termination, ω. We find very high values of n(OH) in the early morning are incompatible with our current understanding of ROx termination routes. We also observe missing reactivity in the rate of ozone production (P(O3)). For example, the integral amount of ozone produced could be under-predicted by a factor of two. We argue that this uncertainty is partly accounted for in lumped chemical codes that are optimized to predict ozone concentrations; however, these codes do not reflect the true uncertainty in oxidative capacity that is relevant to other aspects of air quality management, such as the formation of secondary organic aerosol (SOA). Our analysis highlights that apart from uncertainties in emissions, and meteorology, there is an additional major uncertainty in chemical mechanisms that affects our ability to predict ozone and SOA formation with confidence.

18

Fuchs, Hendrik, Sascha Albrecht, Ismail–Hakki Acir, Birger Bohn, Martin Breitenlechner, Hans-Peter Dorn, Georgios I. Gkatzelis, et al. "Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR." Atmospheric Chemistry and Physics 18, no. 11 (June 7, 2018): 8001–16. http://dx.doi.org/10.5194/acp-18-8001-2018.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO2) mainly reacted with NO (“high NO” case) and for conditions at which other reaction channels could compete (“low NO” case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model–measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO2 plus HO2 reaction channels as proposed in literature for the major RO2 species formed from the reaction of MVK with OH. However, this study shows that also HO2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO2 radical reactions, but indirectly via increased HO2. Quantum chemical calculations show that HO2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO2 species (reaction rate constant 0.003 s−1). However, additional HO2 from this reaction was not sufficiently large to bring modelled HO2 radical concentrations into agreement with measurements due to the small yield of this RO2 species. An additional reaction channel of the major RO2 species with a reaction rate constant of (0.006 ± 0.004) s−1 would be required that produces concurrently HO2 radicals and glycolaldehyde to achieve model–measurement agreement. A unimolecular reaction similar to the 1,5-H shift reaction that was proposed in literature for RO2 radicals from MVK would not explain product yields for conditions of experiments in this study. A set of H-migration reactions for the main RO2 radicals were investigated by quantum chemical and theoretical kinetic methodologies, but did not reveal a contributing route to HO2 radicals or glycolaldehyde.

19

Slater, Eloise J., Lisa K. Whalley, Robert Woodward-Massey, Chunxiang Ye, James D. Lee, Freya Squires, James R. Hopkins, et al. "Elevated levels of OH observed in haze events during wintertime in central Beijing." Atmospheric Chemistry and Physics 20, no. 23 (December 2, 2020): 14847–71. http://dx.doi.org/10.5194/acp-20-14847-2020.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Wintertime in situ measurements of OH, HO2 and RO2 radicals and OH reactivity were made in central Beijing during November and December 2016. Exceptionally elevated NO was observed on occasions, up to ∼250 ppbv. The daily maximum mixing ratios for radical species varied significantly day-to-day over the ranges 1–8×106 cm−3 (OH), 0.2–1.5×108 cm−3 (HO2) and 0.3–2.5×108 cm−3 (RO2). Averaged over the full observation period, the mean daytime peak in radicals was 2.7×106, 0.39×108 and 0.88×108 cm−3 for OH, HO2 and total RO2, respectively. The main daytime source of new radicals via initiation processes (primary production) was the photolysis of HONO (∼83 %), and the dominant termination pathways were the reactions of OH with NO and NO2, particularly under polluted haze conditions. The Master Chemical Mechanism (MCM) v3.3.1 operating within a box model was used to simulate the concentrations of OH, HO2 and RO2. The model underpredicted OH, HO2 and RO2, especially when NO mixing ratios were high (above 6 ppbv). The observation-to-model ratio of OH, HO2 and RO2 increased from ∼1 (for all radicals) at 3 ppbv of NO to a factor of ∼3, ∼20 and ∼91 for OH, HO2 and RO2, respectively, at ∼200 ppbv of NO. The significant underprediction of radical concentrations by the MCM suggests a deficiency in the representation of gas-phase chemistry at high NOx. The OH concentrations were surprisingly similar (within 20 % during the day) in and outside of haze events, despite j(O1D) decreasing by 50 % during haze periods. These observations provide strong evidence that gas-phase oxidation by OH can continue to generate secondary pollutants even under high-pollution episodes, despite the reduction in photolysis rates within haze.

20

Cho, Changmin, Hendrik Fuchs, Andreas Hofzumahaus, Frank Holland, William J. Bloss, Birger Bohn, Hans-Peter Dorn, et al. "Experimental chemical budgets of OH, HO₂, and RO₂ radicals in rural air in western Germany during the JULIAC campaign 2019." Atmospheric Chemistry and Physics 23, no. 3 (February 8, 2023): 2003–33. http://dx.doi.org/10.5194/acp-23-2003-2023.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Photochemical processes in ambient air were studied using the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich, Germany. Ambient air was continuously drawn into the chamber through a 50 m high inlet line and passed through the chamber for 1 month in each season throughout 2019. The residence time of the air inside the chamber was about 1 h. As the research center is surrounded by a mixed deciduous forest and is located close to the city Jülich, the sampled air was influenced by both anthropogenic and biogenic emissions. Measurements of hydroxyl (OH), hydroperoxyl (HO2), and organic peroxy (RO2) radicals were achieved by a laser-induced fluorescence instrument. The radical measurements together with measurements of OH reactivity (kOH, the inverse of the OH lifetime) and a comprehensive set of trace gas concentrations and aerosol properties allowed for the investigation of the seasonal and diurnal variation of radical production and destruction pathways. In spring and summer periods, median OH concentrations reached 6 × 106 cm−3 at noon, and median concentrations of both HO2 and RO2 radicals were 3 × 108 cm−3. The measured OH reactivity was between 4 and 18 s−1 in both seasons. The total reaction rate of peroxy radicals with NO was found to be consistent with production rates of odd oxygen (Ox= NO2 + O3) determined from NO2 and O3 concentration measurements. The chemical budgets of radicals were analyzed for the spring and summer seasons, when peroxy radical concentrations were above the detection limit. For most conditions, the concentrations of radicals were mainly sustained by the regeneration of OH via reactions of HO2 and RO2 radicals with nitric oxide (NO). The median diurnal profiles of the total radical production and destruction rates showed maxima between 3 and 6 ppbv h−1 for OH, HO2, and RO2. Total ROX (OH, HO2, and RO2) initiation and termination rates were below 3 ppbv h−1. The highest OH radical turnover rate of 13 ppbv h−1 was observed during a high-temperature (max. 40 ∘C) period in August. In this period, the highest HO2, RO2, and ROX turnover rates were around 11, 10, and 4 ppbv h−1, respectively. When NO mixing ratios were between 1 and 3 ppbv, OH and HO2 production and destruction rates were balanced, but unexplained RO2 and ROX production reactions with median rates of 2 and 0.4 ppbv h−1, respectively, were required to balance their destruction. For NO mixing ratios above 3 ppbv, the peroxy radical reaction rates with NO were highly uncertain due to the low peroxy radical concentrations close to the limit of NO interferences in the HO2 and RO2 measurements. For NO mixing ratios below 1 ppbv, a missing source for OH and a missing sink for HO2 were found with maximum rates of 3.0 and 2.0 ppbv h−1, respectively. The missing OH source likely consisted of a combination of a missing inter-radical HO2 to OH conversion reaction (up to 2 ppbv h−1) and a missing primary radical source (0.5–1.4 ppbv h−1). The dataset collected in this campaign allowed analyzing the potential impact of OH regeneration from RO2 isomerization reactions from isoprene, HO2 uptake on aerosol, and RO2 production from chlorine chemistry on radical production and destruction rates. These processes were negligible for the chemical conditions encountered in this study.

21

Xue, L. K., T. Wang, H. Guo, D. R. Blake, J. Tang, X. C. Zhang, S. M. Saunders, and W. X. Wang. "Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory." Atmospheric Chemistry and Physics Discussions 13, no. 5 (May 2, 2013): 11745–88. http://dx.doi.org/10.5194/acpd-13-11745-2013.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The chemistry of the natural atmosphere and the influence by long-range transport of air pollution are key issues in the atmospheric sciences. Here we present two intensive field measurements of volatile organic compounds (VOCs) in late spring and summer of 2003 at Mt. Waliguan (WLG, 36.28° N, 100.90° E, 3816 m a.s.l.), a baseline station in the northeast part of Qinghai-Tibetan Plateau. Most VOC species exhibited higher concentrations in late spring than in summer. A typical diurnal variation was observed with higher nighttime levels, in contrast to results from other mountainous sites. Five different air masses were identified from backward trajectory analysis showing distinct VOC speciation. Air masses originating from the central Eurasian continent contained the lowest VOC levels compared to the others that were impacted by anthropogenic emissions from China and the Indian sub-continent. The data were compared with the TRACE-P (Transport and Chemical Evolution over the Pacific) data to examine the inflow and outflow of air pollution over the China sub-continent. The results show that the free troposphere over China may be affected by the inflow from the Eurasian continent in spring, and the emissions in China may not have a significant influence on the free tropospheric outflow. A photochemical box model based on the Master Chemical Mechanism (version 3.2) and constrained by a full suite of measurements was developed to probe the photochemistry of atmosphere at WLG. Our results show net ozone production from in-situ photochemistry during both late spring and summer. Oxidation of nitric oxide (NO) by the hydroperoxyl radical (HO2) dominates the ozone production relative to the oxidation by the organic peroxy radicals (RO2), and the ozone is primarily destroyed by photolysis and reactions with the HOx(HOx = OH + HO2) radicals. Ozone photolysis is the predominant primary source of radicals (ROx = OH + HO2 + RO2), followed by the photolysis of oxygenated VOCs and hydrogen peroxides. The radical losses are governed by the self and cross reactions among the radicals. The findings can provide insights into the background chemistry and the impacts of pollution transport on the pristine atmosphere over the Eurasian continent.

