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Formaldehyde (HCHO), hydrogen peroxide (H 2 O 2) and organic hydroperoxides (ROOH) play a key role in atmospheric oxidation processes. They act as sources and sinks for HO x radicals (OH + HO 2), 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, H 2 O 2 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 H 2 O 2 (≤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 H 2 O 2 at night with 0.77±0.29 cm s -1 for HCHO and 1.03±0.52 cm s -1 for H 2 O 2 over the Arabian Sea, which were matched by EMAC. The photochemical budget of H 2 O 2 revealed elevated HO x radical concentrations in EMAC, which resulted in an overestimation of H 2 O 2 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. [ABSTRACT FROM AUTHOR]

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Formaldehyde (HCHO) and hydrogen peroxide (H2O2) 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 evaluation of global chemistry-transport models which need to account for multifarious source distributions, transport and mixing, complex photochemical reaction pathways and deposition processes. HCHO is an intermediate produced during the oxidation of VOCs and is an indicator of photochemical activity and combustion related emissions. Due to its many production pathways and its rather short lifetime of only several hours at noon, accurate modelling of this species is challenging. In this study, we use in situ observations in the marine boundary layer (MBL) to evaluate results of the general circulation model EMAC (ECHAM5/MESSy2 Atmospheric Chemistry). The dataset was obtained during the AQABA ship campaign around the Arabian Peninsula in summer 2017. This region is characterized by high mixing ratios of photochemical air pollution, high humidity and strong solar irradiation, especially in the area around the Suez Canal and the Arabian Gulf. We find that EMAC fails to predict absolute mixing ratios of HCHO, especially during high pollution events, but it reproduces most of the HCHO variability seen in the different regions, while it systematically overestimates H2O2. This is mainly attributed to missing primary VOC emissions and the overestimation of HOx radicals, and also related to the models coarse spatial resolution. [ABSTRACT FROM AUTHOR]

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 ∑26 PAHs, ∑19 RPAHs, ∑11 OPAHs and ∑17 NPAHs, 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 ∑26 PAHs and ∑11 OPAHs, while the ∑17 NPAHs were most abundant over the Arabian Gulf (known also as the Persian Gulf). 1,4-Naphthoquinone (1,4-O 2 NAP) 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 (PM 1). [ABSTRACT FROM AUTHOR]

Polycyclic aromatic hydrocarbons (PAHs), 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 has 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 Σ27PAHs, Σ19RPAHs, Σ11OPAHs and Σ17NPAHs, in the gas and particulate phase, were 2.85 ± 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 Σ26PAHs and Σ11OPAHs, while the Σ17NPAHs were most abundant over the Arabian Gulf (known also as 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-NFLT, which were frequently detected during the campaign, showed elevated concentrations in fresh shipping emissions. In contrast, 2-nitrofluoranthene (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, also benz(a)anthracene-7,12-dione and 1,4-O2NAP 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). [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Background: The incidence of hypoxemia during one-lung ventilation (OLV) is as high as 10%. It is also partially determined by the distribution of perfusion. During thoracic surgery, different body positions are used, such as the supine, semilateral, lateral, and prone positions, with such positions potentially influencing the distribution of perfusion. Furthermore, hypovolemia can impair hypoxic vasoconstriction. However, the effects of body position and hypovolemia on the distribution of perfusion remain poorly defined. We hypothesized that, during OLV, the relative perfusion of the ventilated lung is higher in the lateral decubitus position and that hypovolemia impairs the redistribution of pulmonary blood flow. Methods: Sixteen juvenile pigs were anesthetized, mechanically ventilated, submitted to a right-sided thoracotomy, and randomly assigned to one of two groups: (1) intravascular normovolemia or (2) intravascular hypovolemia, as achieved by drawing ~25% of the estimated blood volume (n = 8/group). Furthermore, to mimic thoracic surgery inflammatory conditions, Escherichia coli lipopolysaccharide was continuously infused at 0.5 μg kg−1 h−1. Under left-sided OLV conditions, the animals were further randomized to one of the four sequences of supine, left semilateral, left lateral, and prone positioning. Measurements of pulmonary perfusion distribution with fluorescence-marked microspheres, ventilation distribution by electrical impedance tomography, and gas exchange were then performed during two-lung ventilation in a supine position and after 30 min in each position and intravascular volume status during OLV. Results: During one-lung ventilation, the relative perfusion of the ventilated lung was higher in the lateral than the supine position. The relative perfusion of the non-ventilated lung was lower in the lateral than the supine and prone positions and in semilateral compared with the prone position. During OLV, the highest arterial partial pressure of oxygen/inspiratory fraction of oxygen (PaO2/ F I O 2) was achieved in the lateral position as compared with all the other positions. The distribution of perfusion, ventilation, and oxygenation did not differ significantly between normovolemia and hypovolemia. Conclusions: During one-lung ventilation in endotoxemic pigs, the relative perfusion of the ventilated lung and oxygenation were higher in the lateral than in the supine position and not impaired by hypovolemia. [ABSTRACT FROM AUTHOR]

