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This study investigates the rain-initiated mixing and variability in the mixing ratio of selected trace gases in the atmosphere over the central Amazon rain forest. It builds on comprehensive data from the Amazon Tall Tower Observatory (ATTO), spanning from 2013 to 2020 and comprising the greenhouse gases (GHGs) carbon dioxide (CO2) and methane (CH4); the reactive trace gases carbon monoxide (CO), ozone (O3), nitric oxide (NO), and nitrogen dioxide (NO2); and selected volatile organic compounds (VOCs). Based on more than 1000 analyzed rainfall events, the study resolves the trace gas mixing ratio patterns before, during, and after the rain events, along with vertical mixing ratio gradients across the forest canopy. The assessment of the rainfall events was conducted independently for daytime and nighttime periods, which allows us to elucidate the influence of solar radiation. The mixing ratios of CO2, CO, and CH4 clearly declined during rainfall, which can be attributed to the downdraft-related entrainment of pristine air from higher altitudes into the boundary layer, a reduction of the photosynthetic activity under increased cloud cover, and changes in the surface fluxes. Notably, CO showed a faster reduction than CO2, and the vertical gradient of CO2 and CO is steeper than for CH4. Conversely, the O3 mixing ratio increased across all measurement heights in the course of the rain-related downdrafts. Following the O3 enhancement by up to a factor of 2, NO, NO2, and isoprene mixing ratios decreased. The temporal and vertical variability of the trace gases is intricately linked to the diverse sink and source processes, surface fluxes, and free-troposphere transport. Within the canopy, several interactions unfold among soil, atmosphere, and plants, shaping the overall dynamics. Also, the mixing ratio of biogenic VOCs (BVOCs) clearly varied with rainfall, driven by factors such as light, temperature, physical transport, and soil processes. Our results disentangle the patterns in the trace gas mixing ratio in the course of sudden and vigorous atmospheric mixing during rainfall events. By selectively uncovering processes that are not clearly detectable under undisturbed conditions, our results contribute to a better understanding of the trace gas life cycle and its interplay with meteorology, cloud dynamics, and rainfall in the Amazon.

This study focuses on the distribution of hydrogen peroxide (H2O2) in the upper tropical troposphere at altitudes between 8 and 15 km based on in situ observations during the Chemistry of the Atmosphere: Field Experiment in Africa (CAFE-Africa) campaign conducted in August–September 2018 over the tropical Atlantic Ocean and western Africa. The measured hydrogen peroxide mixing ratios in the upper troposphere show no clear trend in the latitudinal distribution with locally increased levels (up to 1 ppbv​​​​​​​) within the Intertropical Convergence Zone (ITCZ), over the African coastal area, as well as during measurements performed in proximity to the tropical storm Florence (later developing into a hurricane). The observed H2O2 distribution suggests that mixing ratios in the upper troposphere seem to be far less dependent on latitude than assumed previously and the corresponding factors influencing the photochemical production and loss of H2O2. The observed levels of H2O2 in the upper troposphere indicate the influence of convective transport processes on the distribution of the species not only in the tropical but also in the subtropical regions. The measurements are compared to observation-based photostationary steady-state (PSS) calculations and numerical simulations by the global ECHAM/MESSy Atmospheric Chemistry (EMAC) model. North of the ITCZ, PSS calculations produce mostly lower H2O2 mixing ratios relative to the observations. The observed mixing ratios tend to exceed the PSS calculations by up to a factor of 2. With the exception of local events, the comparison between the calculated PSS values and the observations indicates enhanced H2O2 mixing ratios relative to the expectations based on PSS calculations in the north of the ITCZ. On the other hand, PSS calculations tend to overestimate the H2O2 mixing ratios in most of the sampled area in the south of the ITCZ by a factor of up to 3. The significant influence of convection in the ITCZ and the enhanced presence of clouds towards the Southern Hemisphere indicate contributions of atmospheric transport and cloud scavenging in the sampled region. Simulations performed by the EMAC model also overestimate hydrogen peroxide levels particularly in the Southern Hemisphere, most likely due to underestimated cloud scavenging. EMAC simulations and PSS calculations both indicate a latitudinal gradient from the Equator towards the subtropics. In contrast, the measurements show no clear gradient with latitude in the mixing ratios of H2O2 in the upper troposphere with a slight decrease from the ITCZ towards the subtropics, indicating a relatively low dependency on the solar radiation intensity and the corresponding photolytic activity. The largest model deviations relative to the observations correspond with the underestimated hydrogen peroxide loss due to enhanced cloud presence, scavenging, and rainout in the ITCZ and towards the south.

Formaldehyde (HCHO), hydrogen peroxide (H2O2) and organic hydroperoxides (ROOH) play a key role in atmospheric oxidation processes. They act as sources and sinks for HOx radicals (OH + HO2), with OH as the primary oxidant that governs the atmospheric self-cleaning capacity. Measurements of these species allow for evaluation of chemistry-transport models which need to account for multifarious source distributions, transport, complex photochemical reaction pathways and deposition processes of these species. HCHO is an intermediate during the oxidation of volatile organic compounds (VOCs) and is an indicator of photochemical activity and combustion-related emissions. In this study, we use in situ observations of HCHO, H2O2 and ROOH in the marine boundary layer (MBL) to evaluate results of the general circulation model EMAC (ECHAM5/MESSy2 Atmospheric Chemistry; European Center HAMburg, Modular Earth Submodel System). The dataset was obtained during the Air Quality and Climate Change in the Arabian Basin (AQABA) ship campaign around the Arabian Peninsula in summer 2017. This region is characterized by high levels of photochemical air pollution, humidity and solar irradiation, especially in the areas around the Suez Canal and the Arabian Gulf. High levels of air pollution with up to 12 ppbv HCHO, 2.3 ppbv ROOH and relatively low levels of H2O2 (≤0.5 ppbv) were detected over the Arabian Gulf. We find that EMAC failed to predict absolute mixing ratios of HCHO and ROOH during high-pollution events over the Arabian Gulf, while it reproduced HCHO on average within a factor of 2. Dry deposition velocities were determined for HCHO and H2O2 at night with 0.77±0.29 cm s−1 for HCHO and 1.03±0.52 cm s−1 for H2O2 over the Arabian Sea, which were matched by EMAC. The photochemical budget of H2O2 revealed elevated HOx radical concentrations in EMAC, which resulted in an overestimation of H2O2 by more than a factor of 5 for the AQABA dataset. The underestimated air pollution over the Arabian Gulf was related to EMAC's coarse spatial resolution and missing anthropogenic emissions in the model.

Mineral dust and sea spray aerosol represent important sources of ice-nucleating particles (INPs), the minor fraction of aerosol particles able to trigger cloud ice crystal formation and, consequently, influence multiple climate-relevant cloud properties including lifetime, radiative properties and precipitation initiation efficiency. Mineral dust is considered the dominant INP source in many parts of the world due to its ice nucleation efficiency and its sheer abundance, with global emission rates of up to 4700 Tg a−1. However, INPs emitted from the ocean surface in sea spray aerosol frequently dominate INP populations in remote marine environments, including parts of the Southern Ocean where cloud-resolving model simulations have demonstrated that cloud radiative properties are likely strongly controlled by INPs. Here we report INP concentrations measured in aerosol and seawater samples during Air Quality and Climate Change in the Arabian Basin (AQABA), a shipborne campaign that spanned the Red Sea, Gulf of Aden, Arabian Sea, Arabian Gulf and part of the Mediterranean. In aerosol samples collected within a few hundred kilometers of the first and second ranked sources of dust globally, the Sahara and Arabian Peninsula, INP concentrations ranged from 0.2 to 11 L−1 at −20 ∘C with observed ice-active surface site densities (ns) 1–3 orders of magnitude below levels predicted by mineral dust INP parameterizations. Over half of the samples (at least 14 of 26) were collected during dust storms with average dust mass concentrations between 150 and 490 µg m−3 (PM10), as simulated by the Modern-Era Retrospective analysis for Research and Application, version 2 (MERRA-2). The impacts of heat and peroxide treatments indicate that organics dominated the observed ice nucleation (IN) activity at temperatures ≥ −15 ∘C with proteinaceous (heat-labile) INPs frequently observed at high freezing temperatures >−10 ∘C. INP concentrations in seawater samples ranged between 3 and 46 mL−1 at −19 ∘C, demonstrating the relatively low INP source potential of seawater in the region as compared to seawater from multiple other regions reported previously. Overall, our results demonstrate that despite proximity to the Sahara and the Arabian Peninsula and the dominance of mineral dust in the aerosol sampled, existing mineral dust parameterizations alone would not skillfully represent the near-surface ns in the observed temperature regime (−6 to −25 ∘C). Future efforts to develop or improve representations of dust INPs at modest supercooling (≥-15 ∘C) would benefit from a characterization of the specific organic species associated with dust INPs. More generally, an improved understanding of the organic species associated with increased IN activity and their variability across dust source regions would directly inform efforts to determine whether ns-based parameterizations are appropriate for faithful representation of dust INPs in this sensitive temperature regime, whether region-specific parameterizations are required, or whether an alternative to the ns approach is necessary.

