scholarly journals Intercomparison of nitrous acid (HONO) measurement techniques in a megacity (Beijing)

2019 ◽  
Author(s):  
Leigh R. Crilley ◽  
Louisa J. Kramer ◽  
Bin Ouyang ◽  
Jun Duan ◽  
Wenqian Zhang ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Nitrous Acid ◽  
Measurement Techniques ◽  
Temporal Trends ◽  
Proton Transfer Reaction ◽  
Ionization Mass ◽  
Systematic Bias ◽  
Enhanced Absorption ◽  
Wet Chemical ◽  
Inlet Position

Abstract. Nitrous acid (HONO) is a key determinant of the daytime radical budget in the daytime boundary layer, with quantitative measurement required to understand OH radical abundance. Accurate and precise measurements of HONO are therefore needed; however HONO is a challenging compound to measure in the field, in particular in a chemically complex and highly polluted environment. Here we report an inter-comparison exercise between HONO measurements performed by two wet chemical techniques (the commercially available LOPAP and a custom-built instrument) and two Broadband Cavity Enhanced Absorption Spectrophotometer (BBCEAS) instruments at an urban location in Beijing. In addition, we report a comparison of HONO measurements performed by Time of Flight Chemical Ionization Mass Spectrometer (ToF-CIMS) and Syft Proton Transfer Reaction Mass Spectrometer (PTR-MS) to the more established techniques (wet chemical and BBCEAS). The key finding from the current work was that all instruments agree on the temporal trends/variability in HONO (r2 > 0.97), yet displayed some divergence in absolute concentrations, with the wet chemical methods consistently higher than the BBCEAS systems by between 12 and 39 %. We found no evidence for any systematic bias in any of the instruments, with the exception of measurements near instrument detection limits. The causes of the divergence in absolute HONO concentrations were unclear, and may in part have been due to spatial variability, i.e. differences in instrument location/inlet position.

scholarly journals Intercomparison of nitrous acid (HONO) measurement techniques in a megacity (Beijing)

2019 ◽  
Vol 12 (12) ◽  
pp. 6449-6463 ◽  
Author(s):  
Leigh R. Crilley ◽  
Louisa J. Kramer ◽  
Bin Ouyang ◽  
Jun Duan ◽  
Wenqian Zhang ◽  
...  
Keyword(s):  
Mass Spectrometer ◽  
Nitrous Acid ◽  
Measurement Techniques ◽  
Temporal Trends ◽  
Ionization Mass ◽  
Systematic Bias ◽  
Ion Flow ◽  
Enhanced Absorption ◽  
Selected Ion Flow Tube ◽  
Wet Chemical

Abstract. Nitrous acid (HONO) is a key determinant of the daytime radical budget in the daytime boundary layer, with quantitative measurement required to understand OH radical abundance. Accurate and precise measurements of HONO are therefore needed; however HONO is a challenging compound to measure in the field, in particular in a chemically complex and highly polluted environment. Here we report an intercomparison exercise between HONO measurements performed by two wet chemical techniques (the commercially available a long-path absorption photometer (LOPAP) and a custom-built instrument) and two broadband cavity-enhanced absorption spectrophotometer (BBCEAS) instruments at an urban location in Beijing. In addition, we report a comparison of HONO measurements performed by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) and a selected ion flow tube mass spectrometer (SIFT-MS) to the more established techniques (wet chemical and BBCEAS). The key finding from the current work was that all instruments agree on the temporal trends and variability in HONO (r2 > 0.97), yet they displayed some divergence in absolute concentrations, with the wet chemical methods consistently higher overall than the BBCEAS systems by between 12 % and 39 %. We found no evidence for any systematic bias in any of the instruments, with the exception of measurements near instrument detection limits. The causes of the divergence in absolute HONO concentrations were unclear, and may in part have been due to spatial variability, i.e. differences in instrument location and/or inlet position, but this observation may have been more associative than casual.

scholarly journals The airborne mass spectrometer AIMS – Part 2: Measurements of trace gases with stratospheric or tropospheric origin in the UTLS

2015 ◽  
Vol 8 (12) ◽  
pp. 13567-13607 ◽  
Author(s):  
T. Jurkat ◽  
S. Kaufmann ◽  
C. Voigt ◽  
D. Schäuble ◽  
P. Jeßberger ◽  
...  
Keyword(s):  
Nitrogen Oxide ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Trace Gases ◽  
Measurement Techniques ◽  
Ion Source ◽  
Trace Gas ◽  
Ionization Mass ◽  
Custom Made ◽  
Gas Measurements

