Comparative Reactivity Method Research Articles

Total OH Reactivity Measurements in a Suburban Site of Shanghai

AbstractTotal hydroxyl radicals (OH) reactivity, as a measure of the OH total loss rate and the significance of atmospheric oxidation, is broadly used to evaluate the OH budget in the atmosphere. Here, measurements of the total OH reactivity were performed at a suburban air quality monitoring supersite (Dianshan Lake) of Shanghai, between 1 August and 15 September, 2020, using the Comparative Reactivity Method. The measured total OH reactivity ranged from 13.9 to 107.4 s−1 with an average of 38.4 s−1. Meanwhile, the calculated total OH reactivity varied between 8.9 and 84.4 s−1 from concentrations of atmospheric trace gases measured by multiple in‐situ techniques including an online gas chromatograph equipped with mass spectrometry and flame ionization detection (GC‐MS/FID) and two proton‐transfer‐reaction time‐of‐flight mass spectrometers (PTR‐ToF‐MSs). A 12.1% missing OH reactivity was evident from the comparison between the measured and calculated total OH reactivities. Inorganic trace gases, methane, and 54 observed Photochemical Assessment Monitoring Station compounds detected by GC‐MS/FID, accounted for 25.7%, 1.3%, and 10%, respectively, of the calculated total OH reactivity. In addition, 292 species detected by PTR‐ToF‐MSs contributed the rest 63%. The top 10 VOC contributors to the measured total OH reactivity were C5H8, CH2O, C2H4O, C6H6O, C4H8O, C3H6O, C10H16, C5H10O, C5H8O2, and C8H10, respectively, whose total contribution reached 42%. Correlation analysis for the missing OH reactivity suggests that primary biogenic VOCs could be a potential source for the missing OH reactivity during the daytime, and that secondary oxidation products might also be connected to the missing OH reactivity.

Contributions to OH reactivity from unexplored volatile organic compounds measured by PTR-ToF-MS – a case study in a suburban forest of the Seoul metropolitan area during the Korea–United States Air Quality Study (KORUS-AQ) 2016

Abstract. We report OH reactivity observations by a chemical ionization mass spectrometer–comparative reactivity method (CIMS-CRM) instrument in a suburban forest of the Seoul metropolitan area (SMA) during the Korea–United States Air Quality Study (KORUS-AQ 2016) from mid-May to mid-June of 2016. A comprehensive observational suite was deployed to quantify reactive trace gases inside of the forest canopy including a high-resolution proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS). An average OH reactivity of 30.7±5.1 s−1 was observed, while the OH reactivity calculated from CO, NO+NO2 (NOx), ozone (O3), sulfur dioxide (SO2), and 14 volatile organic compounds (VOCs) was 11.8±1.0 s−1. An analysis of 346 peaks from the PTR-ToF-MS accounted for an additional 6.0±2.2 s−1 of the total measured OH reactivity, leaving 42.0 % missing OH reactivity. A series of analyses indicate that the missing OH reactivity most likely comes from VOC oxidation products of both biogenic and anthropogenic origin.

The improved comparative reactivity method (ICRM): measurements of OH reactivity under high-NO<sub><i>x</i></sub> conditions in ambient air

Abstract. The comparative reactivity method (CRM) was developed more than a decade to measure OH reactivity (i.e., OH loss frequency) in both laboratory and field studies. However, accurate OH reactivity quantification remains challenging under real ambient conditions, especially for OH reactivity measurements in high-NOx (e.g., > 10 ppbv) environments, as ambient NO enhances the regeneration of OH radicals in the CRM reactor. To solve this problem, we design a new and improved CRM reactor (ICRM) and add NO into the system continuously so that the HO2 radical concentration is suppressed. We confirmed the appropriate level of NO by determining the maximum decrease in the pyrrole level caused by regenerated OH radicals from NO + HO2. RO2 radicals induced by volatile organic compounds (VOCs) in the ICRM reactor were also found to react with NO, which led to the regeneration of OH radicals and thus the underestimation of OH reactivity. This effect was quantified by the calibration of representative VOC species at different NO levels, and the correction coefficients obtained were used to correct the measured OH reactivity. All these efforts resulted in reducing the uncertainty of the NO-artifact correction by at least an order of magnitude compared to the original CRM system. Additionally, these technological improvements also considerably reduced the systematic errors from pyrrole photolysis in the original system. A new operation mode was proposed for the ICRM, which is able to avoid the interference resulting from OH radicals produced by photolysis of residual humidity and save time for ambient measurement. The ICRM system was employed in a field campaign to measure OH reactivity and performed well with ambient NO levels ranging from 0 to 50 ppbv, which are typically observed in the urban and suburban atmosphere.