22

Kwan, A. J., A. W. H. Chan, N. L. Ng, H. G. Kjaergaard, J. H. Seinfeld, and P. O. Wennberg. "Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene." Atmospheric Chemistry and Physics Discussions 12, no. 1 (January 24, 2012): 2259–302. http://dx.doi.org/10.5194/acpd-12-2259-2012.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Peroxy radical reactions (RO2 + RO2) from the NO3-initiated oxidation of isoprene are studied with both gas chromatography and a chemical ionization mass spectrometry technique that allows for more specific speciation of products than in previous studies of this system. We find high nitrate yields (>~80%), consistent with other studies. We further see evidence of significant hydroxyl radical (OH) formation in this system, which we propose comes from RO2 + HO2 reactions with a yield of ~42–62%. An additional OH source is the second generation oxidation of the nitrooxyhydroperoxide, which produces OH and a dinitrooxyepoxide with a yield of ~35%. The branching ratio of the radical propagating, carbonyl- and alcohol-forming, and dimer-forming channels of the RO2 + RO2 reaction are found to be ~18–38%, ~59–77%, and ~3–4%, respectively. HO2 formation in this system is lower than has been previously assumed. Addition of RO2 to isoprene is suggested as a possible route to the formation of several isoprene dimer compounds (ROOR). The nitrooxy, allylic, and C5 peroxy radicals present in this system exhibit different behavior than the limited suite of peroxy radicals that have been studied to date.

23

Kwan, A. J., A. W. H. Chan, N. L. Ng, H. G. Kjaergaard, J. H. Seinfeld, and P. O. Wennberg. "Peroxy radical chemistry and OH radical production during the NO3-initiated oxidation of isoprene." Atmospheric Chemistry and Physics 12, no. 16 (August 17, 2012): 7499–515. http://dx.doi.org/10.5194/acp-12-7499-2012.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Peroxy radical reactions (RO2 + RO2) from the NO3-initiated oxidation of isoprene are studied with both gas chromatography and a chemical ionization mass spectrometry technique that allows for more specific speciation of products than in previous studies of this system. We find high nitrate yields (~ 80%), consistent with other studies. We further see evidence of significant hydroxyl radical (OH) formation in this system, which we propose comes from RO2 + HO2 reactions with a yield of ~38–58%. An additional OH source is the second generation oxidation of the nitrooxyhydroperoxide, which produces OH and a dinitrooxyepoxide with a yield of ~35%. The branching ratio of the radical propagating, carbonyl- and alcohol-forming, and organic peroxide-forming channels of the RO2 + RO2 reaction are found to be ~18–38%, ~59–77%, and ~3–4%, respectively. HO2 formation in this system is lower than has been previously assumed. Addition of RO2 to isoprene is suggested as a possible route to the formation of several isoprene C10-organic peroxide compounds (ROOR). The nitrooxy, allylic, and C5 peroxy radicals present in this system exhibit different behavior than the limited suite of peroxy radicals that have been studied to date.

24

Whalley, L. K., M. A. Blitz, M. Desservettaz, P. W. Seakins, and D. E. Heard. "Reporting the sensitivity of laser-induced fluorescence instruments used for HO2 detection to an interference from RO2 radicals and introducing a novel approach that enables HO2 and certain RO2 types to be selectively measured." Atmospheric Measurement Techniques 6, no. 12 (December 9, 2013): 3425–40. http://dx.doi.org/10.5194/amt-6-3425-2013.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Laboratory studies have revealed that alkene-derived RO2 and longer chain alkane-derived RO2 (> C3) radicals rapidly convert to HO2 and then to OH in the presence of NO in a fluorescence assay by gas expansion (FAGE) detection cell (Fuchs et al., 2011). Three different FAGE cells that have been used to make ambient measurements of OH and HO2 in the University of Leeds ground-based instrument have been assessed to determine the sensitivity of each cell, when operating in HO2 detection mode, to RO2 radicals. The sensitivity to this interference was found to be highly dependent on cell design and operating parameters. Under the operating conditions employed, during fieldwork undertaken in the Borneo rainforest in 2008, an OH yield of 17% was experimentally determined for both ethene- and isoprene-derived RO2 radicals. The high pumping capacity of this system, resulting in a short residence time in the cell, coupled with poor mixing of NO into the ambient air-stream for the titration of HO2 to OH effectively minimised this potential interference. An OH yield of 46% was observed for ethene-derived RO2 radicals when a smaller detection cell was used, in which the mixing of NO into the ambient air was improved and the cell residence times were much longer. For a newly developed ROxLIF cell, used for detection of HO2 and RO2 radicals an OH yield of 95% was observed for ethene-derived RO2 radicals, when running in HO2 mode. In experiments in which conditions ensured the conversion of RO2 to OH were complete, the yields of OH from a range of different RO2 species agreed well with model predictions based on the Master Chemical Mechanism version 3.2. For ethene and isoprene-derived RO2 species, the relative sensitivity of FAGE was found to be close to that for HO2, with an OH yield of 100% and 92%, respectively. For the longer chain or cyclic alkane-derived RO2 radicals (> C3), model predicted OH yields were highly dependent upon temperature. A model predicted OH yield of 74% at 298 K and 36% at 255 K were calculated for cyclohexane-derived RO2 radicals, and an experimental yield of 38% was observed indicating that the temperature within the cell was below ambient owing to the supersonic expansion of the airstream in the low pressure cell. These findings suggest that observations of HO2 by some LIF instruments worldwide may be higher than the true value if the instruments were sensitive to these RO2 species. If this is the case, it becomes necessary to compare atmospheric chemistry model simulations to HO2* observations, where HO2* = [HO2] + Σi αi [RO2i], and αi is the mean fractional contribution of the RO2 species that interfere (RO2i). This methodology, however, relies on model simulations of speciated RO2 radicals, as instrumentation to make speciated RO2 measurements does not currently exist. Here we present an approach that enables the concentration of HO2 and RO2i to be selectively determined by varying the concentration of NO injected into a FAGE cell. Measurements of [HO2] and [RO2i] taken in London are presented.

25

Stone, D., M. J. Evans, H. M. Walker, T. Ingham, S. Vaughan, B. Ouyang, O. J. Kennedy, et al. "Radical chemistry at night: comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project." Atmospheric Chemistry and Physics Discussions 13, no. 4 (April 11, 2013): 9519–66. http://dx.doi.org/10.5194/acpd-13-9519-2013.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The RONOCO aircraft campaign during July 2010 and January 2011 made observations of OH, HO2, NO3, N2O5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurement of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model, constrained by the concentrations of the longer lived species, using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with the model predictions. The model systematically underpredicts HO2 by a factor of ~2 and overpredicts NO3 and N2O5 by factors of around 75% and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3x = NO3 + N2O5) family. Production of NO3x is overwhelmingly dominated by the reaction of NO2 with O3, whereas its loss is dominated by aerosol uptake of N2O5, with NO3 + VOCs and NO3 + RO2 playing smaller roles. The production of HOx and ROx radicals is mainly due to the reaction of NO3 with VOCs. The loss of these radicals occurs through a combination of HO2 + RO2 reactions, heterogeneous processes and production of HNO3 from OH + NO2, with radical propagation primarily achieved through reactions of NO3 with peroxy radicals. Thus NO3 at night plays a similar role to both OH and NO during the day in that it both initiates ROx radical production and acts to propagate the oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed, and we find that a value of γN2O5 = 0.05 improves model simulations for NO3 and N2O5, but that these improvements are at the expense of model success for HO2. Improvements to model simulations for HO2, NO3 and N2O5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.