Aerosols influence the Earth's energy balance directly by modifying the radiation transfer and indirectly by altering the cloud microphysics. Anthropogenic aerosol emissions dropped considerably when the global COVID-19 pandemic resulted in severe restraints on mobility, production, and public life in spring 2020. We assess the effects of these reduced emissions on direct and indirect aerosol radiative forcing over Europe, excluding contributions from contrails. We simulate the atmospheric composition with the ECHAM5/MESSy Atmospheric Chemistry (EMAC) model in a baseline (business-as-usual) and a reduced emission scenario. The model results are compared to aircraft observations from the BLUESKY aircraft campaign performed in May–June 2020 over Europe. The model agrees well with most of the observations, except for sulfur dioxide, particulate sulfate, and nitrate in the upper troposphere, likely due to a biased representation of stratospheric aerosol chemistry and missing information about volcanic eruptions. The comparison with a baseline scenario shows that the largest relative differences for tracers and aerosols are found in the upper troposphere, around the aircraft cruise altitude, due to the reduced aircraft emissions, while the largest absolute changes are present at the surface. We also find an increase in all-sky shortwave radiation of 0.21 ± 0.05 W m−2 at the surface in Europe for May 2020, solely attributable to the direct aerosol effect, which is dominated by decreased aerosol scattering of sunlight, followed by reduced aerosol absorption caused by lower concentrations of inorganic and black carbon aerosols in the troposphere. A further increase in shortwave radiation from aerosol indirect effects was found to be much smaller than its variability. Impacts on ice crystal concentrations, cloud droplet number concentrations, and effective crystal radii are found to be negligible.

Polycyclic aromatic hydrocarbons (PAHs) and their alkylated (RPAHs), nitrated (NPAHs) and oxygenated (OPAHs) derivatives are air pollutants. Many of these substances are long-lived, can undergo long-range atmospheric transport and adversely affect human health upon exposure. However, the occurrence and fate of these air pollutants have hardly been studied in the marine atmosphere. In this study, we report the atmospheric concentrations over the Mediterranean Sea, the Red Sea, the Arabian Sea, the Gulf of Oman and the Arabian Gulf, determined during the AQABA (Air Quality and Climate Change in the Arabian Basin) project, a comprehensive ship-borne campaign in summer 2017. The average concentrations of ∑26PAHs, ∑19RPAHs, ∑11OPAHs and ∑17NPAHs, in the gas and particulate phases, were 2.99 ± 3.35 ng m−3, 0.83 ± 0.87 ng m−3, 0.24 ± 0.25 ng m−3 and 4.34 ± 7.37 pg m−3, respectively. The Arabian Sea region was the cleanest for all substance classes, with concentrations among the lowest ever reported. Over the Mediterranean Sea, we found the highest average burden of ∑26PAHs and ∑11OPAHs, while the ∑17NPAHs were most abundant over the Arabian Gulf (known also as the Persian Gulf). 1,4-Naphthoquinone (1,4-O2NAP) followed by 9-fluorenone and 9,10-anthraquinone were the most abundant studied OPAHs in most samples. The NPAH composition pattern varied significantly across the regions, with 2-nitronaphthalene (2-NNAP) being the most abundant NPAH. According to source apportionment investigations, the main sources of PAH derivatives in the region were ship exhaust emissions, residual oil combustion and continental pollution. All OPAHs and NPAHs except 2-nitrofluoranthene (2-NFLT), which were frequently detected during the campaign, showed elevated concentrations in fresh shipping emissions. In contrast, 2-NFLT and 2-nitropyrene (2-NPYR) were highly abundant in aged shipping emissions due to secondary formation. Apart from 2-NFLT and 2-NPYR, benz(a)anthracene-7,12-dione and 2-NNAP also had significant photochemical sources. Another finding was that the highest concentrations of PAHs, OPAHs and NPAHs were found in the sub-micrometre fraction of particulate matter (PM1).

The COVID-19 (coronavirus disease 2019) European lockdowns have led to a significant reduction in the emissions of primary pollutants such as NO (nitric oxide) and NO2 (nitrogen dioxide). As most photochemical processes are related to nitrogen oxide (NOx≡ NO + NO2) chemistry, this event has presented an exceptional opportunity to investigate its effects on air quality and secondary pollutants, such as tropospheric ozone (O3). In this study, we present the effects of the COVID-19 lockdown on atmospheric trace gas concentrations, net ozone production rates (NOPRs) and the dominant chemical regime throughout the troposphere based on three different research aircraft campaigns across Europe. These are the UTOPIHAN (Upper Tropospheric Ozone: Processes Involving HOx and NOx) campaigns in 2003 and 2004, the HOOVER (HOx over Europe) campaigns in 2006 and 2007, and the BLUESKY campaign in 2020, the latter performed during the COVID-19 lockdown. We present in situ observations and simulation results from the ECHAM5 (fifth-generation European Centre Hamburg general circulation model, version 5.3.02)/MESSy2 (second-generation Modular Earth Submodel System, version 2.54.0) Atmospheric Chemistry (EMAC), model which allows for scenario calculations with business-as-usual emissions during the BLUESKY campaign, referred to as the “no-lockdown scenario”. We show that the COVID-19 lockdown reduced NO and NO2 mixing ratios in the upper troposphere by around 55 % compared to the no-lockdown scenario due to reduced air traffic. O3 production and loss terms reflected this reduction with a deceleration in O3 cycling due to reduced mixing ratios of NOx, while NOPRs were largely unaffected. We also study the role of methyl peroxyradicals forming HCHO (αCH3O2) to show that the COVID-19 lockdown shifted the chemistry in the upper-troposphere–tropopause region to a NOx-limited regime during BLUESKY. In comparison, we find a volatile organic compound (VOC)-limited regime to be dominant during UTOPIHAN.

Formaldehyde (HCHO) is the most abundant aldehyde in the troposphere. While its background mixing ratio is mostly determined by the oxidation of methane, in many environments, especially in the boundary layer, HCHO can have a large variety of precursors, in particular biogenic and anthropogenic volatile organic compounds (VOCs) and their oxidation products. Here we present shipborne observations of HCHO, hydroxyl radical (OH) and OH reactivity (R(OH)), which were obtained during the Air Quality and Climate Change in the Arabian Basin (AQABA) campaign in summer 2017. The loss rate of HCHO was inferred from its reaction with OH, measured photolysis rates and dry deposition. In photochemical steady state, the HCHO loss is balanced by production via OH-initiated degradation of VOCs, photolysis of oxygenated VOCs (OVOCs) and the ozonolysis of alkenes. The slope αeff from a scatter plot of the HCHO production rate versus the product of OH and R(OH)eff (excluding inorganic contribution) yields the fraction of OH reactivity that contributes to HCHO production. Values of αeff varied between less than 2 % in relatively clean air over the Arabian Sea and the southern Red Sea and up to 32 % over the polluted Arabian Gulf (also known as Persian Gulf), signifying that polluted areas harbor a larger variety of HCHO precursors. The separation of R(OH)eff into individual compound classes revealed that elevated values of αeff coincided with increased contribution of alkanes and OVOCs, with the highest reactivity of all VOCs over the Arabian Gulf.

Various atmospheric sources and sinks regulate the abundance of tropospheric formaldehyde (HCHO), which is an important trace gas impacting the HOx (≡ HO2 + OH) budget and the concentration of ozone (O3). In this study, we present the formation and destruction terms of ambient HCHO and O3 calculated from in situ observations of various atmospheric trace gases measured at three different sites across Europe during summertime. These include a coastal site in Cyprus, in the scope of the Cyprus Photochemistry Experiment (CYPHEX) in 2014, a mountain site in southern Germany, as part of the Hohenpeißenberg Photochemistry Experiment (HOPE) in 2012, and a forested site in Finland, where measurements were performed during the Hyytiälä United Measurements of Photochemistry and Particles (HUMPPA) campaign in 2010. We show that, at all three sites, formaldehyde production from the OH oxidation of methane (CH4), acetaldehyde (CH3CHO), isoprene (C5H8) and methanol (CH3OH) can almost completely balance the observed loss via photolysis, OH oxidation and dry deposition. Ozone chemistry is clearly controlled by nitrogen oxides (NOx ≡ NO + NO2) that include O3 production from NO2 photolysis and O3 loss via the reaction with NO. Finally, we use the HCHO budget calculations to determine whether net ozone production is limited by the availability of VOCs (volatile organic compounds; VOC-limited regime) or NOx (NOx-limited regime). At the mountain site in Germany, O3 production is VOC limited, whereas it is NOx limited at the coastal site in Cyprus. The forested site in Finland is in the transition regime.