We present shipborne measurements of NO x (≡ NO + NO 2) and NO y (≡ NO x+ 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 NO x and NO z (≡ NO y -NO x) 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 NO x emissions and their influence on the NO y 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 NO 2 data sets from a chemiluminescence detector (CLD) were used in the analysis. In all regions, we find that NO x 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 NO x production rate from its photolysis. Mean NO 2 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 NO 2 during the night (reaction with O 3) 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 O x and NO z , where O x= O 3+ NO 2) ranged from 10.5 ± 0.9 to 19.1 ± 1.1. This metric quantifies the relative strength of photochemical O 3 production from NO x compared to the competing sequestering into NO z species. The largest values were found over the Arabian Gulf, consistent with high levels of O 3 found in that region (10–90 percentiles range: 23–108 ppbv). The fractional contribution of individual NO z species to NO y exhibited a large regional variability, with HNO 3 generally the dominant component (on average 33 % of NO y) with significant contributions from organic nitrates (11 %) and particulate nitrates in the PM 1 size range (8 %). [ABSTRACT FROM AUTHOR]

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)), 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 photo-stationary state, the HCHO loss is balanced by production via OH initiated degradation of volatile organic compounds (VOCs), photolysis of oxygenated volatile organic compounds (OVOCs) and the ozonolysis of alkenes. The slope α from a scatter plot of the HCHO production rate versus the product of R(OH) and OH yields the fraction of R(OH) that contributes to HCHO production. Values of α varied between less than 2 % in rather clean air over the Arabian Sea and the southern Red Sea, and up to 32 % over the polluted Arabian Gulf (also known as the Persian Gulf), signifying that polluted areas harbour a larger variety of HCHO precursors. The HCHO yield from R(OH) depends on the absolute and relative contributions of alkanes, alkenes, oxygenated volatile organic compounds (OVOCs) and aromatics to R(OH), while no significant correlation to NOx mixing ratios was found, indicating that HCHO production was not NOx limited. [ABSTRACT FROM AUTHOR]

Background: Continuous external negative pressure (CENP) during positive pressure ventilation can recruit dependent lung regions. We hypothesised that CENP applied regionally to the thorax or the abdomen only, increases the caudal end-expiratory transpulmonary pressure depending on positive end-expiratory pressure (PEEP) in lung-injured pigs. Eight pigs were anesthetised and mechanically ventilated in the supine position. Pressure sensors were placed in the left pleural space, and a lung injury was induced by saline lung lavages. A CENP shell was placed at the abdomen and thorax (randomised order), and animals were ventilated with PEEP 15, 7 and zero cmH2O (15 min each). On each PEEP level, CENP of − 40, − 30, − 20, − 10 and 0 cmH2O was applied (3 min each). Respiratory and haemodynamic variables were recorded. Electrical impedance tomography allowed assessment of centre of ventilation. Results: Compared to positive pressure ventilation alone, the caudal transpulmonary pressure was significantly increased by CENP of ≤ 20 cmH2O at all PEEP levels. CENP of – 20 cmH2O reduced the mean airway pressure at zero PEEP (P = 0.025). The driving pressure decreased at CENP of ≤ 10 at PEEP of 0 and 7 cmH2O (P < 0.001 each) but increased at CENP of – 30 cmH2O during the highest PEEP (P = 0.001). CENP of – 30 cmH2O reduced the mechanical power during zero PEEP (P < 0.001). Both elastance (P < 0.001) and resistance (P < 0.001) were decreased at CENP ≤ 30 at PEEP of 0 and 7 cmH2O. Oxygenation increased at CENP of ≤ 20 at PEEP of 0 and 7 cmH2O (P < 0.001 each). Applying external negative pressure significantly shifted the centre of aeration towards dorsal lung regions irrespectively of the PEEP level. Cardiac output decreased significantly at CENP -20 cmH2O at all PEEP levels (P < 0.001). Effects on caudal transpulmonary pressure, elastance and cardiac output were more pronounced when CENP was applied to the abdomen compared with the thorax. Conclusions: In this lung injury model in pigs, CENP increased the end-expiratory caudal transpulmonary pressure. This lead to a shift of lung aeration towards dependent zones as well as improved respiratory mechanics and oxygenation, especially when CENP was applied to the abdomen as compared to the thorax. CENP values ≤ 20 cmH2O impaired the haemodynamics. [ABSTRACT FROM AUTHOR]