26

Tan, Zhaofeng, Franz Rohrer, Keding Lu, Xuefei Ma, Birger Bohn, Sebastian Broch, Huabin Dong, et al. "Wintertime photochemistry in Beijing: observations of ROx radical concentrations in the North China Plain during the BEST-ONE campaign." Atmospheric Chemistry and Physics 18, no. 16 (August 27, 2018): 12391–411. http://dx.doi.org/10.5194/acp-18-12391-2018.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The first wintertime in situ measurements of hydroxyl (OH), hydroperoxy (HO2) and organic peroxy (RO2) radicals (ROx=OH+HO2+RO2) in combination with observations of total reactivity of OH radicals, kOH in Beijing are presented. The field campaign “Beijing winter finE particle STudy – Oxidation, Nucleation and light Extinctions” (BEST-ONE) was conducted at the suburban site Huairou near Beijing from January to March 2016. It aimed to understand oxidative capacity during wintertime and to elucidate the secondary pollutants' formation mechanism in the North China Plain (NCP). OH radical concentrations at noontime ranged from 2.4×106cm-3 in severely polluted air (kOH∼27s-1) to 3.6×106cm-3 in relatively clean air (kOH∼5s-1). These values are nearly 2-fold larger than OH concentrations observed in previous winter campaigns in Birmingham, Tokyo, and New York City. During this campaign, the total primary production rate of ROx radicals was dominated by the photolysis of nitrous acid accounting for 46 % of the identified primary production pathways for ROx radicals. Other important radical sources were alkene ozonolysis (28 %) and photolysis of oxygenated organic compounds (24 %). A box model was used to simulate the OH, HO2 and RO2 concentrations based on the observations of their long-lived precursors. The model was capable of reproducing the observed diurnal variation of the OH and peroxy radicals during clean days with a factor of 1.5. However, it largely underestimated HO2 and RO2 concentrations by factors up to 5 during pollution episodes. The HO2 and RO2 observed-to-modeled ratios increased with increasing NO concentrations, indicating a deficit in our understanding of the gas-phase chemistry in the high NOx regime. The OH concentrations observed in the presence of large OH reactivities indicate that atmospheric trace gas oxidation by photochemical processes can be highly effective even during wintertime, thereby facilitating the vigorous formation of secondary pollutants.

27

Richters, Stefanie, Hartmut Herrmann та Torsten Berndt. "Different pathways of the formation of highly oxidized multifunctional organic compounds (HOMs) from the gas-phase ozonolysis of β-caryophyllene". Atmospheric Chemistry and Physics 16, № 15 (4 серпня 2016): 9831–45. http://dx.doi.org/10.5194/acp-16-9831-2016.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The gas-phase mechanism of the formation of highly oxidized multifunctional organic compounds (HOMs) from the ozonolysis of β-caryophyllene was investigated in a free-jet flow system at atmospheric pressure and a temperature of 295 ± 2 K. Reaction products, mainly highly oxidized RO2 radicals containing up to 14 oxygen atoms, were detected using chemical ionization – atmospheric pressure interface – time-of-flight mass spectrometry with nitrate and acetate ionization. These highly oxidized RO2 radicals react with NO, NO2, HO2 and other RO2 radicals under atmospheric conditions forming the first-generation HOM closed-shell products. Mechanistic information on the formation of the highly oxidized RO2 radicals is based on results obtained with isotopically labelled ozone (18O3) in the ozonolysis reaction and from hydrogen/deuterium (H/D) exchange experiments of acidic H atoms in the products. The experimental findings indicate that HOM formation in this reaction system is considerably influenced by the presence of a double bond in the RO2 radicals primarily formed from the β-caryophyllene ozonolysis. Three different reaction types for HOM formation can be proposed, allowing for an explanation of the detected main products: (i) the simple autoxidation, corresponding to the repetitive reaction sequence of intramolecular H-abstraction of a RO2 radical, RO2 → QOOH, and subsequent O2 addition, next forming a peroxy radical, QOOH + O2 → R′O2; (ii) an extended autoxidation mechanism additionally involving the internal reaction of a RO2 radical with a double bond forming most likely an endoperoxide and (iii) an extended autoxidation mechanism including CO2 elimination. The individual reaction steps of the reaction types (ii) and (iii) are uncertain at the moment. From the product analysis it can be followed that the simple autoxidation mechanism accounts only for about one-third of the formed HOMs. Time-dependent measurements showed that the HOM formation proceeds at a timescale of 3 s or less under the concentration regime applied here. The new reaction pathways represent an extension of the mechanistic understanding of HOM formation via autoxidation in the atmosphere, as recently discovered from laboratory investigations on monoterpene ozonolysis.

28

Tan, Zhaofeng, Keding Lu, Andreas Hofzumahaus, Hendrik Fuchs, Birger Bohn, Frank Holland, Yuhan Liu, et al. "Experimental budgets of OH, HO2, and RO2 radicals and implications for ozone formation in the Pearl River Delta in China 2014." Atmospheric Chemistry and Physics 19, no. 10 (May 29, 2019): 7129–50. http://dx.doi.org/10.5194/acp-19-7129-2019.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Hydroxyl (OH) and peroxy radicals (HO2 and RO2) were measured in the Pearl River Delta, which is one of the most polluted areas in China, in autumn 2014. The radical observations were complemented by measurements of OH reactivity (inverse OH lifetime) and a comprehensive set of trace gases including carbon monoxide (CO), nitrogen oxides (NOx=NO, NO2) and volatile organic compounds (VOCs). OH reactivity was in the range from 15 to 80 s−1, of which about 50 % was unexplained by the measured OH reactants. In the 3 weeks of the campaign, maximum median radical concentrations were 4.5×106 cm−3 for OH at noon and 3×108 and 2.0×108 cm−3 for HO2 and RO2, respectively, in the early afternoon. The completeness of the daytime radical measurements made it possible to carry out experimental budget analyses for all radicals (OH, HO2, and RO2) and their sum (ROx). The maximum loss rates for OH, HO2, and RO2 reached values between 10 and 15 ppbv h−1 during the daytime. The largest fraction of this can be attributed to radical interconversion reactions while the real loss rate of ROx remained below 3 ppbv h−1. Within experimental uncertainties, the destruction rates of HO2 and the sum of OH, HO2, and RO2 are balanced by their respective production rates. In case of RO2, the budget could be closed by attributing the missing OH reactivity to unmeasured VOCs. Thus, the presumption of the existence of unmeasured VOCs is supported by RO2 measurements. Although the closure of the RO2 budget is greatly improved by the additional unmeasured VOCs, a significant imbalance in the afternoon remains, indicating a missing RO2 sink. In case of OH, the destruction in the morning is compensated by the quantified OH sources from photolysis (HONO and O3), ozonolysis of alkenes, and OH recycling (HO2+NO). In the afternoon, however, the OH budget indicates a missing OH source of 4 to 6 ppbv h−1. The diurnal variation of the missing OH source shows a similar pattern to that of the missing RO2 sink so that both largely compensate each other in the ROx budget. These observations suggest the existence of a chemical mechanism that converts RO2 to OH without the involvement of NO, increasing the RO2 loss rate during the daytime from 5.3 to 7.4 ppbv h−1 on average. The photochemical net ozone production rate calculated from the reaction of HO2 and RO2 with NO yields a daily integrated amount of 102 ppbv ozone, with daily integrated ROx primary sources being 22 ppbv in this campaign. The produced ozone can be attributed to the oxidation of measured (18 %) and unmeasured (60 %) hydrocarbons, formaldehyde (14 %), and CO (8 %). An even larger integrated net ozone production of 140 ppbv would be calculated from the oxidation rate of VOCs with OH if HO2 and all RO2 radicals react with NO. However, the unknown RO2 loss (evident in the RO2 budget) causes 30 ppbv less ozone production than would be expected from the VOC oxidation rate.