Nitrogen oxides (NOx≡NO+NO2) are centrally involved in the photochemical processes taking place in the Earth's atmosphere. Measurements of NO2, particularly in remote areas where concentrations are of the order of parts per trillion by volume (pptv), are still a challenge and subject to extensive research. In this study, we present NO2 measurements via photolysis–chemiluminescence during the research aircraft campaign CAFE Africa (Chemistry of the Atmosphere – Field Experiment in Africa) 2018 around Cabo Verde and the results of laboratory experiments to characterize the photolytic converter used. We find the NO2 reservoir species MPN (methyl peroxy nitrate) to produce the only relevant thermal interference in the converter under the operating conditions during CAFE Africa. We identify a memory effect within the conventional photolytic converter (type 1) associated with high NO concentrations and rapidly changing water vapor concentrations, accompanying changes in altitude during aircraft measurements, which is due to the porous structure of the converter material. As a result, NO2 artifacts, which are amplified by low conversion efficiencies, and a varying instrumental background adversely affect the NO2 measurements. We test and characterize an alternative photolytic converter (type 2) made from quartz glass, which improves the reliability of NO2 measurements in laboratory and field studies.

The increase of atmospheric methane (CH4) and carbon dioxide (CO2), two of the main anthropogenic greenhouse gases, is largely driven by fossil sources. Sources and sinks remain insufficiently characterized in the Mediterranean and Middle East areas, where very few in situ measurements are available. We measured the atmospheric mixing ratios of CH4 and CO2 by ship in the region in July and August 2017. High mixing ratios were observed over the Suez Canal, Red Sea and Arabian Gulf, while generally lower mixing ratios were observed over the Gulf of Aden and Gulf of Oman. We probe the origin of the CO2 and CH4 excess mixing ratio by using correlations with light alkanes and through the use of a Lagrangian model coupled to two different emission inventories of anthropogenic sources. We find that the CO2 and especially the CH4 enhancements are mainly linked to nearby oil and gas (OG) activities over the Arabian Gulf and a mixture of other sources over the Red Sea. The isomeric ratio of pentane is shown to be a useful indicator of the OG component of atmospheric CH4 at the regional level. Upstream emissions linked to oil in the northern Arabian Gulf seem to be underestimated, while gas-related emissions in the southern Gulf are overestimated in our simulations. Our results highlight the need for improvement of inventories in the area to better characterize the changes in magnitude and the complex distribution of the OG sources in the Middle East.

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 %).

Hurricane Florence was the sixth named storm in the Atlantic hurricane season 2018. It caused dozens of deaths and major economic damage. In this study, we present in situ observations of trace gases within tropical storm Florence on 2 September 2018, after it had developed a rotating nature, and of a tropical wave observed close to the African continent on 29 August 2018 as part of the research campaign CAFE Africa (Chemistry of the Atmosphere: Field Experiment in Africa) with HALO (High Altitude and LOng Range Research Aircraft). We show the impact of deep convection on atmospheric composition by measurements of the trace gases nitric oxide (NO), ozone (O3), carbon monoxide (CO), hydrogen peroxide (H2O2), dimethyl sulfide (DMS) and methyl iodide (CH3I) and by the help of color-enhanced infrared satellite imagery taken by GOES-16. While both systems, i.e., the tropical wave and the tropical storm, are deeply convective, we only find evidence for lightning in the tropical wave using both in situ NO measurements and data from the World Wide Lightning Location Network (WWLLN).

Mechanisms of tropospheric ozone (O3) formation are generally well understood. However, studies reporting on net ozone production rates (NOPRs) directly derived from in situ observations are challenging and are sparse in number. To analyze the role of nitric oxide (NO) in net ozone production in the upper tropical troposphere above the Atlantic Ocean and western Africa, we present in situ trace gas observations obtained during the CAFE-Africa (Chemistry of the Atmosphere: Field Experiment in Africa) campaign in August and September 2018. The vertical profile of in situ measured NO along the flight tracks reveals lowest NO mixing ratios of less than 20 pptv between 2 and 8 km altitude and highest mixing ratios of 0.15–0.2 ppbv above 12 km altitude. Spatial distribution of tropospheric NO above 12 km altitude shows that the sporadically enhanced local mixing ratios (>0.4 ppbv) occur over western Africa, which we attribute to episodic lightning events. Measured O3 shows little variability in mixing ratios at 60–70 ppbv, with slightly decreasing and increasing tendencies towards the boundary layer and stratosphere, respectively. Concurrent measurements of CO, CH4, OH, HO2 and H2O enable calculations of NOPRs along the flight tracks and reveal net ozone destruction at −0.6 to −0.2 ppbv h−1 below 6 km altitude and balance of production and destruction around 7–8 km altitude. We report vertical average NOPRs of 0.2–0.4 ppbv h−1 above 12 km altitude with NOPRs occasionally larger than 0.5 ppbv h−1 over western Africa coincident with enhanced NO. We compare the observational results to simulated data retrieved from the general circulation model ECHAM/MESSy Atmospheric Chemistry (EMAC). Although the comparison of mean vertical profiles of NO and O3 indicates good agreement, local deviations between measured and modeled NO are substantial. The vertical tendencies in NOPRs calculated from simulated data largely reproduce those from in situ experimental data. However, the simulation results do not agree well with NOPRs over western Africa. Both measurements and simulations indicate that ozone formation in the upper tropical troposphere is NOx limited.

During the OMO (Oxidation Mechanism Observation) mission, trace gas measurements were performed on board the HALO (High Altitude Long Range) research aircraft in summer 2015 in order to investigate the outflow of the South Asian summer monsoon and its influence on the composition of the Asian monsoon anticyclone (AMA) in the upper troposphere over the eastern Mediterranean and the Arabian Peninsula. This study focuses on in situ observations of hydrogen peroxide (H2O2obs) and organic hydroperoxides (ROOHobs) as well as their precursors and loss processes. Observations are compared to photostationary-state (PSS) calculations of H2O2PSS and extended by a separation of ROOHobs into methyl hydroperoxide (MHPPSS) and inferred unidentified hydroperoxide (UHPPSS) mixing ratios using PSS calculations. Measurements are also contrasted to simulations with the general circulation ECHAM–MESSy for Atmospheric Chemistry (EMAC) model. We observed enhanced mixing ratios of H2O2obs (45 %), MHPPSS (9 %), and UHPPSS (136 %) in the AMA relative to the northern hemispheric background. Highest concentrations for H2O2obs and MHPPSS of 211 and 152 ppbv, respectively, were found in the tropics outside the AMA, while for UHPPSS, with 208 pptv, highest concentrations were found within the AMA. In general, the observed concentrations are higher than steady-state calculations and EMAC simulations by a factor of 3 and 2, respectively. Especially in the AMA, EMAC underestimates the H2O2EMAC (medians: 71 pptv vs. 164 pptv) and ROOHEMAC (medians: 25 pptv vs. 278 pptv) mixing ratios. Longitudinal gradients indicate a pool of hydroperoxides towards the center of the AMA, most likely associated with upwind convection over India. This indicates main contributions of atmospheric transport to the local budgets of hydroperoxides along the flight track, explaining strong deviations from steady-state calculations which only account for local photochemistry. Underestimation of H2O2EMAC by approximately a factor of 2 in the Northern Hemisphere (NH) and the AMA and overestimation in the Southern Hemisphere (SH; factor 1.3) are most likely due to uncertainties in the scavenging efficiencies for individual hydroperoxides in deep convective transport to the upper troposphere, corroborated by a sensitivity study. It seems that the observed excess UHPPSS is excess MHP transported to the west from an upper tropospheric source related to convection in the summer monsoon over Southeast Asia.

Strongly enhanced tropospheric ozone (O3) mixing ratios have been reported in the Arabian Basin, a region with intense solar radiation and high concentrations of O3 precursors such as nitrogen oxides (NOx) and volatile organic compounds (VOCs). To analyze photochemical O3 production in the marine boundary layer (MBL) around the Arabian Peninsula, we use shipborne observations of NO, NO2, O3, OH, HO2, HCHO, the actinic flux, water vapor, pressure and temperature obtained during the summer 2017 Air Quality and Climate in the Arabian Basin (AQABA) campaign, and we compare them to simulation results from the ECHAM-MESSy Atmospheric Chemistry (EMAC) general circulation model. Net O3 production rates (NOPRs) were greatest over both the Gulf of Oman and the northern Red Sea (16 ppbv d−1) and over the Arabian Gulf (32 ppbv d−1). The NOPR over the Mediterranean, the southern Red Sea and the Arabian Sea did not significantly deviate from zero; however, the results for the Arabian Sea indicated weak net O3 production of 5 ppbv d−1 as well as net O3 destruction over the Mediterranean and the southern Red Sea with values of −1 and −4 ppbv d−1, respectively. Constrained by HCHO∕NO2 ratios, our photochemistry calculations show that net O3 production in the MBL around the Arabian Peninsula mostly occurs in NOx-limited regimes with a significant share of O3 production occurring in the transition regime between NOx limitation and VOC limitation over the Mediterranean and more significantly over the northern Red Sea and Oman Gulf.