Abstract. Understanding the role of climate-sensitive trace gas variabilities in the upper troposphere and lower stratosphere region (UTLS) and their impact on its radiative budget requires accurate measurements. The composition of the UTLS is governed by transport and chemistry of stratospheric and tropospheric constituents, such as chlorine, nitrogen oxide and sulphur components. The Airborne chemical Ionization Mass Spectrometer AIMS has been developed to accurately measure a set of these constituents on aircraft by means of chemical ionization. Here we present a setup using chemical ionization with SF5− reagent ions for the simultaneous measurement of trace gas concentrations in the pptv to ppmv (10−12 to 10−6 mol mol−1) range of HCl, HNO3 and SO2 with in-flight and online calibration called AIMS-TG. Part 1 of this paper (Kaufmann et al., 2015) reports on the UTLS water vapour measurements with the AIMS-H2O configuration. The instrument can be flexibly switched between two configurations depending on the scientific objective of the mission. For AIMS-TG, a custom-made gas discharge ion source has been developed generating a characteristic ionization scheme. HNO3 and HCl are routinely calibrated in-flight using permeation devices, SO2 is permanently calibrated during flight adding an isotopically labelled 34SO2 standard. In addition, we report on trace gas measurements of HONO which is sensitive to the reaction with SF5−. The detection limit for the various trace gases is in the low ten pptv range at a 1 s time resolution with an overall uncertainty of the measurement in the order of 20 %. AIMS has been integrated and successfully operated on the DLR research aircraft Falcon and HALO. Exemplarily, measurements conducted during the TACTS/ESMVal mission with HALO in 2012 are presented, focusing on a classification of tropospheric and stratospheric influences in the UTLS region. Comparison of AIMS measurements with other measurement techniques allow to draw a comprehensive picture of the sulphur, chlorine and reactive nitrogen oxide budget in the UTLS. The combination of the trace gases measured with AIMS exhibit the potential to gain a better understanding of the trace gas origin and variability at and near the tropopause.

scholarly journals Coupling a gas chromatograph simultaneously to a flame ionization detector and chemical ionization mass spectrometer for isomer-resolved measurements of particle-phase organic compounds

2020 ◽  
Author(s):  
Chenyang Bi ◽  
Jordan E. Krechmer ◽  
Graham O. Frazier ◽  
Wen Xu ◽  
Andrew T. Lambe ◽  
...  
Keyword(s):  
Functional Groups ◽  
Organic Compounds ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Measurement Techniques ◽  
Oxidation Products ◽  
Ionization Mass ◽  
Particle Phase ◽  
Gas Chromatograph ◽  
New Instrument

Abstract. Atmospheric oxidation products of volatile organic compounds consist of thousands of unique chemicals that have distinctly different physical and chemical properties depending on their detailed structures and functional groups. Measurement techniques that can achieve molecular characterizations with details down to functional groups (i.e., isomer-resolved resolution) are consequently necessary to provide understandings of differences of fate and transport within isomers produced in the oxidation process. We demonstrate a new instrument coupling the thermal desorption aerosol gas chromatograph (TAG), which enables the separation of isomers, with the high-resolution time-of-flight chemical ionization mass spectrometer (HR-ToF-CIMS), which has the capability of classifying unknown compounds by their molecular formulas, and the flame ion detector (FID), which provide a near-universal response to organic compounds. The TAG-CIMS/FID is used to provide isomer-resolved measurements of samples from liquid standard injections and particle-phase organics generated in oxidation flow reactors. By coupling a TAG to a CIMS, the CIMS is enhanced with an additional dimension of information (resolution of individual molecules) at the cost of time resolution (i.e., one sample per hour instead of per minute). We found that isomers are prevalent in sample matrix with an average number of three to five isomers per formula depending on the precursors in the oxidation experiments. Additionally, a multi-reagent ionization mode is investigated in which both zero air and iodide are introduced as reagent ions, to examine the feasibility of extending the use of an individual CIMS to a broader range of analytes with still selective reagent ions. While this approach reduces iodide-adduct ions by a factor of two, [M−H]− and [M+O2]− ions produced from lower-polarity compounds increase by a factor of five to ten, improving their detection by CIMS. The method expands the range of detected chemical species by using two chemical ionization reagents simultaneously, enabled by the pre-separation of analyte molecules before ionization.

scholarly journals The airborne mass spectrometer AIMS – Part 2: Measurements of trace gases with stratospheric or tropospheric origin in the UTLS