Characterization of Total OH Reactivity in a Rapeseed Field: Results from the COV3ER Experiment in April 2017

Croplands remain poorly studied ecosystems in terms of total hydroxyl radical (OH) reactivity, especially when compared to forests. As part of the COV3ER project, total OH reactivity (ROH), defined as the total loss rate of OH due to its reaction with reactive species in the atmosphere, was characterized in a rapeseed field (Grignon, France) during the blooming season in April 2017. Measurements were performed in a dynamic chamber as well as in ambient air using the Comparative Reactivity Method (CRM). Complementary measurements of organic (including a proton transfer reaction quadrupole ion–time of flight mass spectrometry, PTRQi-ToFMS) and inorganic compounds were also performed in order to calculate the expected OH reactivity and evaluate the missing fraction. Measured ROH varied diurnally in the dynamic chamber (mROHchamber) with maxima around 20 to 30 s−1 at midday and minima during dark hours, following the variability of the enclosed branch VOCsrapeseed, which is light- and temperature-dependent. Oxygenated VOCs were the major compounds emitted by the rapeseed crop. However, in terms of contribution to OH reactivity, isoprene accounted for 40% during the daytime, followed by acetaldehyde (21%) and monoterpenes (18%). The comparison between mROHchamber and calculated ROH (cROHchamber) exhibited little or no difference during dark hours, whereas a maximum difference appeared around midday, highlighting a significant missing fraction (46% on average during daytime) mainly related to biogenic temperature- and/or light-dependent emissions.

Variability of hydroxyl radical (OH) reactivity in the Landes maritime pine forest: results from the LANDEX campaign 2017

Abstract. Total hydroxyl radical (OH) reactivity measurements were conducted during the LANDEX intensive field campaign in a coniferous temperate forest located in the Landes area, southwestern France, during July 2017. In order to investigate inter-canopy and intra-canopy variability, measurements were performed inside (6 m) and above the canopy level (12 m), as well as at two different locations within the canopy, using a comparative reactivity method (CRM) and a laser photolysis–laser-induced fluorescence (LP-LIF) instrument. The two techniques were intercompared at the end of the campaign by performing measurements at the same location. Volatile organic compounds were also monitored at both levels with a proton transfer time-of-flight mass spectrometer and online gas chromatography instruments to evaluate their contribution to total OH reactivity, with monoterpenes being the main reactive species emitted in this forest dominated by Pinus pinaster Aiton. Total OH reactivity varied diurnally, following the trend of biogenic volatile organic compounds (BVOCs), the emissions and concentrations of which were dependent on meteorological parameters. Average OH reactivity was around 19.2 and 16.5 s−1 inside and above the canopy, respectively. The highest levels of total OH reactivity were observed during nights with a low turbulence (u*≤0.2 m s−1), leading to lower mixing of emitted species within the canopy and thus an important vertical stratification characterized by a strong concentration gradient. Comparing the measured and the calculated OH reactivity highlighted an average missing OH reactivity of 22 % and 33 % inside and above the canopy, respectively. A day–night variability was observed on missing OH reactivity at both heights. Investigations showed that during daytime, missing OH sinks could be due to primary emissions and secondary products linked to a temperature-enhanced photochemistry. Regarding nighttime missing OH reactivity, higher levels were seen for the stable and warm night of 4–5 July, showing that these conditions could have been favorable for the accumulation of long-lived species (primary and secondary species) during the transport of the air mass from nearby forests.

Intercomparison of OH and OH reactivity measurements in a high isoprene and low NO environment during the Southern Oxidant and Aerosol Study (SOAS)

We intercompare OH and OH reactivity datasets from two different techniques, chemical ionization mass spectrometry (CIMS) and laser-induced fluorescence (LIF) in a high isoprene and low NO environment in a southeastern US forest during the Southern Oxidant and Aerosol Study (SOAS). An LIF instrument measured OH and OH reactivity at the top of a tower, a CIMS instrument measured OH at the top of the tower, and a CIMS based comparative reactivity method (CRM-CIMS) instrument deployed at the base of the tower measured OH reactivity. Averaged diel variations of OH and OH reactivity from these datasets agree within analytical uncertainty and correlations of LIF versus CIMS for OH and OH reactivity have slopes of 0.65 and 0.97, respectively. However, there are systematic differences between the measurement datasets. The CRM-CIMS measurements of OH reactivity were ∼16% lower than those by the LIF technique in the late afternoon. We speculate that it is caused by losses in the sampling line down to the CRM-CIMS instrument. On the other hand, we could not come up with a reasonable explanation for the difference in the LIF and CIMS OH datasets for early morning and late afternoon when OH is below 1 × 106 molecules cm−3. Nonetheless, results of this intercomparison exercise strengthen previous publications from the field site on OH concentrations and atmospheric reactivity.