Laser-induced fluorescence (LIF) is a widely used technique for both laboratory-based and ambient atmospheric chemistry measurements. However, LIF instruments require calibrations in order to translate instrument response into concentrations of chemical species. Calibration of LIF instruments measuring OH and HO2 (HOx) typically involves the photolysis of water vapor by 184.9 nm light, thereby producing quantitative amounts of OH and HO2. For ground-based HOx instruments, this method of calibration is done at one pressure (typically ambient pressure) at the instrument inlet. However, airborne HOx instruments can experience varying cell pressures, internal residence times, temperatures, and humidity during flight. Therefore, replication of such variances when calibrating in the lab is essential to acquire the appropriate sensitivities. This requirement resulted in the development of the APACHE (All Pressure Altitude-based Calibrator for HOx Experimentation) chamber to characterize the sensitivity of the airborne LIF-FAGE (fluorescence assay by gas expansion) HOx instrument, HORUS, which took part in an intensive airborne campaign, OMO-Asia 2015. It utilizes photolysis of water vapor but has the additional ability to alter the pressure at the nozzle of the HORUS instrument. With APACHE, the HORUS instrument sensitivity towards OH (26.1–7.8 cts s−1 pptv−1 mW−1, ±22.6 % 1σ; cts stands for counts by the detector) and HO2 (21.2–8.1 cts s−1 pptv−1 mW−1, ±22.1 % 1σ) was characterized to the external pressure range at the instrument nozzle of 227–900 mbar. Measurements supported by a computational fluid dynamics model, COMSOL Multiphysics, revealed that, for all pressures explored in this study, APACHE is capable of initializing a homogenous flow and maintaining near-uniform flow speeds across the internal cross section of the chamber. This reduces the uncertainty regarding average exposure times across the mercury (Hg) UV ring lamp. Two different actinometrical approaches characterized the APACHE UV ring lamp flux as 6.37×1014(±1.3×1014) photons cm−2 s−1. One approach used the HORUS instrument as a transfer standard in conjunction with a calibrated on-ground calibration system traceable to NIST standards, which characterized the UV ring lamp flux to be 6.9(±1.1)×1014 photons cm−2 s−1. The second approach involved measuring ozone production by the UV ring lamp using an ANSYCO O3 41 M ozone monitor, which characterized the UV ring lamp flux to be 6.11(±0.8)×1014 photons cm−2 s−1. Data presented in this study are the first direct calibrations of an airborne HOx instrument, performed in a controlled environment in the lab using APACHE.

A total of 252 emission plumes of ships operating in the Mediterranean Sea and around the Arabian Peninsula were investigated using a comprehensive dataset of gas- and submicron-particle-phase properties measured during the 2-month shipborne AQABA (Air Quality and Climate Change in the Arabian Basin) field campaign in summer 2017. The post-measurement identification of the corresponding ship emission events in the measured data included the determination of the plume sources (up to 38 km away) as well as the plume ages (up to 115 min) and was based on commercially available historical records of the Automatic Identification System. The dispersion lifetime of chemically inert CO2 in the ship emission plumes was determined as 70±15 min, resulting in levels indistinguishable from the marine background after 260±60 min. Emission factors (EFs) as quantities that are independent of plume dilution were calculated and used for the investigation of influences on ship emission plumes caused by ship characteristics and the combustion process as well as by atmospheric processes during the early stage of exhaust release and during plume ageing. Combustion efficiency and therefore emission factors of black carbon and NOx were identified to depend mostly on the vessel speed and gross tonnage. Moreover, larger ships, associated with higher engine power, were found to use fuel with higher sulfur content and have higher gas-phase SO2, particulate sulfate, particulate organics, and particulate matter EFs. Despite the independence of EFs of dilution, a significant influence of the ambient wind speed on the particle number and mass EFs was observed that can be traced back to enhanced particle coagulation in the case of slower dilution and suppressed vapour condensation on particles in the case of faster dilution of the emission plume. Atmospheric reactions and processes in ship emission plumes were investigated that include NOx and O3 chemistry, gas-to-particle conversion of NOx and SO2, and the neutralisation of acids in the particle phase through the uptake of ambient gas-phase ammonia, the latter two of which cause the inorganic particulate content to increase and the organic fraction to decrease with increasing plume age. The results allow for us to describe the influences on (or processes in) ship emission plumes quantitatively by parameterisations, which could be used for further refinement of atmospheric models, and to identify which of these processes are the most important ones.

Shipborne measurements of nitryl chloride (ClNO2), hydrogen chloride (HCl) and sulfur dioxide (SO2) were made during the AQABA (Air Quality and climate change in the Arabian BAsin) ship campaign in summer 2017. The dataset includes measurements over the Mediterranean Sea, the Suez Canal, the Red Sea, the Gulf of Aden, the Arabian Sea, the Gulf of Oman, and the Arabian Gulf (also known as Persian Gulf) with observed ClNO2 mixing ratios ranging from the limit of detection to ≈600 pptv. We examined the regional variability in the generation of ClNO2 via the uptake of dinitrogen pentoxide (N2O5) to Cl-containing aerosol and its importance for Cl atom generation in a marine boundary layer under the (variable) influence of emissions from shipping and the oil industry. The yield of ClNO2 formation per NO3 radical generated was generally low (median of ≈1 %–5 % depending on the region), mainly as a result of gas-phase loss of NO3 dominating over heterogeneous loss of N2O5, the latter being disfavoured by the high temperatures found throughout the campaign. The contributions of ClNO2 photolysis and OH-induced HCl oxidation to Cl-radical formation were derived and their relative contributions over the diel cycle compared. The results indicate that over the northern Red Sea, the Gulf of Suez, and the Gulf of Oman the formation of Cl atoms will enhance the oxidation rates of some volatile organic compounds (VOCs), especially in the early morning.

Hydrogen peroxide (H2O2) plays a significant role in the oxidizing capacity of the atmosphere. It is an efficient oxidant in the liquid phase and serves as a temporary reservoir for the hydroxyl radical (OH), the most important oxidizing agent in the gas phase. Due to its high solubility, removal of H2O2 due to wet and dry deposition is efficient, being a sink of HOx (OH+HO2) radicals. In the continental boundary layer, the H2O2 budget is controlled by photochemistry, transport and deposition processes. Here we use in situ observations of H2O2 and account for chemical source and removal mechanisms to study the interplay between these processes. The data were obtained during five ground-based field campaigns across Europe from 2008 to 2014 and bring together observations in a boreal forest, two mountainous sites in Germany, and coastal sites in Spain and Cyprus. Most campaigns took place in the summer, while the measurements in the south-west of Spain took place in early winter. Diel variations in H2O2 are strongly site-dependent and indicate a significant altitude dependence. While boundary-layer mixing ratios of H2O2 at low-level sites show classical diel cycles with the lowest values in the early morning and maxima around local noon, diel profiles are reversed on mountainous sites due to transport from the nocturnal residual layer and the free troposphere. The concentration of hydrogen peroxide is largely governed by its main precursor, the hydroperoxy radical (HO2), and shows significant anti-correlation with nitrogen oxides (NOx) that remove HO2. A budget calculation indicates that in all campaigns, the noontime photochemical production rate through the self-reaction of HO2 radicals was much larger than photochemical loss due to reaction with OH and photolysis, and that dry deposition is the dominant loss mechanism. Estimated dry deposition velocities varied between approximately 1 and 6 cm s−1, with relatively high values observed during the day in forested regions, indicating enhanced uptake of H2O2 by vegetation. In order to reproduce the change in H2O2 mixing ratios between sunrise and midday, a variable contribution from transport (10 %–100 %) is required to balance net photochemical production and deposition loss. Transport is most likely related to entrainment from the residual layer above the nocturnal boundary layer during the growth of the boundary layer in the morning.

We present version 4.0 of the atmospheric chemistry box model CAABA/MECCA that now includes a number of new features: (i) skeletal mechanism reduction, (ii) the Mainz Organic Mechanism (MOM) chemical mechanism for volatile organic compounds, (iii) an option to include reactions from the Master Chemical Mechanism (MCM) and other chemical mechanisms, (iv) updated isotope tagging, and (v) improved and new photolysis modules (JVAL, RADJIMT, DISSOC). Further, when MECCA is connected to a global model, the new feature of coexisting multiple chemistry mechanisms (PolyMECCA/CHEMGLUE) can be used. Additional changes have been implemented to make the code more user-friendly and to facilitate the analysis of the model results. Like earlier versions, CAABA/MECCA-4.0 is a community model published under the GNU General Public License.