2016 ◽  
Vol 9 (4) ◽  
pp. 1907-1923 ◽  
Author(s):  
Tina Jurkat ◽  
Stefan Kaufmann ◽  
Christiane Voigt ◽  
Dominik Schäuble ◽  
Philipp Jeßberger ◽  
...  
Keyword(s):  
Nitrogen Oxide ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Trace Gases ◽  
Measurement Techniques ◽  
Ion Source ◽  
Trace Gas ◽  
Ionization Mass ◽  
Custom Made ◽  
Research Aircraft

Abstract. Understanding the role of climate-sensitive trace gas variabilities in the upper troposphere and lower stratosphere region (UTLS) and their impact on its radiative budget requires accurate measurements. The composition of the UTLS is governed by transport and chemistry of stratospheric and tropospheric constituents, such as chlorine, nitrogen oxide and sulfur compounds. The Atmospheric chemical Ionization Mass Spectrometer AIMS has been developed to accurately measure a set of these constituents on aircraft by means of chemical ionization. Here we present a setup using SF5− reagent ions for the simultaneous measurement of trace gas concentrations of HCl, HNO3 and SO2 in the  pptv to ppmv (10−12 to 10−6 mol mol−1) range with in-flight and online calibration called AIMS-TG (Atmospheric chemical Ionization Mass Spectrometer for measurements of trace gases). Part 1 of this paper (Kaufmann et al., 2016) reports on the UTLS water vapor measurements with the AIMS-H2O configuration. The instrument can be flexibly switched between two configurations depending on the scientific objective of the mission. For AIMS-TG, a custom-made gas discharge ion source has been developed for generation of reagent ions that selectively react with HCl, HNO3, SO2 and HONO. HNO3 and HCl are routinely calibrated in-flight using permeation devices; SO2 is continuously calibrated during flight adding an isotopically labeled 34SO2 standard. In addition, we report on trace gas measurements of HONO, which is sensitive to the reaction with SF5−. The detection limit for the various trace gases is in the low 10 pptv range at a 1 s time resolution with an overall uncertainty of the measurement of the order of 20 %. AIMS has been integrated and successfully operated on the DLR research aircraft Falcon and HALO (High Altitude LOng range research aircraft). As an example, measurements conducted during the TACTS/ESMVal (Transport and Composition of the LMS/UT and Earth System Model Validation) mission with HALO in 2012 are presented, focusing on a classification of tropospheric and stratospheric influences in the UTLS region. The combination of AIMS measurements with other measurement techniques yields a comprehensive picture of the sulfur, chlorine and reactive nitrogen oxide budget in the UTLS. The different trace gases measured with AIMS exhibit the potential to gain a better understanding of the trace gas origin and variability at and near the tropopause.

scholarly journals A high-resolution time-of-flight chemical ionization mass spectrometer utilizing hydronium ions (H<sub>3</sub>O<sup>+</sup> ToF-CIMS) for measurements of volatile organic compounds in the atmosphere

2016 ◽  
Author(s):  
Bin Yuan ◽  
Abigail Koss ◽  
Carsten Warneke ◽  
Jessica B. Gilman ◽  
Brian M. Lerner ◽  
...  
Keyword(s):  
High Resolution ◽  
Proton Transfer ◽  
Mass Spectrometer ◽  
Chemical Ionization ◽  
Transfer Reaction ◽  
Proton Transfer Reaction ◽  
Reaction Mass ◽  
Ionization Mass ◽  
Hydronium Ions ◽  
Volatile Organic

Abstract. Proton transfer reactions between hydronium ions (H3O+) and volatile organic compounds (VOCs) provide a fast and high sensitive measurement technique for VOCs, leading to extensive use of proton-transfer-reaction mass spectrometry (PTR-MS) in atmospheric research. Based on the same ionization approach, we describe the development of a high-resolution (HR) time of flight chemical ionization mass spectrometer (ToF-CIMS) utilizing H3O+ as the reagent ions. The new H3O+ ToF-CIMS has sensitivities of 100–1000 cps/ppb (ion counts per second per part-per-billion mixing ratio of VOC) and detection limits of 20–600 ppt at 3σ for a 1-second integration time for simultaneous measurements of many VOC species of atmospheric relevance. Compared with similar instruments with quadrupole mass spectrometer, e.g. proton-transfer-reaction mass spectrometers, the ToF analyzer with mass resolution (m/Δm) of up to 6000 not only increases measurement frequency of the instrument, but also expands the number of measurable species. The humidity dependence of the instrument was characterized for various VOC species and the behaviors for different species can be explained by compound-specific properties that affect the ion chemistry. The new H3O+ ToF-CIMS was successfully deployed on the NOAA WP-3D research aircraft for the SONGNEX campaign in spring of 2015. The measured mixing ratios of several aromatics from the H3O+ ToF-CIMS agreed within ±10 % with independent gas chromatography (GC) measurements from whole air samples. Initial results from the SONGNEX measurements demonstrate that the H3O+ ToF-CIMS dataset will be valuable for the identification and characterization of emissions from various sources, investigation of secondary formation of many photochemical organic products and therefore the chemical evolution of gas-phase organic carbon in the atmosphere.

