Extreme Concentrations of Nitric Oxide Control Daytime Oxidation and Quench Nocturnal Oxidation Chemistry in Delhi during Highly Polluted Episodes.

Delhi, India, suffers from periods of very poor air quality, but little is known about the chemical production of secondary pollutants in this highly polluted environment. During the postmonsoon period in 2018, extremely high nighttime concentrations of NOx (NO and NO2) and volatile organic compounds (VOCs) were observed, with median NOx mixing ratios of ∼200 ppbV (maximum of ∼700 ppbV). A detailed chemical box model constrained to a comprehensive suite of speciated VOC and NOx measurements revealed very low nighttime concentrations of oxidants, NO3, O3, and OH, driven by high nighttime NO concentrations. This results in an atypical NO3 diel profile, not previously reported in other highly polluted urban environments, significantly perturbing nighttime radical oxidation chemistry. Low concentrations of oxidants and high nocturnal primary emissions coupled with a shallow boundary layer led to enhanced early morning photo-oxidation chemistry. This results in a temporal shift in peak O3 concentrations when compared to the premonsoon period (12:00 and 15:00 local time, respectively). This shift will likely have important implications on local air quality, and effective urban air quality management should consider the impacts of nighttime emission sources during the postmonsoon period.

Chemical source profiles of fine particles for five different sources in Delhi.

Increasing emissions from sources such as construction and burning of biomass from crop residues, roadside and municipal solid waste have led to a rapid increase in the atmospheric concentrations of fine particulate matter (≤2.5 µm; PM2.5) over many Indian cities. Analyses of their chemical profiles are important for receptor models to accurately estimate the contributions from different sources. We have developed chemical source profiles for five important pollutant sources - construction (CON), paved road dust (PRD), roadside biomass burning (RBB), solid waste burning (SWB), and crop residue burning (CPB) - during three intensive campaigns (winter, summer and post-monsoon) in and around Delhi. We obtained chemical characterisations of source profiles incorporating carbonaceous material such as organic carbon (OC) and elemental carbon (EC), water-soluble ions (F-, Cl-, NO2-, NO3-, SO42-, PO43-, Na+ and NH4+), and elements (Mg, Al, Si, P, S, Cl, K, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br, Rb, Sr, Ba, and Pb). CON was dominated by the most abundant elements, K, Si, Fe, Al, and Ca. PRD was also dominated by crustal elements, accounting for 91% of the total analysed elements. RBB, SWB and CPB profiles were dominated by organic matter, which accounted for 94%, 86.2% and 86% of the total PM2.5, respectively. The database of PM emission profiles developed from the sources investigated can be used to assist source apportionment studies for accurate quantification of the causes of air pollution and hence assist governmental bodies in formulating relevant countermeasures.

Neighbourhood-scale dispersion of traffic-induced ultrafine particles in central London: WRF large eddy simulations.

Traffic-generated ultrafine particles (UFPs) in the urban atmosphere have a high proportion of their composition comprised of semi-volatile compounds (SVOCs). The evaporation/condensation processes of these SVOCs can alter UFP number size distributions and play an important role in determining the fate of UFPs in urban areas. The neighbourhood-scale dispersion (over distances < 1 km) and evolution of traffic-generated UFPs for a real-world street network in central London was simulated by using the WRF-LES model (the large eddy simulation mode of the Weather Research and Forecasting modelling system) coupled with multicomponent microphysics. The neighbourhood scale dispersion of UFPs was significantly influenced by the spatial pattern of the real-world street emissions. Model output indicated the shrinkage of the peak diameter from the emitted profile to the downwind profile, due to an evaporation process during neighbourhood-scale dispersion. The dilution process and the aerosol microphysics interact with each other during the neighbourhood dispersion of UFPs, yielding model output that compares well with measurements made at a location downwind of an intense roadside source. The model captured the total SVOC concentrations well, with overestimations for gas concentrations and underestimations for particle concentrations, particularly of the lighter SVOCs. The contribution of the intense source, Marylebone Road (MR) in London, to concentrations at the downwind location (as estimated by a model scenario with emissions from MR only) is comparable with that of the rest of the street network (a scenario without emissions from MR), implying that both are important. An appreciable level of non-linearity is demonstrated for nucleation mode UFPs and medium range carbon SVOCs at the downwind receptor site.

Behaviour of traffic emitted semi-volatile and intermediate volatility organic compounds within the urban atmosphere.