Comparison of OH reactivity measurements in the atmospheric simulation chamber SAPHIR

Abstract. Hydroxyl (OH) radical reactivity (kOH) has been measured for 18 years with different measurement techniques. In order to compare the performances of instruments deployed in the field, two campaigns were conducted performing experiments in the atmospheric simulation chamber SAPHIR at Forschungszentrum Jülich in October 2015 and April 2016. Chemical conditions were chosen either to be representative of the atmosphere or to test potential limitations of instruments. All types of instruments that are currently used for atmospheric measurements were used in one of the two campaigns. The results of these campaigns demonstrate that OH reactivity can be accurately measured for a wide range of atmospherically relevant chemical conditions (e.g. water vapour, nitrogen oxides, various organic compounds) by all instruments. The precision of the measurements (limit of detection < 1 s−1 at a time resolution of 30 s to a few minutes) is higher for instruments directly detecting hydroxyl radicals, whereas the indirect comparative reactivity method (CRM) has a higher limit of detection of 2 s−1 at a time resolution of 10 to 15 min. The performances of the instruments were systematically tested by stepwise increasing, for example, the concentrations of carbon monoxide (CO), water vapour or nitric oxide (NO). In further experiments, mixtures of organic reactants were injected into the chamber to simulate urban and forested environments. Overall, the results show that the instruments are capable of measuring OH reactivity in the presence of CO, alkanes, alkenes and aromatic compounds. The transmission efficiency in Teflon inlet lines could have introduced systematic errors in measurements for low-volatile organic compounds in some instruments. CRM instruments exhibited a larger scatter in the data compared to the other instruments. The largest differences to reference measurements or to calculated reactivity were observed by CRM instruments in the presence of terpenes and oxygenated organic compounds (mixing ratio of OH reactants were up to 10 ppbv). In some of these experiments, only a small fraction of the reactivity is detected. The accuracy of CRM measurements is most likely limited by the corrections that need to be applied to account for known effects of, for example, deviations from pseudo first-order conditions, nitrogen oxides or water vapour on the measurement. Methods used to derive these corrections vary among the different CRM instruments. Measurements taken with a flow-tube instrument combined with the direct detection of OH by chemical ionisation mass spectrometry (CIMS) show limitations in cases of high reactivity and high NO concentrations but were accurate for low reactivity (< 15 s−1) and low NO (< 5 ppbv) conditions.

OH reactivity of the urban air in Helsinki, Finland, during winter

A new instrument to measure total OH reactivity in ambient air based on the Comparative Reactivity Method (CRM) has been built and characterized at the Finnish Meteorological Institute in Helsinki, Finland. The system is based on the detection of pyrrole by a gas chromatograph with a photoionization detector and designed for long term studies. It was tested in a container close to the SMEAR III semi-urban station in Helsinki during the winter in February 2016. The sampling location next to the delivery area of the institute was influenced by local vehicle emissions and cannot be considered representative of background conditions in Helsinki. However, effects of nitrogen oxides on the measurements could be investigated there. During this campaign, 56 compounds were measured individually by 1) an in-situ gas chromatograph coupled to a mass spectrometer (GC/MS) and by 2) off-line sampling in canisters and on adsorbent filled cartridges taken at the container and subsequently analysed by GC-FID and liquid chromatography, respectively. In addition, nitrogen oxides were measured at the same location, while ozone, carbon monoxide and sulfur dioxide concentrations have been retrieved from the SMEAR III mast data. The comparison between the total OH reactivity measured and the OH reactivity derived from individual compound measurements are in better agreement for lower reactivity levels. Possible explanations for the differences are discussed in detail.