scholarly journals Online gas- and particle-phase measurements of organosulfates, organosulfonates and nitrooxy organosulfates in Beijing utilizing a FIGAERO ToF-CIMS

2018 ◽  
Vol 18 (14) ◽  
pp. 10355-10371 ◽  
Author(s):  
Michael Le Breton ◽  
Yujue Wang ◽  
Åsa M. Hallquist ◽  
Ravi Kant Pathak ◽  
Jing Zheng ◽  
...  
Keyword(s):  
Gas Phase ◽  
Mass Spectrometer ◽  
Glycolic Acid ◽  
Measurement Techniques ◽  
Ambient Air ◽  
Ionization Mass ◽  
Particle Phase ◽  
Acid Sulfate ◽  
Phase Measurements ◽  
Sulfate Production

Abstract. A time-of-flight chemical ionization mass spectrometer (CIMS) utilizing the Filter Inlet for Gas and Aerosol (FIGAERO) was deployed at a regional site 40 km north-west of Beijing and successfully identified and measured 17 sulfur-containing organics (SCOs are organo/nitrooxy organosulfates and sulfonates) with biogenic and anthropogenic precursors. The SCOs were quantified using laboratory-synthesized standards of lactic acid sulfate and nitrophenol organosulfate (NP OS). The variation in field observations was confirmed by comparison to offline measurement techniques (orbitrap and high-performance liquid chromatography, HPLC) using daily averages. The mean total (of the 17 identified by CIMS) SCO particle mass concentration was 210 ± 110 ng m−3 and had a maximum of 540 ng m−3, although it contributed to only 2 ± 1 % of the organic aerosol (OA). The CIMS identified a persistent gas-phase presence of SCOs in the ambient air, which was further supported by separate vapour-pressure measurements of NP OS by a Knudsen Effusion Mass Spectrometer (KEMS). An increase in relative humidity (RH) promoted partitioning of SCO to the particle phase, whereas higher temperatures favoured higher gas-phase concentrations. Biogenic emissions contributed to only 19 % of total SCOs measured in this study. Here, C10H16NSO7, a monoterpene-derived SCO, represented the highest fraction (10 %) followed by an isoprene-derived SCO. The anthropogenic SCOs with polycyclic aromatic hydrocarbon (PAH) and aromatic precursors dominated the SCO mass loading (51 %) with C11H11SO7, derived from methyl naphthalene oxidation, contributing to 40 ng m−3 and 0.3 % of the OA mass. Anthropogenic-related SCOs correlated well with benzene, although their abundance depended highly on the photochemical age of the air mass, tracked using the ratio between pinonic acid and its oxidation product, acting as a qualitative photochemical clock. In addition to typical anthropogenic and biogenic precursors the biomass-burning precursor nitrophenol (NP) provided a significant level of NP OS. It must be noted that the contribution analysis here is only representative of the detected SCOs. There are likely to be many more SCOs present which the CIMS has not identified. Gas- and particle-phase measurements of glycolic acid suggest that partitioning towards the particle phase promotes glycolic acid sulfate production, contrary to the current formation mechanism suggested in the literature. Furthermore, the HSO4⋅H2SO4- cluster measured by the CIMS was utilized as a qualitative marker for acidity and indicates that the production of total SCOs is efficient in highly acidic aerosols with high SO42- and organic content. This dependency becomes more complex when observing individual SCOs due to variability of specific VOC precursors.

scholarly journals Comparison of different real time VOC measurement techniques in a ponderosa pine forest