29

Whalley, Lisa K., Eloise J. Slater, Robert Woodward-Massey, Chunxiang Ye, James D. Lee, Freya Squires, James R. Hopkins, et al. "Evaluating the sensitivity of radical chemistry and ozone formation to ambient VOCs and NOx in Beijing." Atmospheric Chemistry and Physics 21, no. 3 (February 12, 2021): 2125–47. http://dx.doi.org/10.5194/acp-21-2125-2021.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Measurements of OH, HO2, complex RO2 (alkene- and aromatic-related RO2) and total RO2 radicals taken during the integrated Study of AIR Pollution PROcesses in Beijing (AIRPRO) campaign in central Beijing in the summer of 2017, alongside observations of OH reactivity, are presented. The concentrations of radicals were elevated, with OH reaching up to 2.8×107moleculecm-3, HO2 peaking at 1×109moleculecm-3 and the total RO2 concentration reaching 5.5×109moleculecm-3. OH reactivity (k(OH)) peaked at 89 s−1 during the night, with a minimum during the afternoon of ≈22s-1 on average. An experimental budget analysis, in which the rates of production and destruction of the radicals are compared, highlighted that although the sources and sinks of OH were balanced under high NO concentrations, the OH sinks exceeded the known sources (by 15 ppbv h−1) under the very low NO conditions (<0.5 ppbv) experienced in the afternoons, demonstrating a missing OH source consistent with previous studies under high volatile organic compound (VOC) emissions and low NO loadings. Under the highest NO mixing ratios (104 ppbv), the HO2 production rate exceeded the rate of destruction by ≈50ppbvh-1, whilst the rate of destruction of total RO2 exceeded the production by the same rate, indicating that the net propagation rate of RO2 to HO2 may be substantially slower than assumed. If just 10 % of the RO2 radicals propagate to HO2 upon reaction with NO, the HO2 and RO2 budgets could be closed at high NO, but at low NO this lower RO2 to HO2 propagation rate revealed a missing RO2 sink that was similar in magnitude to the missing OH source. A detailed box model that incorporated the latest Master Chemical Mechanism (MCM3.3.1) reproduced the observed OH concentrations well but over-predicted the observed HO2 under low concentrations of NO (<1 ppbv) and under-predicted RO2 (both the complex RO2 fraction and other RO2 types which we classify as simple RO2) most significantly at the highest NO concentrations. The model also under-predicted the observed k(OH) consistently by ≈10s-1 across all NOx levels, highlighting that the good agreement for OH was fortuitous due to a cancellation of missing OH source and sink terms in its budget. Including heterogeneous loss of HO2 to aerosol surfaces did reduce the modelled HO2 concentrations in line with the observations but only at NO mixing ratios <0.3 ppbv. The inclusion of Cl atoms, formed from the photolysis of nitryl chloride, enhanced the modelled RO2 concentration on several mornings when the Cl atom concentration was calculated to exceed 1×104atomscm-3 and could reconcile the modelled and measured RO2 concentrations at these times. However, on other mornings, when the Cl atom concentration was lower, large under-predictions in total RO2 remained. Furthermore, the inclusion of Cl atom chemistry did not enhance the modelled RO2 beyond the first few hours after sunrise and so was unable to resolve the modelled under-prediction in RO2 observed at other times of the day. Model scenarios, in which missing VOC reactivity was included as an additional reaction that converted OH to RO2, highlighted that the modelled OH, HO2 and RO2 concentrations were sensitive to the choice of RO2 product. The level of modelled to measured agreement for HO2 and RO2 (both complex and simple) could be improved if the missing OH reactivity formed a larger RO2 species that was able to undergo reaction with NO, followed by isomerisation reactions reforming other RO2 species, before eventually generating HO2. In this work an α-pinene-derived RO2 species was used as an example. In this simulation, consistent with the experimental budget analysis, the model underestimated the observed OH, indicating a missing OH source. The model uncertainty, with regards to the types of RO2 species present and the radicals they form upon reaction with NO (HO2 directly or another RO2 species), leads to over an order of magnitude less O3 production calculated from the predicted peroxy radicals than calculated from the observed peroxy radicals at the highest NO concentrations. This demonstrates the rate at which the larger RO2 species propagate to HO2, to another RO2 or indeed to OH needs to be understood to accurately simulate the rate of ozone production in environments such as Beijing, where large multifunctional VOCs are likely present.

30

George, Midhun, Maria Dolores Andrés Hernández, Vladyslav Nenakhov, Yangzhuoran Liu, John Philip Burrows, Birger Bohn, Eric Förster, et al. "Airborne observations of peroxy radicals during the EMeRGe campaign in Europe." Atmospheric Chemistry and Physics 23, no. 13 (July 14, 2023): 7799–822. http://dx.doi.org/10.5194/acp-23-7799-2023.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. In this study, airborne measurements of the sum of hydroperoxyl (HO2) and organic peroxy (RO2) radicals that react with nitrogen monoxide (NO) to produce nitrogen dioxide (NO2), coupled with actinometry and other key trace gases measurements, have been used to test the current understanding of the fast photochemistry in the outflow of major population centres. The measurements were made during the airborne campaign of the EMeRGe (Effect of Megacities on the transport and transformation of pollutants on the Regional to Global scales) project in Europe on board the High Altitude and Long Range Research Aircraft (HALO). The measurements of RO2∗ on HALO were made using the in situ instrument Peroxy Radical Chemical Enhancement and Absorption Spectrometer (PeRCEAS). RO2∗ is to a good approximation the sum of peroxy radicals reacting with NO to produce NO2. RO2∗ mixing ratios up to 120 pptv were observed in air masses of different origins and composition under different local actinometric conditions during seven HALO research flights in July 2017 over Europe. Radical production rates were estimated using knowledge of the photolysis frequencies and the RO2∗ precursor concentrations measured on board, as well as the relevant rate coefficients. Generally, high RO2∗ concentrations were measured in air masses with high production rates. In the air masses investigated, RO2∗ is primarily produced by the reaction of O1D with water vapour and the photolysis of nitrous acid (HONO) and of the oxygenated volatile organic compounds (OVOCs, e.g. formaldehyde (HCHO) and glyoxal (CHOCHO)). Due to their short lifetime in most environments, the RO2∗ concentrations are expected to be in a photostationary steady state (PSS), i.e. a balance between production and loss rates is assumed. The RO2∗ production and loss rates and the suitability of PSS assumptions to estimate the RO2∗ mixing ratios and variability during the airborne observations are discussed. The PSS assumption for RO2∗ is considered robust enough to calculate RO2∗ mixing ratios for most conditions encountered in the air masses measured. The similarities and discrepancies between measured and PSS calculated RO2∗ mixing ratios are discussed. The dominant terminating processes for RO2∗ in the pollution plumes measured up to 2000 m are the formation of nitrous acid, nitric acid, and organic nitrates. Above 2000 m, HO2–HO2 and HO2–RO2 reactions dominate the RO2∗ removal. RO2∗ calculations by the PSS analytical expression inside the pollution plumes probed often underestimated the measurements. The underestimation is attributed to the limitations of the PSS equation used for the analysis. In particular, this expression does not account for the yields of RO2∗ from the oxidation and photolysis of volatile organic compounds, VOCs, and OVOCs other than those measured during the EMeRGe research flights in Europe. In air masses with NO mixing ratios ≤50 pptv and low VOC/NO ratios, the RO2∗ measured is overestimated by the analytical expression. This may be caused by the formation of H2O and O2 from OH and HO2, being about 4 times faster than the rate of the OH oxidation reaction of the dominant OVOCs considered.

31

Sommariva, R., M. J. Pilling, W. J. Bloss, D. E. Heard, J. D. Lee, Z. L. Fleming, P. S. Monks, et al. "Night-time radical chemistry during the NAMBLEX campaign." Atmospheric Chemistry and Physics Discussions 6, no. 4 (August 9, 2006): 7715–45. http://dx.doi.org/10.5194/acpd-6-7715-2006.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Night-time chemistry in the Marine Boundary Layer has been modelled using a number of observationally constrained zero-dimensional box-models. The models were based upon the Master Chemical Mechanism (MCM) and the measurements were taken during the North Atlantic Marine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head, Ireland in July–September 2002. The model could reproduce, within the combined uncertainties, the measured concentration of HO2 (within 30–40%) during the night 31 August–1 September and of HO2+RO2 (within 15–30%) during several nights of the campaign. The model always overestimated the NO3 measurements made by Differential Optical Absorption Spectroscopy (DOAS) by up to an order of magnitude or more, but agreed with the NO3 Cavity Ring-Down Spectroscopy (CRDS) measurements to within 30–50%. The most likely explanation of the discrepancy between the two instruments and the model is reaction of the nitrate radical with inhomogeneously distributed NO, which was measured at concentrations of up to 10 ppt, even though this is not enough to fully explain the difference between the DOAS measurements and the model. A rate of production and destruction analysis showed that radicals were generated during the night mainly by the reaction of ozone with light alkenes. The cycling between HO2/RO2 and OH was maintained during the night by the low concentrations of NO and the overall radical concentration was limited by slow loss of peroxy radicals to form peroxides. A strong peak in [NO2] during the night 31 August–1 September allowed an insight into the radical fluxes and the connections between the HOx and the NO3 cycles.

32

Sommariva, R., M. J. Pilling, W. J. Bloss, D. E. Heard, J. D. Lee, Z. L. Fleming, P. S. Monks, et al. "Night-time radical chemistry during the NAMBLEX campaign." Atmospheric Chemistry and Physics 7, no. 3 (February 7, 2007): 587–98. http://dx.doi.org/10.5194/acp-7-587-2007.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Night-time chemistry in the Marine Boundary Layer has been modelled using a number of observationally constrained zero-dimensional box-models. The models were based upon the Master Chemical Mechanism (MCM) and the measurements were taken during the North Atlantic Marine Boundary Layer Experiment (NAMBLEX) campaign at Mace Head, Ireland in July–September 2002. The model could reproduce, within the combined uncertainties, the measured concentration of HO2 (within 30–40%) during the night 31 August–1 September and of HO2+RO2 (within 15–30%) during several nights of the campaign. The model always overestimated the NO3 measurements made by Differential Optical Absorption Spectroscopy (DOAS) by up to an order of magnitude or more, but agreed with the NO3 Cavity Ring-Down Spectroscopy (CRDS) measurements to within 30–50%. The most likely explanation of the discrepancy between the two instruments and the model is the reaction of the nitrate radical with inhomogeneously distributed NO, which was measured at concentrations of up to 10 ppt, even though this is not enough to fully explain the difference between the DOAS measurements and the model. A rate of production and destruction analysis showed that radicals were generated during the night mainly by the reaction of ozone with light alkenes. The cycling between HO2/RO2 and OH was maintained during the night by the low concentrations of NO and the overall radical concentration was limited by slow loss of peroxy radicals to form peroxides. A strong peak in [NO2] during the night 31 August–1 September allowed an insight into the radical fluxes and the connections between the HOx and the NO3 cycles.

