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

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. <br><br> 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<sup>−1</sup>) 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

Unexpected seasonality in quantity and composition of Amazon rainforest air reactivity

The hydroxyl radical (OH) removes most atmospheric pollutants from air. The loss frequency of OH radicals due to the combined effect of all gas-phase OH reactive species is a measureable quantity termed total OH reactivity. Here we present total OH reactivity observations in pristine Amazon rainforest air, as a function of season, time-of-day and height (0–80 m). Total OH reactivity is low during wet (10 s^(−1)) and high during dry season (62 s^(−1)). Comparison to individually measured trace gases reveals strong variation in unaccounted for OH reactivity, from 5 to 15% missing in wet-season afternoons to mostly unknown (average 79%) during dry season. During dry-season afternoons isoprene, considered the dominant reagent with OH in rainforests, only accounts for ~20% of the total OH reactivity. Vertical profiles of OH reactivity are shaped by biogenic emissions, photochemistry and turbulent mixing. The rainforest floor was identified as a significant but poorly characterized source of OH reactivity

Introducing the novel concept of cumulative concentration roses for studying the transport of ultrafine particles from an airport to adjacent residential areas

Airports are often surrounded by urban residential areas, which is both a motivation and challenge for studying their potential impact on local air quality. Airports are a relevant source of ultrafine particles (UFPs), which can pose a risk to human health due to their small size (particle diameter Dp≤100 nm). However, in urban environments, UFPs originate from a multitude of biogenic and anthropogenic sources. Here, we investigate UFPs in close proximity to an airport to disentangle their impact on local air quality from other urban sources. We present observations and analyses of airborne UFP concentrations and size distributions determined at two sites in close proximity to Munich Airport. Therefore, two novel measurement stations were established north and south of the airport but were neither situated on the axis of prevailing wind directions nor impacted by fly overs. This set-up allowed us to explore a mainly advection-driven distribution of UFPs into the most populated adjacent residential areas. The observation period covered a full year from August 2021 to July 2022. We analysed the data set in three steps. (1) First, we derived UFP concentration roses using the wind data as reported at 10 m height at the airport to represent the local wind field. An increase in particle number concentrations and a shift of the modal maximum towards smaller mobility diameters became evident for wind directions, including those approaching from the airport. During the airport's operation hours during the daytime, median particle number concentrations were 2.2- and 1.6-fold compared to nighttime at the northern station and the southern station. However, our data had a high variability, and the direction-based analysis was uncertain due to other potential UFP sources in the surroundings and the assumption of a homogeneous, local wind field. (2) Next, we derived concentration roses employing the airflow observations from the two measuring stations at 5.3 m height. While the annual concentration rose in principle yielded the same conclusions as the first analysis step, a significant seasonal and diurnal variability of UFPs and wind became evident. The influencing factors were likely other urban local UFP sources, an increased surface roughness due to green vegetation, and the atmospheric boundary layer development. (3) In order to assess the possible advection of UFPs from the direction of Munich Airport relative to all other directions over the course of the year, we calculated cumulative concentration roses with both local- and site-scale wind data. Under the assumption of a homogeneous local wind field, the fraction of all UFPs sampled in airflows approaching from the airport's direction was 21 % (N322) and 40 % (S229). Considering a local background, the range of UFP advection from Munich Airport to the adjacent residential areas was up to 10 % in the north and 14 % in the south. It has to be noted that these values highlight the relative magnitude of the maximum impact of the airport on local air quality as they do not distinguish between UFP sources from the airport and other measuring sites. Additionally, they integrate over a time period during which the airport did not reach its full capacity compared to pre-COVID-19 times.</p

Atmospheric mixing ratios of methyl ethyl ketone (2-butanone) in tropical, boreal, temperate and marine environments

Methyl ethyl ketone (MEK) enters the atmosphere following direct emission from vegetation and anthropogenic activities, as well as being produced by the gas-phase oxidation of volatile organic compounds (VOCs) such as n-butane. This study presents the first overview of ambient MEK measurements at six different locations, characteristic of forested, urban and marine environments. In order to understand better the occurrence and behaviour of MEK in the atmosphere, we analyse diel cycles of MEK mixing ratios, vertical profiles, ecosystem flux data, and HYSPLIT back trajectories, and compare with co-measured VOCs. MEK measurements were primarily conducted with proton-transfer-reaction mass spectrometer (PTR-MS) instruments. Results from the sites under biogenic influence demonstrate that vegetation is an important source of MEK. The diel cycle of MEK follows that of ambient temperature and the forest structure plays an important role in air mixing. At such sites, a high correlation of MEK with acetone was observed (e.g. r2 = 0.96 for the SMEAR Estonia site in a remote hemiboreal forest in Tartumaa, Estonia, and r2 = 0.89 at the ATTO pristine tropical rainforest site in central Amazonia). Under polluted conditions, we observed strongly enhanced MEK mixing ratios. Overall, the MEK mixing ratios and flux data presented here indicate that both biogenic and anthropogenic sources contribute to its occurrence in the global atmosphere

How the OH reactivity affects the ozone production efficiency: case studies in Beijing and Heshan, China