2013 ◽  
Vol 13 (5) ◽  
pp. 2893-2906 ◽  
Author(s):  
L. Kaser ◽  
T. Karl ◽  
R. Schnitzhofer ◽  
M. Graus ◽  
I. S. Herdlinger-Blatt ◽  
...  
Keyword(s):  
Proton Transfer ◽  
Mass Spectrometer ◽  
Ponderosa Pine ◽  
Transfer Reaction ◽  
Thermal Dissociation ◽  
Proton Transfer Reaction ◽  
Ionization Mass ◽  
Mixing Ratios ◽  
Relative Contribution ◽  
Tof Ms

Abstract. Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa) during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser-Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK + MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK + MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and likely points to an offset in calibration, rather than a difference in the ability to measure the sum of terpenes. The contribution of isoprene relative to MBO inferred from PTR-MS and PTR-TOF-MS was smaller than 12% while GC-MS data suggested an average of 21% of isoprene relative to MBO. This comparison demonstrates that the current capability of VOC measurements to account for OH reactivity associated with the measured VOCs is within 20%.

scholarly journals Fragmentation inside PTR-based mass spectrometers limits the detection of ROOR and ROOH peroxides

2021 ◽  
Author(s):  
Haiyan Li ◽  
Thomas Golin Almeida ◽  
Yuanyuan Luo ◽  
Jian Zhao ◽  
Brett B. Palm ◽  
...  
Keyword(s):  
Electric Fields ◽  
Mass Spectrometer ◽  
Full Range ◽  
Proton Transfer Reaction ◽  
Ionization Mass ◽  
Proton Affinities ◽  
Ionization Source ◽  
Additional Energy ◽  
Mass Spectrometers ◽  
Noisy Signals

Abstract. Proton-transfer-reaction (PTR) is a commonly applied ionization technique for mass spectrometers, where hydronium ions (H3O+) transfer a proton to analytes with higher proton affinities than the water molecule. This method has most commonly been used to quantify volatile hydrocarbons, but later generation PTR-instruments have been designed for better throughput of less volatile species, allowing detection of more functionalized molecules as well. For example, the recently developed Vocus PTR time-of-flight mass spectrometer (PTR-TOF) has been shown to agree well with an iodide adduct based chemical ionization mass spectrometer (CIMS) for products with 3-5 O-atoms from oxidation of monoterpenes (C10H16). However, while several different types of CIMS instruments (including those using iodide) detect abundant signals also at “dimeric” species, believed to be primarily ROOR peroxides, no such signals have been observed in the Vocus PTR, even though these compounds fulfil the condition of having higher proton affinity than water. More traditional PTR instruments have been limited to volatile molecules as the inlets have not been designed for transmission of easily condensable species. Some newer instruments, like the Vocus PTR, have overcome this limitation, but are still not able to detect the full range of functionalized products, suggesting that other limitations need to be considered. One such limitation, well-documented in PTR literature, is the tendency of protonation to lead to fragmentation of some analytes. In this work, we evaluate the potential for PTR to detect dimers and the most oxygenated compounds, as these have been shown to be crucial for forming atmospheric aerosol particles. We studied the detection of dimers using a Vocus PTR-TOF in laboratory experiments as well as through quantum chemical calculations. Only noisy signals of potential dimers were observed during experiments on the ozonolysis of the monoterpene α-pinene, while a few small signals of dimeric compounds were detected during the ozonolysis of cyclohexene. During the latter experiments, we also tested varying the pressures and electric fields in the ionization region of the Vocus PTR-TOF, finding that only small improvements were possible in the relative dimer contributions. Calculations for model ROOR and ROOH systems showed that most of these peroxides should fragment partially following protonation. With inclusion of additional energy from the ion-molecule collisions driven by the electric fields in the ionization source, computational results suggest substantial or nearly complete fragmentation of dimers. Our study thus suggests that while the improved versions of PTR-based mass spectrometers are very powerful tools for measuring hydrocarbons and their moderately oxidized products, other types of CIMS are likely more suitable for the detection of ROOR and ROOH species.

scholarly journals Comparison of different real time VOC measurement techniques in a ponderosa pine forest

2012 ◽  
Vol 12 (10) ◽  
pp. 27955-27988 ◽  
Author(s):  
L. Kaser ◽  
T. Karl ◽  
R. Schnitzhofer ◽  
M. Graus ◽  
I. S. Herdlinger-Blatt ◽  
...  
Keyword(s):  
Proton Transfer ◽  
Mass Spectrometer ◽  
Ponderosa Pine ◽  
Transfer Reaction ◽  
Thermal Dissociation ◽  
Proton Transfer Reaction ◽  
Ionization Mass ◽  
Mixing Ratios ◽  
Relative Contribution ◽  
Tof Ms

