Abstract. Hydroxyl (OH) radical reactivity (k OH ) 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 reactivPublished by Copernicus Publications on behalf of the European Geosciences Union. H. Fuchs et al.: OH reactivity comparison in SAPHIRity 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 flowtube 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.
An experimental forest ecosystem drought Drought is affecting many of the world’ s forested ecosystems, but it has proved challenging to develop an ecosystem-level mechanistic understanding of the ways that drought affects carbon and water fluxes through forest ecosystems. Werner et al . used an experimental approach by imposing an artificial drought on an entire enclosed ecosystem: the Biosphere 2 Tropical Rainforest in Arizona (see the Perspective by Eisenhauer and Weigelt). The authors show that ecosystem-scale plant responses to drought depend on distinct plant functional groups, differing in their water-use strategies and their position in the forest canopy. The balance of these plant functional groups drives changes in carbon and water fluxes, as well as the release of volatile organic compounds into the atmosphere. —AMS
Abstract. The Arabian Peninsula is characterized by high and increasing levels of photochemical air pollution. Strong solar irradiation, high temperatures and large anthropogenic emissions of reactive trace gases result in intense photochemical activity, especially during the summer months. However, air chemistry measurements in the region are scarce. In order to assess regional pollution sources and oxidation rates, the first ship-based direct measurements of total OH reactivity were performed in summer 2017 from a vessel traveling around the peninsula during the AQABA (Air Quality and Climate Change in the Arabian Basin) campaign. Total OH reactivity is the total loss frequency of OH radicals due to all reactive compounds present in air and defines the local lifetime of OH, the most important oxidant in the troposphere. During the AQABA campaign, the total OH reactivity ranged from below the detection limit (5.4 s−1) over the northwestern Indian Ocean (Arabian Sea) to a maximum of 32.8±9.6 s−1 over the Arabian Gulf (also known as Persian Gulf) when air originated from large petroleum extraction/processing facilities in Iraq and Kuwait. In the polluted marine regions, OH reactivity was broadly comparable to highly populated urban centers in intensity and composition. The permanent influence of heavy maritime traffic over the seaways of the Red Sea, Gulf of Aden and Gulf of Oman resulted in median OH sinks of 7.9–8.5 s−1. Due to the rapid oxidation of direct volatile organic compound (VOC) emissions, oxygenated volatile organic compounds (OVOCs) were observed to be the main contributor to OH reactivity around the Arabian Peninsula (9 %–35 % by region). Over the Arabian Gulf, alkanes and alkenes from the petroleum extraction and processing industry were an important OH sink with ∼9 % of total OH reactivity each, whereas NOx and aromatic hydrocarbons (∼10 % each) played a larger role in the Suez Canal, which is influenced more by ship traffic and urban emissions. We investigated the number and identity of chemical species necessary to explain the total OH sink. Taking into account ∼100 individually measured chemical species, the observed total OH reactivity can typically be accounted for within the measurement uncertainty (50 %), with 10 dominant trace gases accounting for 20 %–39 % of regional total OH reactivity. The chemical regimes causing the intense ozone pollution around the Arabian Peninsula were investigated using total OH reactivity measurements. Ozone vs. OH reactivity relationships were found to be a useful tool for differentiating between ozone titration in fresh emissions and photochemically aged air masses. Our results show that the ratio of NOx- and VOC-attributed OH reactivity was favorable for ozone formation almost all around the Arabian Peninsula, which is due to NOx and VOCs from ship exhausts and, often, oil/gas production. Therewith, total OH reactivity measurements help to elucidate the chemical processes underlying the extreme tropospheric ozone concentrations observed in summer over the Arabian Basin.
Abstract. We present the first ambient measurements of a new marine emission methane sulfonamide (MSAM: CH5NO2S), along with dimethyl sulfide (DMS) and dimethyl sulfone (DMSO2) over the Arabian Sea. Two shipborne transects (W → E, E → W) were made during the AQABA (Air Quality and Climate Change in the Arabian Basin) measurement campaign. Molar mixing ratios in picomole of species per mole of air (throughout this paper abbreviated as ppt) of DMS were in the range of 300–500 ppt during the first traverse of the Arabian Sea (first leg) and 100–300 ppt on the second leg. On the first leg DMSO2 was always below 40 ppt and MSAM was close to the limit of detection. During the second leg DMSO2 was between 40 and 120 ppt and MSAM was mostly in the range of 20–50 ppt with maximum values of 60 ppt. An analysis of HYSPLIT back trajectories combined with calculations of the exposure of these trajectories to underlying chlorophyll in the surface water revealed that most MSAM originates from the Somalia upwelling region, known for its high biological activity. MSAM emissions can be as high as one-third of DMS emissions over the upwelling region. This new marine emission is of particular interest as it contains both sulfur and nitrogen, making it potentially relevant to marine nutrient cycling and marine atmospheric particle formation.