Background: Flow-controlled ventilation (FCV) allows expiratory flow control, reducing the collapse of the airways during expiration. The performance of FCV during one-lung ventilation (OLV) under intravascular normo- and hypovolaemia is currently unknown. In this explorative study, we hypothesised that OLV with FCV improves PaO2 and reduces mechanical power compared to volume-controlled ventilation (VCV). Sixteen juvenile pigs were randomly assigned to one of two groups: (1) intravascular normovolaemia (n = 8) and (2) intravascular hypovolaemia (n = 8). To mimic inflammation due to major thoracic surgery, a thoracotomy was performed, and 0.5 μg/kg/h lipopolysaccharides from Escherichia coli continuously administered intravenously. Animals were randomly assigned to OLV with one of two sequences (60 min per mode): (1) VCV–FCV or (2) FCV–VCV. Variables of gas exchange, haemodynamics and respiratory signals were collected 20, 40 and 60 min after initiation of OLV with each mechanical ventilation mode. The distribution of ventilation was determined using electrical impedance tomography (EIT). Results: Oxygenation did not differ significantly between modes (P = 0.881). In the normovolaemia group, the corrected expired minute volume (P = 0.022) and positive end-expiratory pressure (PEEP) were lower during FCV than VCV. The minute volume (P ≤ 0.001), respiratory rate (P ≤ 0.001), total PEEP (P ≤ 0.001), resistance of the respiratory system (P ≤ 0.001), mechanical power (P ≤ 0.001) and resistive mechanical power (P ≤ 0.001) were lower during FCV than VCV irrespective of the volaemia status. The distribution of ventilation did not differ between both ventilation modes (P = 0.103). Conclusions: In a model of OLV in normo- and hypovolemic pigs, mechanical power was lower during FCV compared to VCV, without significant differences in oxygenation. Furthermore, the efficacy of ventilation was higher during FCV compared to VCV during normovolaemia. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Strongly enhanced tropospheric ozone mixing ratios have been reported in the Arabian Basin, a region with intense solar radiation and high concentrations of ozone precursors such as nitrogen oxides and volatile organic compounds. To analyze photochemical ozone production in the marine boundary layer (MBL) around the Arabian Peninsula, we use ship-borne observations of NO, NO2, O3, OH, HO2, HCHO, actinic flux, water vapor, pressure and temperature obtained during the summer 2017 Air Quality and Climate in the Arabian Basin (AQABA) campaign, compare them to simulation results of the ECHAM-MESSy atmospheric chemistry (EMAC) general circulation model. Net ozone production rates (NOPR) were greatest over the Gulf of Oman, the Northern Red Sea and the Arabian Gulf with median values of 14 ppbv day−1, 16 ppbv day−1 and 28 ppbv day−1, respectively. NOPR over the Mediterranean, the Southern Red Sea and the Arabian Sea did not significantly deviate from zero; however, results for the Arabian Sea indicate weak net ozone production of 5 ppbv day−1, and net ozone destruction over the Mediterranean and the Southern Red Sea with −2 ppbv day−1 and −4 ppbv day−1, respectively. Constrained by measured HCHO/NO2-ratios, our photochemistry calculations show that net ozone production in the MBL around the Arabian Peninsula occurs mostly in a transition regime between NOx and VOC-limitation with a tendency towards NOx-limitation except over the Northern Red Sea and the Oman Gulf. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

Shipborne measurements of nitryl chloride (ClNO2), hydrogen chloride (HCl) and sulphur 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 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 VOCs, especially in the early morning. [ABSTRACT FROM AUTHOR]

In the atmospheric boundary layer (ABL), incomplete mixing (i.e., segregation) results in reduced chemical reaction rates compared to those expected from mean values and rate constants derived under well mixed conditions. Recently, segregation has been suggested as a potential cause of discrepancies between modelled and measured OH radical concentrations, especially under high isoprene conditions. Therefore, the influence of segregation on the reaction of OH radicals with isoprene has been investigated by modelling studies and one ground-based and one aircraft campaign. In this study, we measured isoprene and OH radicals with high time resolution in order to directly calculate the influence of segregation in a low-NOx and high-isoprene environment in the central Amazon basin. The calculated intensities of segregation (Is) at the Amazon Tall Tower Observatory (ATTO) above canopy top are in the range of values determined at a temperate deciduous forest (ECHO-campaign) in a high-NOx low-isoprene environment, but stay below 10%. To establish a more general idea about the causes of segregation and their potential limits, further analysis was based on the budget equations of isoprene mixing ratios, the variance of mixing ratios, and the balance of the intensity of segregation itself. Furthermore, it was investigated if a relation of Is to the turbulent isoprene surface flux can be established theoretically and empirically, as proposed previously. A direct relation is not given and the amount of variance in Is explained by the isoprene flux will be higher the less the influence from other processes (e.g., vertical advection) is and will therefore be greater near the surface. Although ground based values of Is from ATTO and ECHO are in the same range, we could identify different dominating processes driving Is. For ECHO the normalized variance of isoprene had the largest contribution, whereas for ATTO the different transport terms expressed as a residual were dominating. To get a more general picture of Is and its potential limits in the ABL, we also compared these ground based measurements to ABL modelling studies and results from an aircraft campaign. The ground based measurements show the lowest values of the degree of inhomogenous mixing (<20%, mostly below 10%). These values increase if the contribution of lower frequencies is added. Values integrated over the whole boundary layer (modelling studies) are in the range from 10% to 30% and aircraft measurements integrating over different landscapes are amongst the largest reported. This presents evidence that larger scale heterogeneities in land surface properties contribute substantially to Is. [ABSTRACT FROM AUTHOR]

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. [ABSTRACT FROM AUTHOR]

We present version 4.0gmdd of the atmospheric chemistry box model CAABA/MECCA which now includes a number of new features: (i) skeletal mechanism reduction, (ii) the 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-4.0gmdd is a community model published under the GNU General Public License. [ABSTRACT FROM AUTHOR]