Abstract. Volatile organic compound (VOC) mixing ratios measured by five independent instruments are compared at a forested site dominated by ponderosa pine (Pinus Ponderosa) during the BEACHON-ROCS field study in summer 2010. The instruments included a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), a Proton Transfer Reaction Quadrupole Mass Spectrometer (PTR-MS), a Fast Online Gas-Chromatograph coupled to a Mass Spectrometer (GC/MS; TOGA), a Thermal Dissociation Chemical Ionization Mass Spectrometer (PAN-CIMS) and a Fiber Laser-Induced Fluorescence Instrument (FILIF). The species discussed in this comparison include the most important biogenic VOCs and a selected suite of oxygenated VOCs that are thought to dominate the VOC reactivity at this particular site as well as typical anthropogenic VOCs that showed low mixing ratios at this site. Good agreement was observed for methanol, the sum of the oxygenated hemiterpene 2-methyl-3-buten-2-ol (MBO) and the hemiterpene isoprene, acetaldehyde, the sum of acetone and propanal, benzene and the sum of methyl ethyl ketone (MEK) and butanal. Measurements of the above VOCs conducted by different instruments agree within 20%. The ability to differentiate the presence of toluene and cymene by PTR-TOF-MS is tested based on a comparison with GC-MS measurements, suggesting a study-average relative contribution of 74% for toluene and 26% for cymene. Similarly, 2-hydroxy-2-methylpropanal (HMPR) is found to interfere with the sum of methyl vinyl ketone and methacrolein (MVK+MAC) using PTR-(TOF)-MS at this site. A study-average relative contribution of 85% for MVK+MAC and 15% for HMPR was determined. The sum of monoterpenes measured by PTR-MS and PTR-TOF-MS was generally 20–25% higher than the sum of speciated monoterpenes measured by TOGA, which included α-pinene, β-pinene, camphene, carene, myrcene, limonene, cineole as well as other terpenes. However, this difference is consistent throughout the study, and likely points to an offset in calibration, rather than a difference in the ability to measure the sum of terpenes. The contribution of isoprene relative to MBO inferred from PTR-MS and PTR-TOF-MS was smaller than 12% while GC-MS data suggested an average of 21% of isoprene relative to MBO. This comparison demonstrates that the current capability of VOC measurements to account for OH reactivity associated with the measured VOCs is within 20%.

scholarly journals Oxidation product characterization from ozonolysis of the diterpene ent-kaurene

2021 ◽  
Author(s):  
Yuanyuan Luo ◽  
Olga Garmash ◽  
Haiyan Li ◽  
Frans Graeffe ◽  
Arnaud P. Praplan ◽  
...  
Keyword(s):  
Gas Phase ◽  
Mass Spectrometer ◽  
Atmospheric Chemistry ◽  
Ambient Air ◽  
Proton Transfer Reaction ◽  
Oxidation Products ◽  
Ionization Mass ◽  
Product Characterization ◽  
First Time ◽  
Clustering Patterns

Abstract. Diterpenes (C20H32) are biogenically emitted volatile compounds that only recently have been observed in ambient air. They are expected to be highly reactive, and their oxidation is likely to form condensable vapors. However, until now, no studies have investigated gas-phase diterpene oxidation. In this paper, we explored the ozonolysis of a diterpene, ent-kaurene, in a simulation chamber. Using state-of-the-art mass spectrometry, we characterized diterpene oxidation products for the first time, and we identified several products with varying oxidation levels, including highly oxygenated organic molecules (HOM) monomers and dimers. The most abundant monomers measured using a nitrate chemical ionization mass spectrometer were C19H28O8 and C20H30O5, and dimers were C38H60O6 and C39H62O6. The exact molar yield of HOM from kaurene ozonolysis was hard to quantify due to uncertainties in both the kaurene and HOM concentrations, but our best estimate was a few percent, which is similar to values reported earlier for many monoterpenes. We also monitored the decrease of the gas-phase oxidation products in response to an increased condensation sink in the chamber to deduce their affinity to condense. The oxygen content was a critical parameter affecting the volatility of products, with 4–5 O-atoms needed for the main monomeric species to condense. Finally, we report on the observed fragmentation and clustering patterns of kaurene in a Vocus proton transfer reaction time-of-flight mass spectrometer. Our findings highlight similarities and differences between diterpenes and smaller terpenes during their atmospheric oxidation, but more studies on different diterpenes are needed for a broader view of their role in atmospheric chemistry.

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