Particulate matter originated from traffic has attracted major interest over the last few years. The semi-volatile organic component of the particles may evaporate with dispersion away from the emission source, creating vapour which may oxidise to form secondary organic aerosol. Air samples were collected from a street canyon, the adjacent park and an urban background site during the winter-spring period in central London, UK. Emissions of semi-volatile organic compounds (SVOCs) and intermediate volatility organic compounds (IVOCs) ranging from C10 to C36 in both the gas phase and particle phase were measured by using thermal desorption coupled to comprehensive two-dimensional gas chromatography time-of-flight mass spectrometry (TD-GC × GC-ToF-MS). Main compound groups identified and quantified were grouped alkanes (n-alkanes and branched alkanes), monocyclic alkanes, bicyclic alkanes and monocyclic aromatics. The carbon preference index (CPI) of n-alkanes was estimated to distinguish the emission sources. Pearson correlations between I/SVOCs and traffic tracers (black carbon, NOx and benzene) in different locations were compared to analyse the influence of this emission source. The results indicate that while the major emission source at the roadside site is traffic, the lower correlations at background sites are indicative of other source contributions and/or differential reactivity of compounds. Gas-particle phase partitioning of n-alkanes is evaluated and compared between sites. The potential influence of gas phase I/SVOCs upon OH reactivity and secondary organic aerosol (SOA) formation is estimated and found to be relatively small.

Characterization of Gas and Particulate Phase Organic Emissions (C9-C37) from a Diesel Engine and the Effect of Abatement Devices.

Particulate and vapor phase emissions in the diluted exhaust of a light-duty diesel engine designed for Euro 5 application have been sampled. The engine was operated in three modes, and samples were collected from the exhaust without aftertreatment but also with aftertreatment by an exhaust oxidation catalyst and particle filter. The samples were analyzed by two-dimensional gas chromatography with time-of-flight mass spectral detection. The results show overall removal efficiencies for the organic compound mass by the combination of oxidation catalyst and particle filter of 50, 56, and 74% for the high-speed/high-load, low-speed/low-load, and high-speed/low-load conditions respectively. The results are clearly indicative of substantial repartitioning of the particulate and vapor components within the abatement devices and show an apparently reduced efficiency for the removal of high-molecular-weight alkanes under high-speed/high-load conditions relative to lower-molecular-weight compounds, although this may be due to alkane formation by thermocracking of other species. A notable feature is the presence of oxygenated compounds in the emissions, which are not present in the fuel. These are increased under high-speed/high-load conditions, and the results suggest the formation in the aftertreatment devices as well as in the combustion process.

Diesel exhaust nanoparticles and their behaviour in the atmosphere.

Diesel engine emissions are by far the largest source of nanoparticles in many urban atmospheres, in which they dominate the particle number count, and may present a significant threat to public health. This paper reviews knowledge of the composition and atmospheric properties of diesel exhaust particles, and exemplifies research in this field through a description of the FASTER project (Fundamental Studies of the Sources, Properties and Environmental Behaviour of Exhaust Nanoparticles from Road Vehicles) which studied the size distribution-and, in unprecedented detail, the chemical composition-of nanoparticles sampled from diesel engine exhaust. This information has been systematized and used to inform the development of computational modules that simulate the behaviour of the largely semi-volatile content of the nucleation mode particles, including consequent effects on the particle size distribution, under typical atmospheric conditions. Large-eddy model studies have informed a simpler characterization of flow around the urban built environment, and include aerosol processes. This modelling and engine-laboratory work have been complemented by laboratory measurements of vapour pressures, and the execution of two field measurement campaigns in London. The result is a more robust description of the dynamical behaviour on the sub-kilometre scale of diesel exhaust nanoparticles and their importance as an urban air pollutant.

Relationship of polycyclic aromatic hydrocarbons with oxy(quinone) and nitro derivatives during air mass transport.

Airborne concentrations of Polycyclic Aromatic Hydrocarbons (PAH), quinone and nitro derivatives have been measured at three sites on the coast of Saudi Arabia to the north of the city of Jeddah. The PAH show a general reduction in concentrations from northwest to southeast, consistent with a source from a petrochemical works to the northwest of the sampling sites. In comparison, the concentrations of quinones show little variation between the sampling sites consistent with these being predominantly longer lived secondary pollutants formed from PAH oxidation. The nitro-PAH show a gradient in concentrations similar to but smaller than that for the PAH suggesting a balance between atmospheric formation and removal by photolysis. The 2-nitrofluoranthene:1-nitropyrene ratio increases from north to south, consistent with atmospheric chemical formation of the former compound, while the ratio of 2-nitrofluoranthene:2-nitropyrene is consistent with hydroxyl radical as the dominant reactant. An investigation of the changes in PAH congener ratios during air mass transport along the Red Sea coast shows consistency with reaction with a relatively low concentration of hydroxyl radical only for the day with the highest concentrations. It is concluded that while PAH degradation is occurring by chemical reaction, emissions from other locations along the air mass trajectory are most probably also leading to changes in congener ratios.

The characterisation of diesel exhaust particles - composition, size distribution and partitioning.