Intercomparison of the comparative reactivity method (CRM) and pump–probe technique for measuring total OH reactivity in an urban environment

Abstract. The investigation of hydroxyl radical (OH) chemistry during intensive field campaigns has led to the development of several techniques dedicated to ambient measurements of total OH reactivity, which is the inverse of the OH lifetime. Three techniques are currently used during field campaigns, including the total OH loss rate method, the pump–probe method, and the comparative reactivity method. However, no formal intercomparison of these techniques has been published so far, and there is a need to ensure that measurements of total OH reactivity are consistent among the different techniques. An intercomparison of two OH reactivity instruments, one based on the comparative reactivity method (CRM) and the other based on the pump–probe method, was performed in October 2012 in a NOx-rich environment, which is known to be challenging for the CRM technique. This study presents an extensive description of the two instruments, the CRM instrument from Mines Douai (MD-CRM) and the pump–probe instrument from the University of Lille (UL-FAGE), and highlights instrumental issues associated with the two techniques. It was found that the CRM instrument used in this study underestimates ambient OH reactivity by approximately 20 % due to the photolysis of volatile organic compounds (VOCs) inside the sampling reactor; this value is dependent on the position of the lamp within the reactor. However, this issue can easily be fixed, and the photolysis of VOCs was successfully reduced to a negligible level after this intercomparison campaign. The UL-FAGE instrument may also underestimate ambient OH reactivity due to the difficulty to accurately measure the instrumental zero. It was found that the measurements are likely biased by approximately 2 s-1, due to impurities in humid zero air. Two weeks of ambient sampling indicate that the measurements performed by the two OH reactivity instruments are in agreement, within the measurement uncertainties for each instrument, for NOx mixing ratios up to 100 ppbv. The CRM technique has hitherto mainly been used in low-NOx environments, i.e. environments with ambient NOx mixing ratios lower than a few ppbv, due to a measurement artifact generated by ambient NO inside the sampling reactor. However, this study shows that this technique can also be used under NOx-rich conditions if a NOx-dependent correction is carefully applied on the OH reactivity measurements. A full suite of 52 VOCs, NOx, and other inorganic species were monitored during this intercomparison. An investigation of the OH reactivity budget for this urban site suggests that this suite of trace gases can account for the measured total OH reactivity.

Intercomparison of two comparative reactivity method instruments inf the Mediterranean basin during summer 2013

Abstract. The hydroxyl radical (OH) plays a key role in the atmosphere, as it initiates most of the oxidation processes of volatile organic compounds (VOCs), and can ultimately lead to the formation of ozone and secondary organic aerosols (SOAs). There are still uncertainties associated with the OH budget assessed using current models of atmospheric chemistry and direct measurements of OH sources and sinks have proved to be valuable tools to improve our understanding of the OH chemistry. The total first order loss rate of OH, or total OH reactivity, can be directly measured using three different methods, such as the following: total OH loss rate measurement, laser-induced pump and probe technique and comparative reactivity method. Observations of total OH reactivity are usually coupled to individual measurements of reactive compounds in the gas phase, which are used to calculate the OH reactivity. Studies using the three methods have highlighted that a significant fraction of OH reactivity is often not explained by individually measured reactive compounds and could be associated to unmeasured or unknown chemical species. Therefore accurate and reproducible measurements of OH reactivity are required. The comparative reactivity method (CRM) has demonstrated to be an advantageous technique with an extensive range of applications, and for this reason it has been adopted by several research groups since its development. However, this method also requires careful corrections to derive ambient OH reactivity. Herein we present an intercomparison exercise of two CRM instruments, CRM-LSCE (Laboratoire des Sciences du Climat et de l'Environnement) and CRM-MD (Mines Douai), conducted during July 2013 at the Mediterranean site of Ersa, Cape Corsica, France. The intercomparison exercise included tests to assess the corrections needed by the two instruments to process the raw data sets as well as OH reactivity observations. The observation was divided in three parts: 2 days of plant emissions (8–9 July), 2 days of ambient measurements (10–11 July) and 2 days (12–13 July) of plant emissions. We discuss in detail the experimental approach adopted and how the data sets were processed for both instruments. Corrections required for the two instruments lead to higher values of reactivity in ambient air; overall 20 % increase for CRM-MD and 49 % for CRM-LSCE compared to the raw data. We show that ambient OH reactivity measured by the two instruments agrees very well (correlation described by a linear least squares fit with a slope of 1 and R2 of 0.75). This study highlights that ambient measurements of OH reactivity with differently configured CRM instruments yield consistent results in a low NOx (NO + NO2), terpene rich environment, despite differential corrections relevant to each instrument. Conducting more intercomparison exercises, involving more CRM instruments operated under different ambient and instrumental settings will help in assessing the variability induced due to instrument-specific corrections further.