GANDALF (Gas Analyzer for Nitrogen Dioxide Applying Laser-induced Fluorescence), a new instrument for the detection of nitrogen dioxide based on the laser-induced fluorescence (LIF) technique, is presented in this paper. GANDALF is designed for ground-based and airborne deployment with a robust calibration system. In the current set-up, it uses a multi-mode diode laser (447–450 nm) and performs in situ, continuous, and autonomous measurements with a laser pulse repetition rate of 5 MHz. The performance of GANDALF was tested during the summer of year 2011 (15 August–10 September) in a field experiment at Kleiner Feldberg, Germany. The location is within a forested region with an urban influence, where NOx levels were between 0.12 and 22 parts per billion by volume (ppb). Based on the field results, the limit of detection is estimated at 5–10 parts per trillion by volume (ppt) in 60 s at a signal-to-noise ratio (SNR) of 2. The overall accuracy and precision of the instrument are better than 5 % (1σ) and 0.5 %+3 ppt (1σ min−1), respectively. A comparison of nitrogen dioxide measurements based on several techniques during the field campaign PARADE 2011 is presented to explore methodic differences.

Unlike many oxidised atmospheric trace gases, which have numerous production pathways, peroxyacetic acid (PAA) and PAN are formed almost exclusively in gas-phase reactions involving the hydroperoxy radical (HO2), the acetyl peroxy radical (CH3C(O)O2) and NO2 and are not believed to be directly emitted in significant amounts by vegetation. As the self-reaction of HO2 is the main photochemical route to hydrogen peroxide (H2O2), simultaneous observation of PAA, PAN and H2O2 can provide insight into the HO2 budget. We present an analysis of observations taken during a summertime campaign in a boreal forest that, in addition to natural conditions, was temporarily impacted by two biomass-burning plumes. The observations were analysed using an expression based on a steady-state assumption using relative PAA-to-PAN mixing ratios to derive HO2 concentrations. The steady-state approach generated HO2 concentrations that were generally in reasonable agreement with measurements but sometimes overestimated those observed by factors of 2 or more. We also used a chemically simple, constrained box model to analyse the formation and reaction of radicals that define the observed mixing ratios of PAA and H2O2. After nudging the simulation towards observations by adding extra, photochemical sources of HO2 and CH3C(O)O2, the box model replicated the observations of PAA, H2O2, ROOH and OH throughout the campaign, including the biomass-burning-influenced episodes during which significantly higher levels of many oxidized trace gases were observed. A dominant fraction of CH3O2 radical generation was found to arise via reactions of the CH3C(O)O2 radical. The model indicates that organic peroxy radicals were present at night in high concentrations that sometimes exceeded those predicted for daytime, and initially divergent measured and modelled HO2 concentrations and daily concentration profiles are reconciled when organic peroxy radicals are detected (as HO2) at an efficiency of 35 %. Organic peroxy radicals are found to play an important role in the recycling of OH radicals subsequent to their loss via reactions with volatile organic compounds.

The Mediterranean is a climatically sensitive region located at the crossroads of air masses from three continents: Europe, Africa, and Asia. The chemical processing of air masses over this region has implications not only for the air quality but also for the long-range transport of air pollution. To obtain a comprehensive understanding of oxidation processes over the Mediterranean, atmospheric concentrations of the hydroxyl radical (OH) and the hydroperoxyl radical (HO2) were measured during an intensive field campaign (CYprus PHotochemistry EXperiment, CYPHEX-2014) in the northwest of Cyprus in the summer of 2014. Very low local anthropogenic and biogenic emissions around the measurement location provided a vantage point to study the contrasts in atmospheric oxidation pathways under highly processed marine air masses and those influenced by relatively fresh emissions from mainland Europe.The CYPHEX measurements were used to evaluate OH and HO2 simulations using a photochemical box model (CAABA/MECCA) constrained with CYPHEX observations of O3, CO, NOx, hydrocarbons, peroxides, and other major HOx (OH + HO2) sources and sinks in a low-NOx environment (2 agreed to within 17 % of the in situ observations. However, the model strongly under-predicted HO2 at high terpene concentrations, this under-prediction reaching up to 38 % at the highest terpene levels. Different schemes to improve the agreement between observed and modelled HO2, including changing the rate coefficients for the reactions of terpene-generated peroxy radicals (RO2) with NO and HO2 as well as the autoxidation of terpene-generated RO2 species, are explored in this work. The main source of OH in Cyprus was its primary production from O3 photolysis during the day and HONO photolysis during early morning. Recycling contributed about one-third of the total OH production, and the maximum recycling efficiency was about 0.7. CO, which was the largest OH sink, was also the largest HO2 source. The lowest HOx production and losses occurred when the air masses had higher residence time over the oceans.

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 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 (−1) and low NO (

Deep convection is an efficient mechanism for vertical trace gas transport from Earth's surface to the upper troposphere (UT). The convective redistribution of short-lived trace gases emitted at the surface typically results in a C-shaped profile. This redistribution mechanism can impact photochemical processes, e.g. ozone and radical production in the UT on a large scale due to the generally longer lifetimes of species like formaldehyde (HCHO) and hydrogen peroxide (H2O2), which are important HOx precursors (HOx = OH + HO2 radicals). Due to the solubility of HCHO and H2O2 their transport may be suppressed as they are efficiently removed by wet deposition. Here we present a case study of deep convection over Germany in the summer of 2007 within the framework of the HOOVER II project. Airborne in situ measurements within the in- and outflow regions of an isolated thunderstorm provide a unique data set to study the influence of deep convection on the transport efficiency of soluble and insoluble trace gases. Comparing the in- and outflow indicates an almost undiluted transport of insoluble trace gases from the boundary layer to the UT. The ratios of out : inflow of CO and CH4 are 0.94 ± 0.04 and 0.99 ± 0.01, respectively. For the soluble species HCHO and H2O2 these ratios are 0.55 ± 0.09 and 0.61 ± 0.08, respectively, indicating partial scavenging and washout. Chemical box model simulations show that post-convection secondary formation of HCHO and H2O2 cannot explain their enhancement in the UT. A plausible explanation, in particular for the enhancement of the highly soluble H2O2, is degassing from cloud droplets during freezing, which reduces the retention coefficient.

Ozone (O3) is an important atmospheric oxidant, a greenhouse gas, and a hazard to human health and agriculture. Here we describe airborne in situ measurements and model simulations of O3 and its precursors during tropical and extratropical field campaigns over South America and Europe, respectively. Using the measurements, net ozone formation/destruction tendencies are calculated and compared to 3-D chemistry–transport model simulations. In general, observation-based net ozone tendencies are positive in the continental boundary layer and the upper troposphere at altitudes above ∼ 6 km in both environments. On the other hand, in the marine boundary layer and the middle troposphere, from the top of the boundary layer to about 6–8 km altitude, net O3 destruction prevails. The ozone tendencies are controlled by ambient concentrations of nitrogen oxides (NOx). In regions with net ozone destruction the available NOx is below the threshold value at which production and destruction of O3 balance. While threshold NO values increase with altitude, in the upper troposphere NOx concentrations are generally higher due to the integral effect of convective precursor transport from the boundary layer, downward transport from the stratosphere and NOx produced by lightning. Two case studies indicate that in fresh convective outflow of electrified thunderstorms net ozone production is enhanced by a factor 5–6 compared to the undisturbed upper tropospheric background. The chemistry–transport model MATCH-MPIC generally reproduces the pattern of observation-based net ozone tendencies but mostly underestimates the magnitude of the net tendency (for both net ozone production and destruction).

Lagrangian particle dispersion models (LPDMs) in backward mode are widely used to quantify the impact of transboundary pollution on downwind sites. Most LPDM applications count particles with a technique that introduces a so-called footprint layer (FL) with constant height, in which passing air tracer particles are assumed to be affected by surface emissions. The mixing layer dynamics are represented by the underlying meteorological model. This particle counting technique implicitly assumes that the atmosphere is well mixed in the FL. We have performed backward trajectory simulations with the FLEXPART model starting at Cyprus to calculate the sensitivity to emissions of upwind pollution sources. The emission sensitivity is used to quantify source contributions at the receptor and support the interpretation of ground measurements carried out during the CYPHEX campaign in July 2014. Here we analyse the effects of different constant and dynamic FL height assumptions. The results show that calculations with FL heights of 100 and 300 m yield similar but still discernible results. Comparison of calculations with FL heights constant at 300 m and dynamically following the planetary boundary layer (PBL) height exhibits systematic differences, with daytime and night-time sensitivity differences compensating for each other. The differences at daytime when a well-mixed PBL can be assumed indicate that residual inaccuracies in the representation of the mixing layer dynamics in the trajectories may introduce errors in the impact assessment on downwind sites. Emissions from vegetation fires are mixed up by pyrogenic convection which is not represented in FLEXPART. Neglecting this convection may lead to severe over- or underestimations of the downwind smoke concentrations. Introducing an extreme fire source from a different year in our study period and using fire-observation-based plume heights as reference, we find an overestimation of more than 60  % by the constant FL height assumptions used for surface emissions. Assuming a FL that follows the PBL may reproduce the peak of the smoke plume passing through but erroneously elevates the background for shallow stable PBL heights. It might thus be a reasonable assumption for open biomass burning emissions wherever observation-based injection heights are not available.