Total OH reactivity measurements were conducted on the Peking University campus (Beijing) in August 2013 and in Heshan (Guangdong province) from October to November 2014. The daily median OH reactivity was 20 ± 11 s^(−1) in Beijing and 31 ± 20 s^(−1) in Heshan, respectively. The data in Beijing showed a distinct diurnal pattern with the maxima over 27 s^(−1) in the early morning and minima below 16 s^(−1) in the afternoon. The diurnal pattern in Heshan was not as evident as in Beijing. Missing reactivity, defined as the difference between measured and calculated OH reactivity, was observed at both sites, with 21 % missing reactivity in Beijing and 32 % missing reactivity in Heshan. Unmeasured primary species, such as branched alkenes, could contribute to missing reactivity in Beijing, especially during morning rush hours. An observation-based model with the RACM2 (Regional Atmospheric Chemical Mechanism version 2) was used to understand the daytime missing reactivity in Beijing by adding unmeasured oxygenated volatile organic compounds and simulated intermediates of the degradation from primary volatile organic compounds (VOCs). However, the model could not find a convincing explanation for the missing reactivity in Heshan, where the ambient air was found to be more aged, and the missing reactivity was presumably attributed to oxidized species, such as unmeasured aldehydes, acids and dicarbonyls. The ozone production efficiency was 21 % higher in Beijing and 30 % higher in Heshan when the model was constrained by the measured reactivity, compared to the calculations with measured and modeled species included, indicating the importance of quantifying the OH reactivity for better understanding ozone chemistry

The summertime Boreal forest field measurement intensive (HUMPPA-COPEC-2010): an overview of meteorological and chemical influences

This paper describes the background, instrumentation, goals, and the regional influences on the HUMPPA-COPEC intensive field measurement campaign, conducted at the Boreal forest research station SMEAR II (Station for Measuring Ecosystem-Atmosphere Relation) in Hyytiälä, Finland from 12 July–12 August 2010. The prevailing meteorological conditions during the campaign are examined and contrasted with those of the past six years. Back trajectory analyses show that meteorological conditions at the site in 2010 were characterized by a higher proportion of southerly flow than in the other years studied. As a result the summer of 2010 was anomalously warm and high in ozone making the campaign relevant for the analysis of possible future climates. A comprehensive land use analysis, provided on both 5 and 50 km scales, shows that the main vegetation types surrounding the site on both the regional and local scales are: coniferous forest (Scots pine and/or Norway spruce); mixed forest (Birch and conifers); and woodland scrub (e.g. Willows, Aspen); indicating that the campaign results can be taken as representative of the Boreal forest ecosystem. In addition to the influence of biogenic emissions, the measurement site was occasionally impacted by sources other than vegetation. Specific tracers have been used here to identify the time periods when such sources have impacted the site namely: biomass burning (acetonitrile and CO), urban anthropogenic pollution (pentane and SO&lt;sub&gt;2&lt;/sub&gt;) and the nearby Korkeakoski sawmill (enantiomeric ratio of chiral monoterpenes). None of these sources dominated the study period, allowing the Boreal forest summertime emissions to be assessed and contrasted with various other source signatures

Volatile diterpene emission by two Mediterranean Cistaceae shrubs

Mediterranean vegetation emits a wide range of biogenic volatile organic compounds (BVOCs) among which isoprenoids present quantitatively the most important compound class. Here, we investigated the isoprenoid emission from two Mediterranean Cistaceae shrubs, Halimium halimifolium and Cistus ladanifer, under controlled and natural conditions, respectively. For the first time, diurnal emission patterns of the diterpene kaurene were detected in real-time by Proton-Transfer-Reaction-Timeof- Flight-Mass-Spectrometer. Kaurene emissions were strongly variable among H. halimifolium plants, ranging from 0.01 ± 0.003 to 0.06 ± 0.01 nmol m−2 s−1 in low and high emitting individuals, respectively. They were in the same order of magnitude as monoterpene (0.01 ± 0.01 to 0.11 ± 0.04 nmol m−2 s−1) and sesquiterpene (0.01 ± 0.01 to 0.52 nmol m−2 s−1) emission rates. Comparable range and variability was found for C. ladanifer under natural conditions. Labelling with 13C-pyruvate suggested that emitted kaurene was not derived from de novo biosynthesis. The high kaurene content in leaves, the weak relationship with ecophysiological parameters and the tendency of higher emissions with increasing temperatures in the field indicate an emission from storage pools. This study highlights significant emissions of kaurene from two Mediterranean shrub species, indicating that the release of diterpenes into the atmosphere should probably deserve more attention in the futureinfo:eu-repo/semantics/publishedVersio

Atmospheric benzenoid emissions from plants rival those from fossil fuels

Despite the known biochemical production of a range of aromatic compounds by plants and the presence of benzenoids in floral scents, the emissions of only a few benzenoid compounds have been reported from the biosphere to the atmosphere. Here, using evidence from measurements at aircraft, ecosystem, tree, branch and leaf scales, with complementary isotopic labeling experiments, we show that vegetation (leaves, flowers, and phytoplankton) emits a wide variety of benzenoid compounds to the atmosphere at substantial rates. Controlled environment experiments show that plants are able to alter their metabolism to produce and release many benzenoids under stress conditions. The functions of these compounds remain unclear but may be related to chemical communication and protection against stress. We estimate the total global secondary organic aerosol potential from biogenic benzenoids to be similar to that from anthropogenic benzenoids (~10 Tg y-1), pointing to the importance of these natural emissions in atmospheric physics and chemistry