33

Pang, Jacky Yat Sing, Anna Novelli, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Philip T. M. Carlsson, Changmin Cho, et al. "Investigation of the limonene photooxidation by OH at different NO concentrations in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber)." Atmospheric Chemistry and Physics 22, no. 13 (July 4, 2022): 8497–527. http://dx.doi.org/10.5194/acp-22-8497-2022.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The oxidation of limonene by the hydroxyl (OH) radical and ozone (O3) was investigated in the atmospheric simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a large Reaction Chamber) in experiments performed at different nitric oxide (NO) mixing ratios from nearly 0 up to 10 ppbv. For the experiments dominated by OH oxidation, the formaldehyde (HCHO) yield was experimentally determined and found to be (12 ± 3), (13 ± 3), and (32 ± 5) % for experiments with low (∼ 0.1 ppbv), medium (∼ 0.3 ppbv), and high NO (5 to 10 ppbv), respectively. The yield in an ozonolysis-only experiment was (10 ± 1) %, which agrees with previous laboratory studies. The experimental yield of the first-generation organic nitrates from limonene–OH oxidation is calculated as (34 ± 5) %, about 11 % higher than the value in the Master Chemical Mechanism (MCM), which is derived from structure–activity relationships (SARs). Time series of measured radicals, trace-gas concentrations, and OH reactivity are compared to results from zero-dimensional chemical box model calculations applying MCM v3.3.1. Modeled OH reactivity is 5 to 10 s−1 (25 % to 33 % of the OH reactivity at the start of the experiment) higher than measured values at the end of the experiments under all chemical conditions investigated, suggesting either that there are unaccounted loss processes of limonene oxidation products or that products are less reactive toward OH. In addition, model calculations underestimate measured hydroperoxyl radical (HO2) concentrations by 20 % to 90 % and overestimate organic peroxyl radical (RO2) concentrations by 50 % to 300 %. The largest deviations are found in low-NO experiments and in the ozonolysis experiment. An OH radical budget analysis, which uses only measured quantities, shows that the budget is closed in most of the experiments. A similar budget analysis for RO2 radicals suggests that an additional RO2 loss rate constant of about (1–6) × 10−2 s−1 for first-generation RO2 is required to match the measured RO2 concentrations in all experiments. Sensitivity model runs indicate that additional reactions converting RO2 to HO2 at a rate constant of about (1.7–3.0) × 10−2 s−1 would improve the model–measurement agreement of NOx, HO2, and RO2 concentrations and OH reactivity. Reaction pathways that could lead to the production of additional OH and HO2 are discussed, which include isomerization reactions of RO2 from the oxidation of limonene, different branching ratios for the reaction of RO2 with HO2, and a faster rate constant for RO2 recombination reactions. As the exact chemical mechanisms of the additional HO2 and OH sources could not be identified, further work needs to focus on quantifying organic product species and organic peroxy radicals from limonene oxidation.

34

Sheehy, P. M., R. Volkamer, L. T. Molina, and M. J. Molina. "Oxidative capacity of the Mexico City atmosphere – Part 2: A ROx radical cycling perspective." Atmospheric Chemistry and Physics Discussions 8, no. 2 (March 17, 2008): 5359–412. http://dx.doi.org/10.5194/acpd-8-5359-2008.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. A box model using measurements from the Mexico City Metropolitan Area study in the spring of 2003 (MCMA-2003) is presented to study ROx (ROx=OH+HO2+RO2+RO) radical cycling in the troposphere. Model simulations were performed with the Master Chemical Mechanism (MCMv3.1) constrained with 10 min averaged measurements of major radical sources (i.e., HCHO, HONO, O3, CHOCHO, etc.), radical sink precursors (i.e., NO, NO2, SO2, CO, and 102 volatile organic compounds VOC), meteorological parameters (temperature, pressure, water vapor concentration, dilution), and photolysis frequencies. Modeled HOx concentrations compare favorably with measured concentrations for most of the day; however, the model under-predicts the concentrations of radicals in the early morning. This "missing reactivity" is highest during peak photochemical activity, and is least visible in a direct comparison of HOx radical concentrations. The true uncertainty due to "missing reactivity" is apparent in parameters like chain length, and ozone production (P(O3)). For example, the integral amount of ozone produced could be under-predicted by a factor of two. Our analysis highlights that apart from uncertainties in emissions, and meteorology, there is an additional major chemical uncertainty in current models.

35

Tan, Zhaofeng, Luisa Hantschke, Martin Kaminski, Ismail-Hakki Acir, Birger Bohn, Changmin Cho, Hans-Peter Dorn, et al. "Atmospheric photo-oxidation of myrcene: OH reaction rate constant, gas-phase oxidation products and radical budgets." Atmospheric Chemistry and Physics 21, no. 20 (October 29, 2021): 16067–91. http://dx.doi.org/10.5194/acp-21-16067-2021.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The photo-oxidation of myrcene, a monoterpene species emitted by plants, was investigated at atmospheric conditions in the outdoor simulation chamber SAPHIR (Simulation of Atmospheric PHotochemistry In a Large Reaction Chamber). The chemical structure of myrcene consists of one moiety that is a conjugated π system (similar to isoprene) and another moiety that is a triple-substituted olefinic unit (similar to 2-methyl-2-butene). Hydrogen shift reactions of organic peroxy radicals (RO2) formed in the reaction of isoprene with atmospheric OH radicals are known to be of importance for the regeneration of OH. Structure–activity relationships (SARs) suggest that similar hydrogen shift reactions like in isoprene may apply to the isoprenyl part of RO2 radicals formed during the OH oxidation of myrcene. In addition, SAR predicts further isomerization reactions that would be competitive with bimolecular RO2 reactions for chemical conditions that are typical for forested environments with low concentrations of nitric oxide. Assuming that OH peroxy radicals can rapidly interconvert by addition and elimination of O2 like in isoprene, bulk isomerization rate constants of 0.21 and 0.097 s−1 (T=298 K) for the three isomers resulting from the 3′-OH and 1-OH addition, respectively, can be derived from SAR. Measurements of radicals and trace gases in the experiments allowed us to calculate radical production and destruction rates, which are expected to be balanced. The largest discrepancies between production and destruction rates were found for RO2. Additional loss of organic peroxy radicals due to isomerization reactions could explain the observed discrepancies. The uncertainty of the total radical (ROx=OH+HO2+RO2) production rates was high due to the uncertainty in the yield of radicals from myrcene ozonolysis. However, results indicate that radical production can only be balanced if the reaction rate constant of the reaction between hydroperoxy (HO2) and RO2 radicals derived from myrcene is lower (0.9 to 1.6×10-11 cm3 s−1) than predicted by SAR. Another explanation of the discrepancies would be that a significant fraction of products (yield: 0.3 to 0.6) from these reactions include OH and HO2 radicals instead of radical-terminating organic peroxides. Experiments also allowed us to determine the yields of organic oxidation products acetone (yield: 0.45±0.08) and formaldehyde (yield: 0.35±0.08). Acetone and formaldehyde are produced from different oxidation pathways, so that yields of these compounds reflect the branching ratios of the initial OH addition to myrcene. Yields determined in the experiments are consistent with branching ratios expected from SAR. The yield of organic nitrate was determined from the gas-phase budget analysis of reactive oxidized nitrogen in the chamber, giving a value of 0.13±0.03. In addition, the reaction rate constant for myrcene + OH was determined from the measured myrcene concentration, yielding a value of (2.3±0.3)×10-10 cm3 s−1.