During the summertime CYPHEX campaign (CYprus PHotochemical EXperiment 2014) in the eastern Mediterranean, multiple volatile organic compounds (VOCs) were measured from a 650 m hilltop site in western Cyprus (34° 57′ N/32° 23′ E). Periodic shifts in the northerly Etesian winds resulted in the site being alternately impacted by photochemically processed emissions from western (Spain, France, Italy) and eastern (Turkey, Greece) Europe. Furthermore, the site was situated within the residual layer/free troposphere during some nights which were characterized by high ozone and low relative humidity levels. In this study we examine the temporal variation of VOCs at the site. The sparse Mediterranean scrub vegetation generated diel cycles in the reactive biogenic hydrocarbon isoprene, from very low values at night to a diurnal median level of 80–100 pptv. In contrast, the oxygenated volatile organic compounds (OVOCs) methanol and acetone exhibited weak diel cycles and were approximately an order of magnitude higher in mixing ratio (ca. 2.5–3 ppbv median level by day, range: ca. 1–8 ppbv) than the locally emitted isoprene and aromatic compounds such as benzene and toluene. Acetic acid was present at mixing ratios between 0.05 and 4 ppbv with a median level of ca. 1.2 ppbv during the daytime. When data points directly affected by the residual layer/free troposphere were excluded, the acid followed a pronounced diel cycle, which was influenced by various local effects including photochemical production and loss, direct emission, dry deposition and scavenging from advecting air in fog banks. The Lagrangian model FLEXPART was used to determine transport patterns and photochemical processing times (between 12 h and several days) of air masses originating from eastern and western Europe. Ozone and many OVOC levels were ∼ 20 and ∼ 30–60 % higher, respectively, in air arriving from the east. Using the FLEXPART calculated transport time, the contribution of photochemical processing, sea surface contact and dilution was estimated. Methanol and acetone decreased with residence time in the marine boundary layer (MBL) with loss rate constants of 0.74 and 0.53 day−1 from eastern Europe and 0.70 and 0.34 day−1 from western Europe, respectively. Simulations using the EMAC model underestimate these loss rates. The missing sink in the calculation is most probably an oceanic uptake enhanced by microbial consumption of methanol and acetone, although the temporal and spatial variability in the source strength on the continents might play a role as well. Correlations between acetone and methanol were weaker in western air masses (r2 = 0.68), but were stronger in air masses measured after the shorter transport time from the east (r2 = 0.73).

We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of sulfur dioxide. SCIs also add to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of ∼ 5.0 × 104 molecules cm−3 (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCIs, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere.

Characterization of daytime sources of nitrous acid (HONO) is crucial to understand atmospheric oxidation and radical cycling in the planetary boundary layer. HONO and numerous other atmospheric trace constituents were measured on the Mediterranean island of Cyprus during the CYPHEX (CYprus PHotochemical EXperiment) campaign in summer 2014. Average volume mixing ratios of HONO were 35 pptv (±25 pptv) with a HONO ∕ NOx ratio of 0.33, which was considerably higher than reported for most other rural and urban regions. Diel profiles of HONO showed peak values in the late morning (60 ± 28 pptv around 09:00 local time) and persistently high mixing ratios during daytime (45 ± 18 pptv), indicating that the photolytic loss of HONO is compensated by a strong daytime source. Budget analyses revealed unidentified sources producing up to 3.4 × 106 molecules cm−3 s−1 of HONO and up to 2.0 × 107 molecules cm−3 s−1 NO. Under humid conditions (relative humidity > 70 %), the source strengths of HONO and NO exhibited a close linear correlation (R2 = 0.72), suggesting a common source that may be attributable to emissions from microbial communities on soil surfaces.

Atmospheric concentrations of nitrous acid (HONO), one of the major precursors of the hydroxyl radical (OH) in the troposphere, significantly exceed the values predicted by the assumption of a photostationary state (PSS) during daytime. Therefore, additional sources of HONO were intensively investigated in the last decades. This study presents budget calculations of HONO based on simultaneous measurements of all relevant species, including HONO and OH at two different measurement heights, i.e. 1 m above the ground and about 2 to 3 m above the canopy (24 m above the ground), conducted in a boreal forest environment. We observed mean HONO concentrations of about 6.5 × 108 molecules cm−3 (26 ppt) during daytime, more than 20 times higher than expected from the PSS of 0.2 × 108 molecules cm−3 (1 ppt). To close the budgets at both heights, a strong additional source term during daytime is required. This unidentified source is at its maximum at noon (up to 1.1 × 106 molecules cm−3 s−1, 160 ppt h−1) and in general up to 2.3 times stronger above the canopy than close to the ground. The insignificance of known gas phase reactions and other processes like dry deposition or advection compared to the photolytic decomposition of HONO at this measurement site was an ideal prerequisite to study possible correlations of this unknown term to proposed HONO sources. But neither the proposed emissions from soils nor the proposed photolysis of adsorbed HNO3 contributed substantially to the unknown source. However, the unknown source was found to be perfectly correlated to the unbalanced photolytic loss of HONO.

Atmospheric measurements of hydroxyl radicals (OH) are challenging due to a high reactivity and consequently low concentration. The importance of OH as an atmospheric oxidant has motivated a sustained effort leading to the development of a number of highly sensitive analytical techniques. Recent work has indicated that the laser-induced fluorescence of the OH molecules method based on the fluorescence assay by gas expansion technique (LIF-FAGE) for the measurement of atmospheric OH in some environments may be influenced by artificial OH generated within the instrument, and a chemical method to remove this interference was implemented in a LIF-FAGE system by Mao et al. (2012). While it is not clear whether other LIF-FAGE instruments suffer from the same interference, we have applied this method to our LIF-FAGE HORUS (Hydroxyl Radical Measurement Unit based on fluorescence Spectroscopy) system, and developed and deployed an inlet pre-injector (IPI) to determine the chemical zero level in the instrument via scavenging the ambient OH radical. We describe and characterise this technique in addition to its application at field sites in forested locations in Finland, Spain and Germany. Ambient measurements show that OH generated within the HORUS instrument is a non-negligible fraction of the total OH signal, which can comprise 30 to 80% during daytime and 60 to 100% during the night. The contribution of the background OH varied greatly between measurement sites and was likely related to the type and concentration of volatile organic compounds (VOCs) present at each particular location. Two inter-comparisons in contrasting environments between the HORUS instrument and two different chemical ionisation mass spectrometers (CIMS) are described to demonstrate the efficacy of IPI and the necessity of the chemical zeroing method for our LIF-FAGE instrument in such environments.

Convective redistribution of ozone and its precursors between the boundary layer (BL) and the free troposphere (FT) influences photochemistry, in particular in the middle and upper troposphere (UT). We present a case study of convective transport during the GABRIEL campaign over the tropical rain forest in Suriname in October 2005. During one measurement flight the inflow and outflow regions of a cumulonimbus cloud (Cb) have been characterized. We identified a distinct layer between 9 and 11 km altitude with enhanced mixing ratios of CO, O3, HOx, acetone and acetonitrile. The elevated O3 contradicts the expectation that convective transport brings low-ozone air from the boundary layer to the outflow region. Entrainment of ozone-rich air is estimated to account for 62% (range: 33–91%) of the observed O3. Ozone is enhanced by only 5–6% by photochemical production in the outflow due to enhanced NO from lightning, based on model calculations using observations including the first reported HOx measurements over the tropical rainforest. The "excess" ozone in the outflow is most probably due to direct production by corona discharge associated with lightning. We deduce a production rate of 5.12 × 1028 molecules O3 flash−1 (range: 9.89 × 1026–9.82 × 1028 molecules O3 flash−1), which is at the upper limit of the range reported previously.