Detailed characterizations of the new Mines Douai comparative reactivity method instrument via laboratory experiments and modeling

Abstract. The hydroxyl (OH) radical is an important oxidant in the troposphere, which controls the lifetime of most air quality- and climate-related trace gases. However, there are still uncertainties concerning its atmospheric budget, and integrated measurements of OH sinks have been valuable to improve this aspect. Among the analytical tools used for measuring total OH reactivity in ambient air, the comparative reactivity method (CRM) is spreading rapidly in the atmospheric community. However, measurement artifacts have been highlighted for this technique, and additional work is needed to fully characterize them. In this study, we present the new Mines Douai CRM instrument, with an emphasis on the corrections that need to be applied to ambient measurements of total OH reactivity. Measurement artifacts identified in the literature have been investigated, including (1) a correction for a change in relative humidity between the measurement steps leading to different OH levels, (2) the formation of spurious OH in the sampling reactor when hydroperoxy radicals (HO2) react with nitrogen monoxide (NO), (3) not operating the CRM under pseudo-first-order kinetics, and (4) the dilution of ambient air inside the reactor. The dependences of these artifacts on various measurable parameters, such as the pyrrole-to-OH ratio and the bimolecular reaction rate constants of ambient trace gases with OH, have also been studied. Based on these observations, parameterizations are proposed to correct ambient OH reactivity measurements. On average, corrections of 5.2 ± 3.2, 9.2 ± 15.7, and 8.5 ± 5.8 s−1 were respectively observed for (1), (2) and (3) during a field campaign performed in Dunkirk, France (summer 2014). Numerical simulations have been performed using a box model to check whether experimental observations mentioned above are consistent with our understanding of the chemistry occurring in the CRM reactor. Two different chemical mechanisms have been shown to reproduce the magnitude of corrections (2) and (3). In addition, these simulations reproduce their dependences on the pyrrole-to-OH ratio and on bimolecular reaction rate constants of gases reacting with OH. The good agreement found between laboratory experiments and model simulations gives us confidence in the proposed parameterizations. However, it is worth noting that the numerical values given in this study are suitable for the Mines Douai instrument and may not be appropriate for other CRM instruments. It is recommended that each group characterize its own instrument following the recommendations given in this study. An assessment of performances for the Mines Douai instrument, including a propagation of errors from the different corrections, indicates a limit of detection of 3.0 s−1 and total uncertainties of 17–25 % for OH reactivity values higher than 15 s−1 and NOx mixing ratios lower than 30 ppbv.

Missing in total OH reactivity of VOCs from gasoline evaporation

Abstract Gasoline evaporation is an important anthropogenic source of atmospheric volatile organic compounds (VOCs). Total OH reactivity for gasoline vapor was measured from 4 kinds of gasoline for the first time by comparative reactivity method (CRM) using proton transfer reaction mass spectrometer (PTR-MS). Compositions of 56 PAMS (photochemical assessment monitoring station) nonmethane hydrocarbons (NMHCs) were measured for both liquid and headspace of gasoline. We found high abundance of alkenes and aromatics in gasoline. The calculated OH reactivity derived from quantified NMHCs speciation accounted for only 57 ± 4% of total reactivity obtained from CRM method. N-Alkenes, only 6 wt% in liquid gasoline, contributed to 70% of calculated reactivity. We assume that the undetected branched alkenes are the possible reason for the missing reactivity. We suggest that the priority of gasoline quality improvement is to reduce alkenes content in gasoline in term of reactivity-based control.

Comment on "Observation and modelling of HO<sub>x</sub> radicals in a boreal forest" by Hens et al. (2014)

Though as a researcher one is always happy when peers find one’s work useful and accordingly cite it, it is unfortunate when the respective paper is cited incorrectly. Hens et al. (2014) write “Studies on oxidation processes in monoterpene–dominated environments are rare. Direct OH reactivity measurements in a boreal forest, conducted by Sinha et al. (2008), and a box model study investigating the OH reactivity budget (Mogensen et al., 2011) revealed a significant fraction of ‘unknown OH reactivity’.” Firstly, the reference of Sinha et al. (2008) must be an error, since that refers to a publication about the method development of the comparative reactivity method (CRM) together with first field tests conducted in the tropical rainforest of Suriname and the urban atmosphere of Mainz – but not in a boreal forest. We assume that Hens et al. (2014) instead are thinking of the paper by Sinha et al. (2010). Further, it is correct that Mogensen et al. (2011) found a large fraction of unaccounted OH reactivity; however, they did not reach that conclusion using a box model. Instead they presented the first model study of the total OH reactivity in a boreal forest using a one-dimensional column model with near-explicit chemistry (Boy et al., 2011; Mogensen et al., 2011). There exist earlier publications where the OH reactivity has been addressed using a 1-D model; for example, the OH loss has been simulated with respect to certain primary emitted organic compounds (e.g. Stroud et al., 2005). By including the dimension of the entire column of the boundary layer, we are capable of providing valuable information. For example, as shown in Mogensen et al. (2011), the reactivity of OH has a distinct vertical profile, which is obviously not captured by a box model. Due to practical limitations, one can only measure the reactivity of OH (and other parameters of any other compound) at one or a few points in space. To our knowledge, at the time of publication of Mogensen et al. (2011), there existed no publications describing that the OH reactivity had been measured at more than one height simultaneously at one site. Mao et al. (2012) had conducted such experiments in 2009; however, the article appeared later than Mogensen et al. (2011). Another exception is the aircraft measurements conducted by Mao et al. (2009); however those measurements did not capture the lowest part of the boundary layer. Mogensen et al. (2011) therefore gave the first hints about how the space-dependent canopy emission and boundary layer meteorology could affect the reactivity in a boreal forest. Hereby we got the first glimpse of how the reactivity of OH could look outside of that one measured height. After publication of Mogensen et al. (2011), several measurement and modelling papers have followed investigating the vertical dimension of the OH reactivity (e.g. Mao et al., 2012; Pratt et al., 2012; Hansen et al., 2014).