36

Fuchs, H., T. Brauers, R. Häseler, F. Holland, D. Mihelcic, P. Müsgen, F. Rohrer, R. Wegener, and A. Hofzumahaus. "Intercomparison of peroxy radical measurements obtained at atmospheric conditions by laser-induced fluorescence and electron spin resonance spectroscopy." Atmospheric Measurement Techniques Discussions 1, no. 1 (December 2, 2008): 375–99. http://dx.doi.org/10.5194/amtd-1-375-2008.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Measurements of hydroperoxy radical (HO2) and organic peroxy radical (RO2) concentrations were performed by two different techniques in the atmospheric simulation chamber SAPHIR in Jülich, Germany. The first technique was the well-established Matrix Isolation Electron Spin Resonance (MIESR), which provides absolute measurements with a time resolution of 30 min and high accuracy (10%, 2 σ). The other technique, ROxLIF, has been newly developed. It is based on the selective chemical conversion of ROx radicals (HO2 and RO2) to OH, which is detected with high sensitivity by laser-induced fluorescence (LIF). ROxLIF is calibrated by quantitative photolysis of water vapor at 185 nm and provides ambient measurements at a temporal resolution of 1 min and accuracy of 20% (2 σ). The measurements of HO2 and RO2 obtained by the two techniques were compared for two types of atmospheric simulation experiments. In one experiment, HO2 and CH3O2 radicals were produced by photooxidation of methane in air at tropospheric conditions. In the second experiment, HO2 and C2H5O2 were produced by ozonolysis of 1-butene in air at dark conditions. The radical concentrations were within the range of 16 to 100 pptv for HO2 and 12 to 45 pptv for RO2. Good agreement was found in the comparison of the ROxLIF and MIESR measurements within their combined experimental uncertainties. Linear regressions to the combined data set yield slopes of 1.02±0.13 (1 σ) for RO2 and 0.98±0.08 (1 σ) for HO2 without significant offsets. The results confirm the calibration of the ROxLIF instrument and demonstrate that it can be applied with good accuracy for measurements of atmospheric peroxy radical concentrations.

37

Fuchs, H., T. Brauers, R. Häseler, F. Holland, D. Mihelcic, P. Müsgen, F. Rohrer, R. Wegener, and A. Hofzumahaus. "Intercomparison of peroxy radical measurements obtained at atmospheric conditions by laser-induced fluorescence and electron spin resonance spectroscopy." Atmospheric Measurement Techniques 2, no. 1 (March 9, 2009): 55–64. http://dx.doi.org/10.5194/amt-2-55-2009.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Measurements of hydroperoxy radical (HO2) and organic peroxy radical (RO2) concentrations were performed by two different techniques in the atmospheric simulation chamber SAPHIR in Jülich, Germany. The first technique was the well-established Matrix Isolation Electron Spin Resonance (MIESR), which provides absolute measurements with a time resolution of 30 min and high accuracy (10%, 2 σ). The other technique, ROxLIF, has been newly developed. It is based on the selective chemical conversion of ROx radicals (HO2 and RO2) to OH, which is detected with high sensitivity by laser-induced fluorescence (LIF). ROxLIF is calibrated by quantitative photolysis of water vapor at 185 nm and provides ambient measurements at a temporal resolution of 1 min and accuracy of 20% (2 σ). The measurements of HO2 and RO2 obtained by the two techniques were compared for two types of atmospheric simulation experiments. In one experiment, HO2 and CH3O2 radicals were produced by photooxidation of methane in air at tropospheric conditions. In the second experiment, HO2 and C2H5O2 were produced by ozonolysis of 1-butene in air at dark conditions. The radical concentrations were within the range of 16 to 100 pptv for HO2 and 12 to 45 pptv for RO2. Good agreement was found in the comparison of the ROxLIF and MIESR measurements within their combined experimental uncertainties. Linear regressions to the combined data set yield slopes of 1.02±0.13 (1 σ) for RO2 and 0.98±0.08 (1 σ) for HO2 without significant offsets. The results confirm the calibration of the ROxLIF instrument and demonstrate that it can be applied with good accuracy for measurements of atmospheric peroxy radical concentrations.

38

George, Midhun, Maria Dolores Andrés Hernández, Vladyslav Nenakhov, Yangzhuoran Liu, and John Philip Burrows. "Airborne measurement of peroxy radicals using chemical amplification coupled with cavity ring-down spectroscopy: the PeRCEAS instrument." Atmospheric Measurement Techniques 13, no. 5 (May 20, 2020): 2577–600. http://dx.doi.org/10.5194/amt-13-2577-2020.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Hydroperoxyl (HO2) and organic peroxy (RO2) radicals have an unpaired spin and are highly reactive free radicals. Measurements of the sum of HO2 and RO2 provide unique information about the chemical processing in an air mass. This paper describes the experimental features and capabilities of the Peroxy Radical Chemical Enhancement and Absorption Spectrometer (PeRCEAS). This is an instrument designed to make measurements on aircraft from the boundary layer to the lower stratosphere. PeRCEAS combines the amplified conversion of peroxy radicals to nitrogen dioxide (NO2) with the sensitive detection of NO2 using cavity ring-down spectroscopy (CRDS) at 408 nm. PeRCEAS is a dual-channel instrument, with two identical reactor–detector lines working out of phase with one another at a constant and defined pressure lower than ambient at the aircraft altitude. The suitability of PeRCEAS for airborne measurements in the free troposphere was evaluated by extensive characterisation and calibration under atmospherically representative conditions in the laboratory. The use of alternating modes of the two instrumental channels successfully captures short-term variations in the sum of peroxy radicals, defined as RO2∗ (RO2∗=HO2+∑RO2+OH+∑RO, with R being an organic chain) in ambient air. For a 60 s measurement, the RO2∗ detection limit is < 2 pptv for a minimum (2σ) NO2 detectable mixing ratio < 60 pptv, under laboratory conditions in the range of atmospheric pressures and temperatures expected in the free troposphere. PeRCEAS has been successfully deployed within the OMO (Oxidation Mechanism Observations) and EMeRGe (Effect of Megacities on the transport and transformation of pollutants on the Regional and Global scales) missions in different airborne campaigns aboard the High Altitude LOng range research aircraft (HALO) for the study of the composition of the free troposphere.

39

Stone, D., M. J. Evans, H. Walker, T. Ingham, S. Vaughan, B. Ouyang, O. J. Kennedy, et al. "Radical chemistry at night: comparisons between observed and modelled HOx, NO3 and N2O5 during the RONOCO project." Atmospheric Chemistry and Physics 14, no. 3 (February 5, 2014): 1299–321. http://dx.doi.org/10.5194/acp-14-1299-2014.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The RONOCO (ROle of Nighttime chemistry in controlling the Oxidising Capacity of the AtmOsphere) aircraft campaign during July 2010 and January 2011 made observations of OH, HO2, NO3, N2O5 and a number of supporting measurements at night over the UK, and reflects the first simultaneous airborne measurements of these species. We compare the observed concentrations of these short-lived species with those calculated by a box model constrained by the concentrations of the longer lived species using a detailed chemical scheme. OH concentrations were below the limit of detection, consistent with model predictions. The model systematically underpredicts HO2 by ~200% and overpredicts NO3 and N2O5 by around 80 and 50%, respectively. Cycling between NO3 and N2O5 is fast and thus we define the NO3x (NO3x=NO3+N2O5) family. Production of NO3x is overwhelmingly dominated by the reaction of NO2 with O3, whereas its loss is dominated by aerosol uptake of N2O5, with NO3+VOCs (volatile organic compounds) and NO3+RO2 playing smaller roles. The production of HOx and ROx radicals is mainly due to the reaction of NO3 with VOCs. The loss of these radicals occurs through a combination of HO2+RO2 reactions, heterogeneous processes and production of HNO3 from OH+NO2, with radical propagation primarily achieved through reactions of NO3 with peroxy radicals. Thus NO3 at night plays a similar role to both OH and NO during the day in that it both initiates ROx radical production and acts to propagate the tropospheric oxidation chain. Model sensitivity to the N2O5 aerosol uptake coefficient (γN2O5) is discussed and we find that a value of γN2O5=0.05 improves model simulations for NO3 and N2O5, but that these improvements are at the expense of model success for HO2. Improvements to model simulations for HO2, NO3 and N2O5 can be realised simultaneously on inclusion of additional unsaturated volatile organic compounds, however the nature of these compounds is extremely uncertain.

40

Baker, Yarê, Sungah Kang, Hui Wang, Rongrong Wu, Jian Xu, Annika Zanders, Quanfu He та ін. "Impact of HO₂∕RO₂ ratio on highly oxygenated α-pinene photooxidation products and secondary organic aerosol formation potential". Atmospheric Chemistry and Physics 24, № 8 (22 квітня 2024): 4789–807. http://dx.doi.org/10.5194/acp-24-4789-2024.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Highly oxygenated molecules (HOMs) from the atmospheric oxidation of biogenic volatile organic compounds are important contributors to secondary organic aerosol (SOA). Organic peroxy radicals (RO2) and hydroperoxy radicals (HO2) are key species influencing the HOM product distribution. In laboratory studies, experimental requirements often result in overemphasis on RO2 cross-reactions compared to reactions of RO2 with HO2. We analyzed the photochemical formation of HOMs from α-pinene and their potential to contribute to SOA formation under high (≈1/1) and low (≈1/100) HO2/RO2 conditions. As HO2/RO2 > 1 is prevalent in the daytime atmosphere, sufficiently high HO2/RO2 is crucial to mimic atmospheric conditions and to prevent biases by low HO2/RO2 on the HOM product distribution and thus SOA yield. Experiments were performed under steady-state conditions in the new, continuously stirred tank reactor SAPHIR-STAR at Forschungszentrum Jülich. The HO2/RO2 ratio was increased by adding CO while keeping the OH concentration constant. We determined the HOM's SOA formation potential, considering its fraction remaining in the gas phase after seeding with (NH4)2SO4 aerosol. An increase in HO2/RO2 led to a reduction in SOA formation potential, with the main driver being a ∼ 60 % reduction in HOM-accretion products. We also observed a shift in HOM-monomer functionalization from carbonyl to hydroperoxide groups. We determined a reduction of the HOM's SOA formation potential by ∼ 30 % at HO2/RO2 ≈1/1 compared to HO2/RO2 ≈ 1/100. Particle-phase observations measured a similar decrease in SOA mass and yield. Our study shows that too low HO2/RO2 ratios compared to the atmosphere can lead to an overestimation of SOA yields.