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

The DOMINO (Diel Oxidant Mechanisms in relation to Nitrogen Oxides) campaign was carried out from 21 November to 8 December 2008 at the El Arenosillo station (SW of Spain) in a coastal-rural environment. The main weather conditions are analysed using local meteorological variables, meteorological soundings and synoptic maps, as well as back trajectories of the air masses using the HYSPLIT (Hybrid Single-Particle Lagrangian Integrated Trajectory Model) model and a high spatial resolution of meteorological fields. Measurements of the main meteorological parameters were collected both from the surface and from a tall tower. A detailed land use analysis was performed on a 80 km scale showing the main types of vegetation and land use. Also the main anthropogenic atmospheric emission sources – both industrial-urban from Huelva and from the urban Seville area – are shown. A study to identify air mass origins and their variation with height was carried out. In this intensive campaign, air masses coming from different areas with different emission sources were observed: from the NW, with a highly industrial-urban character; continental flows from northerly directions; from the NE, with a pathway starting over the Seville metropolitan area and then continuing over the Doñana National Park; and maritime air masses coming from the Atlantic Ocean. To study the chemistry in the four atmospheric scenarios identified, gas -phase measurements of primary and secondary species such as ozone, NO, NO2 and SO2, biogenic and anthropogenic VOCs (volatile organic compounds) like benzene and isoprene, as well as total particle concentration and chemical composition of the aerosols are compared and discussed. The highest levels for total particle concentration, NO, NO2, SO2, benzene, PM10, PM2.5 and chemical elements such as As or Cu were found under flows associated with industrial-urban emissions from the Huelva–Portugal sector which are transported to the site before significant removal by chemical or deposition mechanism can occur. The air masses from the north were affected mainly by crustal elements and biogenic sources, the latter being exemplified by the biogenic species such as isoprene, particularly in the first part of the campaign. The urban air from the Seville area, before arriving at El Arenosillo, traversed the Doñana National Park and therefore was affected by industrial-urban and biogenic emissions. This aged air parcel can transport low levels of NOx, total particle concentration and SO2 as well as ozone and isoprene. Marine air masses from the Atlantic Ocean influence El Arenosillo frequently. Under these conditions, the lowest levels of almost all the species – with the exception of ozone levels associated to long-range transport – were measured.

In situ airborne measurements of OH and HO2 with the HORUS (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy) instrument were performed in the summertime upper troposphere across Europe during the HOOVER 2 (HOx OVer EuRope) campaign in July 2007. Complementary measurements of trace gas species and photolysis frequencies were conducted to obtain a broad data set, which has been used to quantify the significant HOx sources and sinks. In this study we compare the in situ measurement of OH and HO2 with simulated mixing ratios from the constrained box model CAABA/MECCA (Chemistry As A Box Model Application/Module Efficiently Calculating the Chemistry of the Atmosphere), and the global circulation model EMAC (ECHAM5/MESSy Atmospheric Chemistry Model). The constrained box model reproduces the observed OH and HO2 mixing ratios with better agreement (obs/mod median 98% OH, 96% HO2) than the global model (median 76% OH, 59% HO2). The observations and the computed HOx sources and sinks are used to identify deviations between the models and their impacts on the calculated HOx budget.

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

In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station – El Arenosillo (37.1° N–6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s−1; range of average diel values: 21.3–40.5 s−1), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s−1; range of average diel values: 7–23.4 s−1) and marine air masses (average: 6.3 ± 6.6 s−1; range of average diel values: below detection limit −21.7 s−1), respectively. The average OH reactivity for the entire campaign period was ~18 s−1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NOx with peak values of around 20 ppbV O3 h−1. Using the OH reactivity based approach, derived ozone production rates indicate that if NOx would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.

We study the interactions between atmospheric boundary layer (ABL) dynamics and atmospheric chemistry using a mixed-layer model coupled to chemical reaction schemes. Guided by both atmospheric and chemical measurements obtained during the DOMINO (Diel Oxidant Mechanisms in relation to Nitrogen Oxides) campaign (2008), numerical experiments are performed to study the role of ABL dynamics and the accuracy of chemical schemes with different complexity: the Model for Ozone and Related chemical Tracers, version 4 (MOZART-4) and a reduced mechanism of this chemical system. Both schemes produce satisfactory results, indicating that the reduced scheme is capable of reproducing the O3-NOx-VOC-HOx diurnal cycle during conditions characterized by a low NOx regime and small O3 tendencies (less than 1 ppb per hour). By focusing on the budget equations of chemical species in the mixed-layer model, we show that for species like O3, NO and NO2, the influence of entrainment and boundary layer growth is of the same order as chemical production/loss. This indicates that an accurate representation of ABL processes is crucial in understanding the diel cycle of chemical species. By comparing the time scales of chemical reactive species with the mixing time scale of turbulence, we propose a classification based on the Damköhler number to further determine the importance of dynamics on chemistry during field campaigns. Our findings advocate an integrated approach, simultaneously solving the ABL dynamics and chemical reactions, in order to obtain a better understanding of chemical pathways and processes and the interpretation of the results obtained during measurement campaigns.

A photochemical box model constrained by ancillary observations was used to simulate OH and HO2 concentrations for three days of ambient observations during the HOxComp field campaign held in Jülich, Germany in July 2005. Daytime OH levels observed by four instruments were fairly well reproduced to within 33% by a base model run (Regional Atmospheric Chemistry Mechanism with updated isoprene chemistry adapted from Master Chemical Mechanism ver. 3.1) with high R2 values (0.72–0.97) over a range of isoprene (0.3–2 ppb) and NO (0.1–10 ppb) mixing ratios. Daytime HO2(*) levels, reconstructed from the base model results taking into account the sensitivity toward speciated RO2 (organic peroxy) radicals, as recently reported from one of the participating instruments in the HO2 measurement mode, were 93% higher than the observations made by the single instrument. This also indicates an overprediction of the HO2 to OH recycling. Together with the good model-measurement agreement for OH, it implies a missing OH source in the model. Modeled OH and HO2(*) could only be matched to the observations by addition of a strong unknown loss process for HO2(*) that recycles OH at a high yield. Adding to the base model, instead, the recently proposed isomerization mechanism of isoprene peroxy radicals (Peeters and Müller, 2010) increased OH and HO2(*) by 28% and 13% on average. Although these were still only 4% higher than the OH observations made by one of the instruments, larger overestimations (42–70%) occurred with respect to the OH observations made by the other three instruments. The overestimation in OH could be diminished only when reactive alkanes (HC8) were solely introduced to the model to explain the missing fraction of observed OH reactivity. Moreover, the overprediction of HO2(*) became even larger than in the base case. These analyses imply that the rates of the isomerization are not readily supported by the ensemble of radical observations. One of the measurement days was characterized by low isoprene concentrations (∼0.5 ppb) and OH reactivity that was well explained by the observed species, especially before noon. For this selected period, as opposed to the general behavior, the model tended to underestimate HO2(*). We found that this tendency is associated with high NOx concentrations, suggesting that some HO2 production or regeneration processes under high NOx conditions were being overlooked; this might require revision of ozone production regimes.

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 SO2) 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.

During the DOMINO (Diel Oxidant Mechanism In relation to Nitrogen Oxides) campaign in southwest Spain we measured simultaneously all quantities necessary to calculate a photostationary state for HONO in the gas phase. These quantities comprise the concentrations of OH, NO, and HONO and the photolysis frequency of NO2, j(NO2) as a proxy for j(HONO). This allowed us to calculate values of the unknown HONO daytime source. This unknown HONO source, normalized by NO2 mixing ratios and expressed as a conversion frequency (% h−1), showed a clear dependence on j(NO2) with values up to 43% h−1 at noon. We compared our unknown HONO source with values calculated from the measured field data for two recently proposed processes, the light-induced NO2 conversion on soot surfaces and the reaction of electronically excited NO2* with water vapour, with the result that these two reactions normally contributed less than 10% (2 + soot + hν; and 2* + H2O) to our unknown HONO daytime source. OH production from HONO photolysis was found to be larger (by 20%) than the "classical" OH formation from ozone photolysis (O(1D)) integrated over the day.

In this study we report measurements of hydrogen peroxide (H2O2), methyl hydroperoxide* (MHP* as a proxy of MHP based on an unspecific measurement of total organic peroxides) and formaldehyde (HCHO) from the HOx OVer EuRope (HOOVER) project (HOx = OH+HO2). HOOVER included two airborne field campaigns, in October 2006 and July 2007. Measurement flights were conducted from the base of operation Hohn (Germany, 54° N, 9° E) towards the Mediterranean and to the subpolar regions over Norway. We find negative concentration gradients with increasing latitude throughout the troposphere for H2O2 and CH3OOH*. In contrast, observed HCHO is almost homogeneously distributed over central and northern Europe and is elevated over the Mediterranean. In general, the measured gradients tend to be steepest entering the Mediterranean region, where we also find the highest abundances of the 3 species. Mixing ratios of these tracers generally decrease with altitude. H2O2 and CH3OOH* show maxima above the boundary layer at 2–5 km, being more distinct over southern than over northern Europe. We also present a comparison of our data with simulations by two global 3-D-models, MATCH-MPIC and EMAC, and with the box model CAABA. The models realistically represent altitude and latitude gradients for both HCHO and hydroperoxides (ROOH). In contrast, the models have problems reproducing the absolute mixing ratios, in particular of H2O2. Large uncertainties about retention coefficients and cloud microphysical parameters suggest that cloud scavenging might be a large source of error for the simulation of H2O2. A sensitivity study with EMAC shows a strong influence of cloud and precipitation scavenging on the budget of H2O2 as simulations improve significantly with this effect switched off.