VOC–OHM: A new technique for rapid measurements of ambient total OH reactivity and volatile organic compounds using a single proton transfer reaction mass spectrometer

Measurements of total hydroxyl radical (OH) reactivity and volatile organic compounds (VOC) are necessary for improving our understanding of reactive emissions and atmospheric oxidation in air pollution and atmospheric chemistry studies. Proton transfer reaction mass spectrometers (PTR-MS) can measure ambient VOCs and the total ambient OH reactivity. However, till date this has always required deployment of two PTR-MS instruments, wherein one instrument measures ambient VOCs and the other instrument measures the total OH reactivity using the comparative reactivity method (CRM). Due to material (e.g. power, space) or financial constraints, deploying two PTR-MS instruments is not always possible and yet it is desirable to quantify both VOCs and OH reactivity. Here, we present a novel hyphenated technique christened VOC-OHM (for Volatile Organic Compounds–OH reactivity Measurement) that enables rapid ambient measurements of both VOCs and total OH reactivity using a single PTR-MS. The technique can provide more specificity for identification of compounds using a PTR-QMS through an estimate of the rate coefficient of the major isobaric contributor with the hydroxyl radical as shown in the case of m/z=69 for isoprene and furan, which are nominal isobars but have rate coefficients that differ by one order of magnitude. It also demonstrates a new safer and portable substitute for pressurized zero air bottles that have been required thus far in CRM OH reactivity deployments. VOC–OHM successfully couples the typical VOC and CRM experimental set ups without undermining the PTR-MS's ability to measure either parameter. The design of the VOC–OHM system, its validation, optimization and results of field tests are described in detail. The VOC–OHM system measures the ambient VOCs and OH reactivity every hour for ∼20min durations each, with an ambient data gap of ∼13min in between. Thus rapid temporal changes in the ambient chemical composition and reactivity are easily quantified. The sampling periods and VOC speciation achieved using VOC–OHM can be customized depending on user preferences, providing more options for the majority of users possessing a single PTR-MS.

Seasonal measurements of total OH reactivity emission rates from Norway spruce in 2011

Abstract. Numerous reactive volatile organic compounds (VOCs) are emitted into the atmosphere by vegetation. Most biogenic VOCs are highly reactive towards the atmosphere's most important oxidant, the hydroxyl (OH) radical. One way to investigate the chemical interplay between biosphere and atmosphere is through the measurement of total OH reactivity, the total loss rate of OH radicals. This study presents the first determination of total OH reactivity emission rates (measurements via the comparative reactivity method) based on a branch cuvette enclosure system mounted on a Norway spruce (Picea abies) throughout spring, summer and autumn 2011. In parallel VOC emission rates were monitored by a second proton-transfer-reaction mass spectrometer (PTR-MS), and total ozone (O3) loss rates were obtained inside the cuvette. Total OH reactivity emission rates were in general temperature and light dependent, showing strong diel cycles with highest values during daytime. Monoterpene emissions contributed most, accounting for 56–69% of the measured total OH reactivity flux in spring and early summer. However, during late summer and autumn the monoterpene contribution decreased to 11–16%. At this time, a large missing fraction of the total OH reactivity emission rate (70–84%) was found when compared to the VOC budget measured by PTR-MS. Total OH reactivity and missing total OH reactivity emission rates reached maximum values in late summer corresponding to the period of highest temperature. Total O3 loss rates within the closed cuvette showed similar diel profiles and comparable seasonality to the total OH reactivity fluxes. Total OH reactivity fluxes were also compared to emissions from needle storage pools predicted by a temperature-only-dependent algorithm. Deviations of total OH reactivity fluxes from the temperature-only-dependent emission algorithm were observed for occasions of mechanical and heat stress. While for mechanical stress, induced by strong wind, measured VOCs could explain total OH reactivity emissions, during heat stress they could not. The temperature-driven algorithm matched the diel variation of total OH reactivity emission rates much better in spring than in summer, indicating a different production and emission scheme for summer and early autumn. During these times, unmeasured and possibly unknown primary biogenic emissions contributed significantly to the observed total OH reactivity flux.