41

Whalley, Lisa K., Daniel Stone, Rachel Dunmore, Jacqueline Hamilton, James R. Hopkins, James D. Lee, Alastair C. Lewis, et al. "Understanding in situ ozone production in the summertime through radical observations and modelling studies during the Clean air for London project (ClearfLo)." Atmospheric Chemistry and Physics 18, no. 4 (February 21, 2018): 2547–71. http://dx.doi.org/10.5194/acp-18-2547-2018.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Measurements of OH, HO2, RO2i (alkene and aromatic-related RO2) and total RO2 radicals taken during the ClearfLo campaign in central London in the summer of 2012 are presented. A photostationary steady-state calculation of OH which considered measured OH reactivity as the OH sink term and the measured OH sources (of which HO2+ NO reaction and HONO photolysis dominated) compared well with the observed levels of OH. Comparison with calculations from a detailed box model utilising the Master Chemical Mechanism v3.2, however, highlighted a substantial discrepancy between radical observations under lower NOx conditions ([NO] < 1 ppbv), typically experienced during the afternoon hours, and indicated that the model was missing a significant peroxy radical sink; the model overpredicted HO2 by up to a factor of 10 at these times. Known radical termination steps, such as HO2 uptake on aerosols, were not sufficient to reconcile the model–measurement discrepancies alone, suggesting other missing termination processes. This missing sink was most evident when the air reaching the site had previously passed over central London to the east and when elevated temperatures were experienced and, hence, contained higher concentrations of VOCs. Uncertainties in the degradation mechanism at low NOx of complex biogenic and diesel related VOC species, which were particularly elevated and dominated OH reactivity under these easterly flows, may account for some of the model–measurement disagreement. Under higher [NO] (> 3 ppbv) the box model increasingly underpredicted total [RO2]. The modelled and observed HO2 were in agreement, however, under elevated NO concentrations ranging from 7 to 15 ppbv. The model uncertainty under low NO conditions leads to more ozone production predicted using modelled peroxy radical concentrations (∼ 3 ppbv h−1) versus ozone production from peroxy radicals measured (∼ 1 ppbv h−1). Conversely, ozone production derived from the predicted peroxy radicals is up to an order of magnitude lower than from the observed peroxy radicals as [NO] increases beyond 7 ppbv due to the model underprediction of RO2 under these conditions.

42

Thomas, J. L., J. E. Dibb, L. G. Huey, J. Liao, D. Tanner, B. Lefer, R. von Glasow, and J. Stutz. "Modeling chemistry in and above snow at Summit, Greenland − Part 2: Impact of snowpack chemistry on the oxidation capacity of the boundary layer." Atmospheric Chemistry and Physics Discussions 12, no. 2 (February 21, 2012): 5551–600. http://dx.doi.org/10.5194/acpd-12-5551-2012.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The chemical composition of the boundary layer in snow covered regions is impacted by chemistry in the snowpack via uptake, processing, and emission of atmospheric trace gases. We use the coupled one-dimensional (1-D) snow chemistry and atmospheric boundary layer model MISTRA-SNOW to study the impact of snowpack chemistry on the oxidation capacity of the boundary layer. The model includes gas phase photochemistry and chemical reactions both in the interstitial air and the atmosphere. Chemistry on snow grains is simulated assuming a liquid-like layer (LLL), treated as an aqueous layer on the snow grain surface. The model has been recently compared with BrO and NO data taken on 10 June–13 June 2008 as part of the Greenland Summit Halogen-HOx experiment (GSHOX). In the present study, we use the same focus period to investigate the influence of snowpack derived chemistry on OH and HOx + RO2 in the boundary layer. We compare model results with chemical ionization mass spectrometry (CIMS) measurements of the hydroxyl radical (OH) and of the hydroperoxyl radical (HO2) plus the sum of all organic peroxy radicals (RO2) taken at Summit during summer 2008. Using sensitivity runs we show that snowpack influenced nitrogen cycling and bromine chemistry both increase the oxidation capacity of the boundary layer and that together they increase the mid-day OH concentrations by approximately a factor of 2. We show for the first time, using an unconstrained coupled one-dimensional snowpack-boundary layer model, that air-snow interactions impact the oxidation capacity of the boundary layer and that it is not possible to match measured OH levels without snowpack NOx and halogen emissions. Model predicted HONO compared with mistchamber measurements suggests there may be an unknown HONO source at Summit. Other model predicted HOx precursors, H2O2 and HCHO, compare well with measurements taken in summer 2000. Over 3 days, snow sourced NOx contributes an additional 2 ppb to boundary layer ozone production, while snow sourced bromine has the opposite effect and contributes 1 ppb to boundary layer ozone loss.

43

Kim, S., S. Y. Kim, M. Lee, H. Shim, G. M. Wolfe, A. B. Guenther, A. He, Y. Hong, and J. Han. "Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest." Atmospheric Chemistry and Physics 15, no. 8 (April 29, 2015): 4357–71. http://dx.doi.org/10.5194/acp-15-4357-2015.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NOx, SO2, ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HOx (OH, HO2, and RO2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HOx distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO2 + HO2 or HO2 + RO2) could be more efficient than radical recycling (RO2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NOx sensitivity and VOC oxidation product formation rates. Overall, the NOx limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.

44

Gong, Yiwei, Feng Jiang, Yanxia Li, Thomas Leisner та Harald Saathoff. "Impact of temperature on the role of Criegee intermediates and peroxy radicals in dimer formation from β-pinene ozonolysis". Atmospheric Chemistry and Physics 24, № 1 (8 січня 2024): 167–84. http://dx.doi.org/10.5194/acp-24-167-2024.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Stabilized Criegee intermediates (SCIs) and organic peroxy radicals (RO2) are critical in atmospheric oxidation processes and secondary organic aerosol (SOA) formation. However, the influence of temperature on their corresponding reaction mechanisms in SOA formation is unclear. Through utilizing formic acid as a SCI scavenger and regulating the ratio of hydroperoxyl radials (HO2) to RO2 ([HO2]/[RO2]) from ∼ 0.3 to ∼ 1.9 using different concentrations of CO, the roles of RO2 and SCIs in SOA formation were investigated from 248 to 298 K, particularly for dimer formation in β-pinene ozonolysis. The SOA yield increased by 21 % from 298 to 273 K, while it decreased by 40 % from 273 to 248 K. Both changing [HO2]/[RO2] and scavenging SCIs significantly affect SOA yield and composition. SCI reactions accounted for more than 40 % of dimer and SOA mass formation for all temperatures. Increasing [HO2]/[RO2] inhibited dimer and SOA formation, and this inhibition became larger with decreasing temperature. Compared to low [HO2]/[RO2] (0.30–0.34), the dimer abundance at high [HO2]/[RO2] (1.53–1.88) decreased by about 31 % at 298 K and 70 % at 248 K. [HO2]/[RO2] has a specific impact on SCI-controlled dimers at lower temperatures by especially influencing the C9–SCI reactions with RO2. The dimers formed from C9–SCI reactions with RO2 were estimated to decrease by 61 % at high [HO2]/[RO2] compared to low [HO2]/[RO2] at 248 K. The high reactivity and substantial contribution to SOA of β-pinene-derived SCIs at lower temperatures observed in this study suggest that monoterpene-derived SCI reactions should be accounted for in describing colder regions of the atmosphere.

45

Miyazaki, K., A. E. Parker, C. Fittschen, P. S. Monks, and Y. Kajii. "A new technique for the selective measurement of atmospheric peroxy radical concentrations of HO2 and RO2 using denuding method." Atmospheric Measurement Techniques Discussions 2, no. 6 (December 15, 2009): 3291–307. http://dx.doi.org/10.5194/amtd-2-3291-2009.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. A technique for the selective measurement of atmospheric HO2 and RO2 using peroxy radical chemical amplification coupled to laser-induced fluorescence NO2 detection (PERCA-LIF) technique is proposed. By pulling the air through a filled pre-inlet advantage can be taken of the higher heterogeneous loss rate of HO2 relative to CH3O2. Pre-inlet conditions have been found where ca. 90% of HO2 was removed whereas the comparable CH3O2 loss was 15%. The dependence of loss rate on humidity and peroxy radicals' concentration has also been investigated. When using glass beads as the surface for peroxy radical remove, the influence of the relative humidity on the removal efficiency becomes negligible. It may therefore be possible to apply this technique to the measurement of absolute concentrations of solely RO2 as well as the sum of HO2 and RO2. The application of this technique to atmospheric measurements is suggested.