We present version 3.0 of the atmospheric chemistry box model CAABA/MECCA. In addition to a complete update of the rate coefficients to the most recent recommendations, a number of new features have been added: chemistry in multiple aerosol size bins; automatic multiple simulations reaching steady-state conditions; Monte-Carlo simulations with randomly varied rate coefficients within their experimental uncertainties; calculations along Lagrangian trajectories; mercury chemistry; more detailed isoprene chemistry; tagging of isotopically labeled species. Further changes have been implemented to make the code more user-friendly and to facilitate the analysis of the model results. Like earlier versions, CAABA/MECCA-3.0 is a community model published under the GNU General Public License.

Hydroperoxy radical (HO2) concentrations were measured during the formal blind intercomparison campaign HOxComp carried out in Jülich, Germany, in 2005. Three instruments detected HO2 via chemical conversion to hydroxyl radicals (OH) and subsequent detection of the sum of OH and HO2 by laser induced fluorescence (LIF). All instruments were based on the same detection and calibration scheme. Because measurements by a MIESR instrument failed during the campaign, no absolute reference measurement was available, so that the accuracy of individual instruments could not be addressed. Instruments sampled ambient air for three days and were attached to the atmosphere simulation chamber SAPHIR during the second part of the campaign. Six experiments of one day each were conducted in SAPHIR, where air masses are homogeneously mixed, in order to investigate the performance of instruments and to determine potential interferences of measurements under well-controlled conditions. Linear correlation coefficients (R2) between measurements of the LIF instruments are generally high and range from 0.82 to 0.98. However, the agreement between measurements is variable. The regression analysis of the entire data set of measurements in SAPHIR yields slopes between 0.69 to 1.26 and intercepts are smaller than typical atmospheric daytime concentrations (less than 1 pptv). The quality of fit parameters improves significantly, when data are grouped into data subsets of similar water vapor concentrations. Because measurements of LIF instruments were corrected for a well-characterized water dependence of their sensitivities, this indicates that an unknown factor related to water vapor affected measurements in SAPHIR. Measurements in ambient air are also well-correlated, but regression parameters differ from results obtained from SAPHIR experiments. This could have been caused by differences in HO2 concentrations in the sampled air at the slightly different locations of instruments.

As a major source region of the hydroxyl radical OH, the Tropics largely control the oxidation capacity of the atmosphere on a global scale. However, emissions of hydrocarbons from the tropical rainforest that react rapidly with OH can potentially deplete the amount of OH and thereby reduce the oxidation capacity. The airborne GABRIEL field campaign in equatorial South America (Suriname) in October 2005 investigated the influence of the tropical rainforest on the HOx budget (HOx = OH + HO2). The first observations of OH and HO2 over a tropical rainforest are compared to steady state concentrations calculated with the atmospheric chemistry box model MECCA. The important precursors and sinks for HOx chemistry, measured during the campaign, are used as constraining parameters for the simulation of OH and HO2. Significant underestimations of HOx are found by the model over land during the afternoon, with mean ratios of observation to model of 12.2 ± 3.5 and 4.1 ± 1.4 for OH and HO2, respectively. The discrepancy between measurements and simulation results is correlated to the abundance of isoprene. While for low isoprene mixing ratios (above ocean or at altitudes >3 km), observation and simulation agree fairly well, for mixing ratios >200 pptV (x observations as a function of isoprene. Box model simulations have been performed with the condensed chemical mechanism of MECCA and with the detailed isoprene reaction scheme of MCM, resulting in similar results for HOx concentrations. Simulations with constrained HO2 concentrations show that the conversion from HO2 to OH in the model is too low. However, by neglecting the isoprene chemistry in the model, observations and simulations agree much better. An OH source similar to the strength of the OH sink via isoprene chemistry is needed in the model to resolve the discrepancy. A possible explanation is that the oxidation of isoprene by OH not only dominates the removal of OH but also produces it in a similar amount. Several additional reactions which directly produce OH have been implemented into the box model, suggesting that upper limits in producing OH are still not able to reproduce the observations (improvement by factors of ≈2.4 and ≈2 for OH and HO2, respectively). We determine that OH has to be recycled to 94% instead of the simulated 38% to match the observations, which is most likely to happen in the isoprene degradation process, otherwise additional sources are required.

Direct measurements of OH and HO2 over a tropical rainforest were made for the first time during the GABRIEL campaign in October 2005, deploying the custom-built HORUS instrument (HydrOxyl Radical measurement Unit based on fluorescence Spectroscopy), adapted to fly in a Learjet wingpod. Biogenic hydrocarbon emissions were expected to strongly reduce the OH and HO2 mixing ratios as the air is transported from the ocean over the forest. However, surprisingly high mixing ratios of both OH and HO2 were encountered in the boundary layer over the rainforest. The HORUS instrumentation and calibration methods are described in detail and the measurement results obtained are discussed. The extensive dataset collected during GABRIEL, including measurements of many other trace gases and photolysis frequencies, has been used to quantify the main sources and sinks of OH. Comparison of these measurement-derived formation and loss rates of OH indicates strong previously overlooked recycling of OH in the boundary layer over the tropical rainforest, occurring in chorus with isoprene emission.

Hydroxyl radicals (OH) are the major oxidizing species in the troposphere. Because of their central importance, absolute measurements of their concentrations are needed to validate chemical mechanisms of atmospheric models. The extremely low and highly variable concentrations in the troposphere, however, make measurements of OH difficult. Three techniques are currently used worldwide for tropospheric observations of OH after about 30~years of technical developments: Differential Optical Laser Absorption Spectroscopy (DOAS), Laser-Induced Fluorescence Spectroscopy (LIF), and Chemical Ionisation Mass Spectrometry (CIMS). Even though many measurement campaigns with OH data were published, the question of accuracy and precision is still under discussion. Here, we report results of the first formal, blind intercomparison of these techniques. Six OH instruments (4~LIF, 1~CIMS, 1~DOAS) participated successfully in the ground-based, international HOxComp campaign carried out in Jülich, Germany, in summer 2005. Comparisons were performed for three days in ambient air (3~LIF, 1 CIMS) and for six days in the atmosphere simulation chamber SAPHIR (3~LIF, 1~DOAS). All instruments were found to measure tropospheric OH concentrations with high sensitivity and good time resolution. The pairwise correlations between different data sets were linear and yielded high correlation coefficients (r2=0.75−0.96). Excellent absolute agreement was observed for the instruments at the SAPHIR chamber, yielding slopes between 1.01 and 1.13 in the linear regressions. In ambient air, the slopes deviated from unity by factors of 1.06 to 1.69, which can partly be explained by the stated instrumental accuracies. In addition, sampling inhomogeneities and calibration problems have apparently contributed to the discrepancies. The absolute intercepts of the linear regressions did not exceed 0.6×106 cm−3, mostly being insignificant and of minor importance for daytime observations of OH. No relevant interferences with respect to ozone, water vapour, NOx and peroxy radicals could be detected. The HOxComp campaign has demonstrated that OH can be measured reasonably well by current instruments, but also that there is still room for improvement of calibrations.

Tropical forests are a strong source of biogenic volatile organic compounds (BVOCs) to the atmosphere which can potentially impact the atmospheric oxidation capacity. Here we present airborne and ground-based BVOC measurements representative for the long dry season covering a large area of the northern Amazonian rainforest (6–3° N, 50–59° W). The measurements were conducted during the October 2005 GABRIEL (Guyanas Atmosphere-Biosphere exchange and Radicals Intensive Experiment with the Learjet) campaign. The vertical (35 m to 10 km) and diurnal (09:00–16:00) profiles of isoprene, its oxidation products methacrolein and methyl vinyl ketone and methanol and acetone, measured by PTR-MS (Proton Transfer Reaction Mass Spectrometry), have been used to empirically estimate their emission fluxes from the forest canopy on a regional scale. The mixed layer isoprene emission flux, inferred from the airborne measurements above 300 m, is 5.7 mg isoprene m−2 h−1 after compensating for chemistry and ~6.9 mg isoprene m−2 h−1 taking detrainment into account. This surface flux is in general agreement with previous tropical forest studies. Inferred methanol and acetone emission fluxes are 0.5 mg methanol m−2 h−1 and 0.35 mg acetone m−2 h−1, respectively. The BVOC measurements were compared with fluxes and mixing ratios simulated with a single-column chemistry and climate model (SCM). The inferred isoprene flux is substantially smaller than that simulated with an implementation of a commonly applied BVOC emission algorithm in the SCM.