Atmospheric OH Reactivity Measurement Using Comparative Reactivity Method Followed by Gas Chromatography or Proton Transfer Reaction Mass Spectrometry

大気質を判断するのに，通常は大気中に存在するそれぞれの成分を個別に測定して濃度を知る必要がある．しかし，それぞれの濃度を測るのではなく，全OHラジカル反応性を直接測定するという，新たな大気質診断の指標・測定法が提案されてきた．しかし，直接OHラジカル反応性を測定するシステムはレーザーを複数台使用する高価で操作が難しいものであるため，一般に広く普及しづらいものであった．そこで，より一般的な装置を用いてOHラジカル反応性を測定するシステムを開発した．競争反応法の応用である反応性比較法を原理として用いており，反応性比較物質を導入した大気試料に，OHラジカルを混合して競争反応を起こし，反応性比較物質の減少から大気試料のOHラジカル反応性を求める方法である．反応性比較物質の濃度測定は陽子移動反応質量分析計やガスクロマトグラフィー－水素イオン化検出器（GC-FID）を用いて行った．これらの反応性比較法を原理としたOHラジカル反応性測定システムを用いて，実際の大気で測定を行い，これまで測定されてきたレーザー法との比較や問題点についての検討を行った．

Total OH reactivity measurements using a new fast Gas Chromatographic Photo-Ionization Detector (GC-PID)

Abstract. The primary and most important oxidant in the atmosphere is the hydroxyl radical (OH). Currently OH sinks, particularly gas phase reactions, are poorly constrained. One way to characterize the overall sink of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. To date, direct measurements of total OH reactivity have been either performed using a Laser-Induced Fluorescence (LIF) system ("pump-and-probe" or "flow reactor") or the Comparative Reactivity Method (CRM) with a Proton-Transfer-Reaction Mass Spectrometer (PTR-MS). Both techniques require large, complex and expensive detection systems. This study presents a feasibility assessment for CRM total OH reactivity measurements using a new detector, a Gas Chromatographic Photoionization Detector (GC-PID). Such a system is smaller, more portable, less power consuming and less expensive than other total OH reactivity measurement techniques. Total OH reactivity is measured by the CRM using a competitive reaction between a reagent (here pyrrole) with OH alone and in the presence of atmospheric reactive molecules. The new CRM method for total OH reactivity has been tested with parallel measurements of the GC-PID and the previously validated PTR-MS as detector for the reagent pyrrole during laboratory experiments, plant chamber and boreal field studies. Excellent agreement of both detectors was found when the GC-PID was operated under optimum conditions. Time resolution (60–70 s), sensitivity (LOD 3–6 s−1) and overall uncertainty (25% in optimum conditions) for total OH reactivity were similar to PTR-MS based total OH reactivity measurements. One drawback of the GC-PID system was the steady loss of sensitivity and accuracy during intensive measurements lasting several weeks, and a possible toluene interference. Generally, the GC-PID system has been shown to produce closely comparable results to the PTR-MS and thus in suitable environments (e.g. forests) it presents a viably economical alternative for groups interested in total OH reactivity observations.

Total OH reactivity measurements in Paris during the 2010 MEGAPOLI winter campaign

Abstract. Hydroxyl radicals play a central role in the troposphere as they control the lifetime of many trace gases. Measurement of OH reactivity (OH loss rate) is important to better constrain the OH budget and also to evaluate the completeness of measured VOC budget. Total atmospheric OH reactivity was measured for the first time in an European Megacity: Paris and its surrounding areas with 12 million inhabitants, during the MEGAPOLI winter campaign 2010. The method deployed was the Comparative Reactivity Method (CRM). The measured dataset contains both measured and calculated OH reactivity from CO, NOx and VOCs measured via PTR-MS, GC-FID and GC-MS instruments. The reactivities observed in Paris covered a range from 10 s−1 to 130 s−1, indicating a large loading of chemical reactants. The present study showed that, when clean marine air masses influenced Paris, the purely local OH reactivity (20 s−1) is well explained by the measured species. Nevertheless, when there is a continental import of air masses, high levels of OH reactivity were obtained (120–130 s−1) and the missing OH reactivity measured in this case jumped to 75%. Using covariations of the missing OH reactivity to secondary inorganic species in fine aerosols, we suggest that the missing OH reactants were most likely highly oxidized compounds issued from photochemically processed air masses of anthropogenic origin.