46

Mallik, Chinmay, Laura Tomsche, Efstratios Bourtsoukidis, John N. Crowley, Bettina Derstroff, Horst Fischer, Sascha Hafermann, et al. "Oxidation processes in the eastern Mediterranean atmosphere: evidence from the modelling of HOx measurements over Cyprus." Atmospheric Chemistry and Physics 18, no. 14 (July 31, 2018): 10825–47. http://dx.doi.org/10.5194/acp-18-10825-2018.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. The Mediterranean is a climatically sensitive region located at the crossroads of air masses from three continents: Europe, Africa, and Asia. The chemical processing of air masses over this region has implications not only for the air quality but also for the long-range transport of air pollution. To obtain a comprehensive understanding of oxidation processes over the Mediterranean, atmospheric concentrations of the hydroxyl radical (OH) and the hydroperoxyl radical (HO2) were measured during an intensive field campaign (CYprus PHotochemistry EXperiment, CYPHEX-2014) in the northwest of Cyprus in the summer of 2014. Very low local anthropogenic and biogenic emissions around the measurement location provided a vantage point to study the contrasts in atmospheric oxidation pathways under highly processed marine air masses and those influenced by relatively fresh emissions from mainland Europe.The CYPHEX measurements were used to evaluate OH and HO2 simulations using a photochemical box model (CAABA/MECCA) constrained with CYPHEX observations of O3, CO, NOx, hydrocarbons, peroxides, and other major HOx (OH + HO2) sources and sinks in a low-NOx environment (< 100 pptv of NO). The model simulations for OH agreed to within 10 % with in situ OH observations. Model simulations for HO2 agreed to within 17 % of the in situ observations. However, the model strongly under-predicted HO2 at high terpene concentrations, this under-prediction reaching up to 38 % at the highest terpene levels. Different schemes to improve the agreement between observed and modelled HO2, including changing the rate coefficients for the reactions of terpene-generated peroxy radicals (RO2) with NO and HO2 as well as the autoxidation of terpene-generated RO2 species, are explored in this work. The main source of OH in Cyprus was its primary production from O3 photolysis during the day and HONO photolysis during early morning. Recycling contributed about one-third of the total OH production, and the maximum recycling efficiency was about 0.7. CO, which was the largest OH sink, was also the largest HO2 source. The lowest HOx production and losses occurred when the air masses had higher residence time over the oceans.

47

Kim, S., S. Y. Kim, M. Lee, H. Shim, G. M. Wolfe, A. B. Guenther, A. He, Y. Hong, and J. Han. "Urban-rural interactions in a South Korean forest: uncertainties in isoprene-OH interactions limit understanding of ozone and secondary organic aerosols production." Atmospheric Chemistry and Physics Discussions 14, no. 11 (June 24, 2014): 16691–729. http://dx.doi.org/10.5194/acpd-14-16691-2014.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Gangzhou, and Beijing are surrounded by densely forested areas and recent research has consistently demonstrated the importance of biogenic volatile organic compounds from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical concentrations, undermine our ability to assess regional photochemical air pollution problems. We present an observational dataset of CO, NOx, SO2, ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa Research Forest (TRF) near the Seoul Metropolitan Area (SMA) in early June 2012. The data show that TRF is influenced both by aged pollution and fresh BVOC emissions. With the dataset, we diagnose HOx (OH, HO2, and RO2) distributions calculated with the University of Washington Chemical Box Model (UWCM v 2.1). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HOx distributions especially OH levels (up to 2.5 times) and (2) radical destruction (HO2+HO2 or HO2+RO2) could be more efficient than radical recycling (HO2+NO) especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone-VOC-NOx sensitivity and oxidation product formation rates. Overall, the VOC limited regime in ozone photochemistry is predicted but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO2 levels are positively correlated with OVOCs production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher than expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.

48

Andrés-Hernández, M. D., D. Stone, D. M. Brookes, R. Commane, C. E. Reeves, H. Huntrieser, D. E. Heard, et al. "Peroxy radical partitioning during the AMMA radical intercomparison exercise." Atmospheric Chemistry and Physics Discussions 10, no. 4 (April 1, 2010): 8447–86. http://dx.doi.org/10.5194/acpd-10-8447-2010.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis) campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE) and total peroxy radicals (RO2*=HO2+ΣRO2, R= organic chain) by two similar instruments based on the peroxy radical chemical amplification (PerCA) technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously. Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

49

Andrés-Hernández, M. D., D. Stone, D. M. Brookes, R. Commane, C. E. Reeves, H. Huntrieser, D. E. Heard, et al. "Peroxy radical partitioning during the AMMA radical intercomparison exercise." Atmospheric Chemistry and Physics 10, no. 21 (November 11, 2010): 10621–38. http://dx.doi.org/10.5194/acp-10-10621-2010.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Peroxy radicals were measured onboard two scientific aircrafts during the AMMA (African Monsoon Multidisciplinary Analysis) campaign in summer 2006. This paper reports results from the flight on 16 August 2006 during which measurements of HO2 by laser induced fluorescence spectroscopy at low pressure (LIF-FAGE) and total peroxy radicals (RO2* = HO2+ΣRO2, R = organic chain) by two similar instruments based on the peroxy radical chemical amplification (PeRCA) technique were subject of a blind intercomparison. The German DLR-Falcon and the British FAAM-BAe-146 flew wing tip to wing tip for about 30 min making concurrent measurements on 2 horizontal level runs at 697 and 485 hPa over the same geographical area in Burkina Faso. A full set of supporting measurements comprising photolysis frequencies, and relevant trace gases like CO, NO, NO2, NOy, O3 and a wider range of VOCs were collected simultaneously. Results are discussed on the basis of the characteristics and limitations of the different instruments used. Generally, no data bias are identified and the RO2* data available agree quite reasonably within the instrumental errors. The [RO2*]/[HO2] ratios, which vary between 1:1 and 3:1, as well as the peroxy radical variability, concur with variations in photolysis rates and in other potential radical precursors. Model results provide additional information about dominant radical formation and loss processes.

50

Hens, K., A. Novelli, M. Martinez, J. Auld, R. Axinte, B. Bohn, H. Fischer, et al. "Observation and modelling of HOx radicals in a boreal forest." Atmospheric Chemistry and Physics 14, no. 16 (August 26, 2014): 8723–47. http://dx.doi.org/10.5194/acp-14-8723-2014.

Повний текст джерела

Стилі APA, Harvard, Vancouver, ISO та ін.

Анотація:

Abstract. Measurements of OH and HO2 radicals were conducted in a pine-dominated forest in southern Finland during the HUMPPA-COPEC-2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) field campaign in summer 2010. Simultaneous side-by-side measurements of hydroxyl radicals were conducted with two instruments using chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF), indicating small systematic disagreement, OHLIF / OHCIMS = (1.31 ± 0.14). Subsequently, the LIF instrument was moved to the top of a 20 m tower, just above the canopy, to investigate the radical chemistry at the ecosystem–atmosphere interface. Comprehensive measurements including observations of many volatile organic compounds (VOCs) and the total OH reactivity were conducted and analysed using steady-state calculations as well as an observationally constrained box model. Production rates of OH calculated from measured OH precursors are consistent with those derived from the steady-state assumption and measured total OH loss under conditions of moderate OH reactivity. The primary photolytic sources of OH contribute up to one-third to the total OH production. OH recycling, which occurs mainly by HO2 reacting with NO and O3, dominates the total hydroxyl radical production in this boreal forest. Box model simulations agree with measurements for hydroxyl radicals (OHmod. / OHobs. = 1.00 ± 0.16), while HO2 mixing ratios are significantly under-predicted (HO2mod. / HO2obs. = 0.3 ± 0.2), and simulated OH reactivity does not match the observed OH reactivity. The simultaneous under-prediction of HO2 and OH reactivity in periods in which OH concentrations were simulated realistically suggests that the missing OH reactivity is an unaccounted-for source of HO2. Detailed analysis of the HOx production, loss, and recycling pathways suggests that in periods of high total OH reactivity there are additional recycling processes forming OH directly, not via reaction of HO2 with NO or O3, or unaccounted-for primary HOx sources. Under conditions of moderate observed OH reactivity and high actinic flux, an additional RO2 source of approximately 1 × 106 molec cm−3 s−1 would be required to close the radical budget. Nevertheless, a major fraction of the OH recycling occurs via the reaction of HO2 with NO and O3 in this terpene-dominated environment.

Статті в журналах з теми "HOx and RO2 radicals"

Оформте джерело за APA, MLA, Chicago, Harvard та іншими стилями