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
The 2015/16 El Niño event caused unprecedented drought and warming in the Amazon basin. How tropical forests react to such extreme events in terms of volatile organic compound (VOC) emissions is of interest as the frequency of these events is predicted to increase through climate change. The diverse VOCs emitted can be significant for plants' carbon budgets, influence ozone and particle production, and through their reactivity impact OH concentrations. Total OH reactivity is a directly measureable quantity that gives the reaction frequency of OH radicals with all reactive species in the atmosphere in s−1. Here we present a comparison of the OH reactivity diel cycle from November 2015, i.e., extreme drought and elevated temperatures associated with strong El Niño conditions, with November 2012, a “normal” El Niño Southern Oscillation (ENSO)-neutral period. Interestingly, the diel maximum of OH reactivity during the El Niño event occurred at sunset instead of, under normal conditions, early afternoon. The absolute total diel OH reactivity, however, did not change significantly. Daytime OH reactivity averages were 24.3 ± 14.5 s−1 in 2012 and 24.6 ± 11.9 s−1 in 2015, respectively. Our findings suggest that a combination of stronger turbulent transport above the canopy with stress-related monoterpene and, possibly, other biogenic volatile organic compound (BVOC) emissions were responsible for the increased reactivity at sunset.
Non-methane hydrocarbons (NMHCs) such as ethane and propane are significant atmospheric pollutants and precursors of tropospheric ozone, while the Middle East is a global emission hotspot due to extensive oil and gas production. Here we compare in situ hydrocarbon measurements, performed around the Arabian Peninsula, with global model simulations that include current emission inventories (EDGAR) and state-of-the-art atmospheric circulation and chemistry mechanisms (EMAC model). While measurements of high mixing ratios over the Arabian Gulf are adequately simulated, strong underprediction by the model was found over the northern Red Sea. By examining the individual sources in the model and by utilizing air mass back-trajectory investigations and Positive Matrix Factorization (PMF) analysis, we deduce that Red Sea Deep Water (RSDW) is an unexpected, potent source of atmospheric NMHCs. This overlooked underwater source is comparable with total anthropogenic emissions from entire Middle Eastern countries, and significantly impacts the regional atmospheric chemistry.
Abstract. We present shipborne measurements of NOx (≡ NO + NO2) and NOy (≡ NOx+ gas- and particle-phase organic and inorganic oxides of nitrogen) in summer 2017 as part of the expedition “Air Quality and climate change in the Arabian BAsin” (AQABA). The NOx and NOz (≡ NOy-NOx) measurements, made with a thermal dissociation cavity ring-down spectrometer (TD-CRDS), were used to examine the chemical mechanisms involved in the processing of primary NOx emissions and their influence on the NOy budget in chemically distinct marine environments, including the Mediterranean Sea, the Red Sea, and the Arabian Gulf, which were influenced to varying extents by emissions from shipping and oil and gas production. Complementing the TD-CRDS measurements, NO and NO2 data sets from a chemiluminescence detector (CLD) were used in the analysis. In all regions, we find that NOx is strongly connected to ship emissions, both via direct emission of NO and via the formation of HONO and its subsequent photolytic conversion to NO. The role of HONO was assessed by calculating the NOx production rate from its photolysis. Mean NO2 lifetimes were 3.9 h in the Mediterranean Sea, 4.0 h in the Arabian Gulf, and 5.0 h in the Red Sea area. The cumulative loss of NO2 during the night (reaction with O3) was more important than daytime losses (reaction with OH) over the Arabian Gulf (by a factor 2.8) and over the Red Sea (factor 2.9), whereas over the Mediterranean Sea, where OH levels were high, daytime losses dominated (factor 2.5). Regional ozone production efficiencies (OPEs; calculated from the correlation between Ox and NOz, where Ox= O3+ NO2) ranged from 10.5 ± 0.9 to 19.1 ± 1.1. This metric quantifies the relative strength of photochemical O3 production from NOx compared to the competing sequestering into NOz species. The largest values were found over the Arabian Gulf, consistent with high levels of O3 found in that region (10–90 percentiles range: 23–108 ppbv). The fractional contribution of individual NOz species to NOy exhibited a large regional variability, with HNO3 generally the dominant component (on average 33 % of NOy) with significant contributions from organic nitrates (11 %) and particulate nitrates in the PM1 size range (8 %).
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