Summertime total OH reactivity measurements from boreal forest during HUMPPA-COPEC 2010

Abstract. Ambient total OH reactivity was measured at the Finnish boreal forest station SMEAR II in Hyytiälä (Latitude 61°51' N; Longitude 24°17' E) in July and August 2010 using the Comparative Reactivity Method (CRM). The CRM – total OH reactivity method – is a direct, in-situ determination of the total loss rate of hydroxyl radicals (OH) caused by all reactive species in air. During the intensive field campaign HUMPPA-COPEC 2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) the total OH reactivity was monitored both inside (18 m) and directly above the forest canopy (24 m) for the first time. The comparison between these two total OH reactivity measurements, absolute values and the temporal variation have been analyzed here. Stable boundary layer conditions during night and turbulent mixing in the daytime induced low and high short-term variability, respectively. The impact on total OH reactivity from biogenic emissions and associated photochemical products was measured under "normal" and "stressed" (i.e. prolonged high temperature) conditions. The advection of biomass burning emissions to the site caused a marked change in the total OH reactivity vertical profile. By comparing the OH reactivity contribution from individually measured compounds and the directly measured total OH reactivity, the size of any unaccounted for or "missing" sink can be deduced for various atmospheric influences. For "normal" boreal conditions a missing OH reactivity of 58%, whereas for "stressed" boreal conditions a missing OH reactivity of 89% was determined. Various sources of not quantified OH reactive species are proposed as possible explanation for the high missing OH reactivity.

Contributions of primary and secondary biogenic VOC tototal OH reactivity during the CABINEX (Community Atmosphere-Biosphere INteractions Experiments)-09 field campaign

Abstract. We present OH reactivity measurements using the comparative reactivity method with a branch enclosure technique for four different tree species (red oak, white pine, beech and red maple) in the UMBS PROPHET tower footprint during the Community Atmosphere Biosphere INteraction EXperiment (CABINEX) field campaign in July of 2009. Proton Transfer Reaction-Mass Spectrometry (PTR-MS) was sequentially used as a detector for OH reactivity and BVOC concentrations including isoprene and monoterpenes (MT) for enclosure air. Therefore, the measurement dataset contains both measured and calculated OH reactivity from well-known BVOC. The results indicate that isoprene and MT, and in one case a sesquiterpene, can account for the measured OH reactivity. Significant discrepancy between measured OH reactivity and calculated OH reactivity from isoprene and MT is found for the red maple enclosure dataset but it can be reconciled by adding reactivity from emission of a sesquiterpene, α-farnesene, detected by GC-MS. This leads us to conclude that no significant unknown BVOC emission contributed to ambient OH reactivity from these trees at least during the study period. However, this conclusion should be followed up by more comprehensive side-by-side intercomparison between measured and calculated OH reactivity and laboratory experiments with controlled temperature and light environments to verify effects of those essential parameters towards unknown/unmeasured reactive BVOC emissions. This conclusion leads us to explore the contribution towards ambient OH reactivity (the dominant OH sink in this ecosystem) oxidation products such as hydroxyacetone, glyoxal, methylglyoxal and C4 and C5-hydroxycarbonyl using recently published isoprene oxidation mechanisms (Mainz Isoprene Mechanism II and Leuven Isoprene Mechanism). Evaluation of conventionally unmeasured first generation oxidation products of isoprene and their possible contribution to ambient missing OH reactivity indicates that the ratio of OH reactivity from unmeasured products over OH reactivity from MVK + MACR is strongly dependent on NO concentrations. The unmeasured oxidation products can contribute ~7.2 % (8.8 % from LIM and 5.6 % by MIM 2 when NO = 100 pptv) of the isoprene contribution towards total ambient OH reactivity. This amount can explain ~8.0 % (9.7 % from LIM and 6.2 % from MIM 2) of missing OH reactivity, reported by Di Carlo et al. (2004) at the same site. Further study on the contribution from further generation of unmeasured oxidation products is needed to constrain tropospheric photochemical reactivity of BVOC that have important implications for both photochemical ozone and secondary organic aerosol formation.