A number of major research questions remain concerning the sources and properties of road traffic generated particulate matter. A full understanding of the composition of primary vehicle exhaust aerosol and its contribution to secondary organic aerosol (SOA) formation still remains elusive, and many uncertainties exist relating to the semi-volatile component of the particles. Semi-Volatile Organic Compounds (SVOCs) are compounds which partition directly between the gas and aerosol phases under ambient conditions. The SVOCs in engine exhaust are typically hydrocarbons in the C15-C35 range, and are largely uncharacterised because they are unresolved by traditional gas chromatography, forming a large hump in the chromatogram referred to as Unresolved Complex Mixture (UCM). In this study, thermal desorption coupled to comprehensive Two Dimensional Gas-Chromatography Time-of-Flight Mass-Spectrometry (TD-GC × GC-ToF-MS) was exploited to characterise and quantify the composition of SVOCs from the exhaust emission. Samples were collected from the exhaust of a diesel engine, sampling before and after a diesel oxidation catalyst (DOC), while testing at steady state conditions. Engine exhaust was diluted with air and collected using both filter and impaction (nano-MOUDI), to resolve total mass and size resolved mass respectively. Adsorption tubes were utilised to collect SVOCs in the gas phase and they were then analysed using thermal desorption, while particle size distribution was evaluated by sampling with a DMS500. The SVOCs were observed to contain predominantly n-alkanes, branched alkanes, alkyl-cycloalkanes, alkyl-benzenes, PAHs and various cyclic aromatics. Particle phase compounds identified were similar to those observed in engine lubricants, while vapour phase constituents were similar to those measured in fuels. Preliminary results are presented illustrating differences in the particle size distribution and SVOCs composition when collecting samples with and without a DOC. The results indicate that the DOC tested is of very limited efficiency, under the studied engine operating conditions, for removal of SVOCs, especially at the upper end of the molecular weight range.

Modelling component evaporation and composition change of traffic-induced ultrafine particles during travel from street canyon to urban background.

We developed a model (CiTTy-Street-UFP) of traffic-related particle behaviour in a street canyon and in the nearby downwind urban background that accounts for aerosol dynamics and the variable vapour pressure of component organics. The model simulates the evolution and fate of traffic generated multicomponent ultrafine particles (UFP) composed of a non-volatile core and 17 Semi-Volatile Organic Compounds (SVOC, modelled as n-alkane proxies). A two-stage modelling approach is adopted: (1) a steady state simulation inside the street canyon is achieved, in which there exists a balance between traffic emissions, condensation/evaporation, deposition, coagulation and exchange with the air above roof-level; and (2) a continuing simulation of the above-roof air parcel advected to the nearby urban park during which evaporation is dominant. We evaluate the component evaporation and associated composition changes of multicomponent organic particles in realistic atmospheric conditions and compare our results with observations from London (UK) in a street canyon and an urban park. With plausible input conditions and parameter settings, the model can reproduce, with reasonable fidelity, size distributions in central London in 2007. The modelled nucleation-mode peak diameter, which is 23 nm in the steady-state street canyon, decreases to 9 nm in a travel time of just 120 s. All modelled SVOC in the sub-10 nm particle size range have evaporated leaving behind only non-volatile material, whereas modelled particle composition in the Aitken mode contains SVOC between C26H54 and C32H66. No data on particle composition are available in the study used for validation, or elsewhere. Measurements addressing in detail the size resolved composition of the traffic emitted UFP in the atmosphere are a high priority for future research. Such data would improve the representation of these particles in dispersion models and provide the data essential for model validation. Enhanced knowledge of the chemical composition of nucleation-mode particles from diesel engine exhaust is needed to predict both their atmospheric behaviour and their implications for human health.

Using Variable Ionization Energy Time-of-Flight Mass Spectrometry with Comprehensive GC×GC To Identify Isomeric Species.

Although GC×GC-ToF-MS allows the separation of thousands of peaks, many of these peaks are not positively identified owing to the lack of mass spectral library data and/or standard materials, leading to a substantial amount of information being inaccessible. The fragmentation patterns of molecules in mass spectrometers using electron impact ionization at 70 eV can be useful for molecule identification, provided a match is available in a published EI MS library, but are indistinguishable for many isomeric organic compounds (for example, linear and branched alkanes). Lower ionization energies have been exploited leading to organic compounds being ionized with lower excess internal energy and less fragmentation, retaining the molecular ion and maximizing its relative signal. This has enabled the identification of a large number of isomeric organic compounds, both aliphatic and aromatic, between C12-C36, in the previously unresolved complex mixture (UCM) of two motor oil samples. This technique also demonstrates problems associated with separation of coeluting isomers, particularly for the n-alkanes, which are routinely measured by 1D GC/MS and may be overestimated, due to coelution. As a consequence retention times in 2 dimensions and mass spectra at variable ionization energies are shown to give unparalleled power to identify specific isomers.

Recent advances in the application of 2-dimensional gas chromatography with soft and hard ionisation time-of-flight mass spectrometry in environmental analysis.

Two-dimensional gas chromatography has huge power for separating complex mixtures. The principles of the technique are outlined together with an overview of detection methods applicable to GC × GC column effluent with a focus on selectivity. Applications of GC × GC techniques in the analysis of petroleum-related and airborne particulate matter samples are reviewed. Mass spectrometric detection can be used alongside spectral libraries to identify eluted compounds, but in complex petroleum-related and atmospheric samples, when used conventionally at high ionisation energies, may not allow differentiation of structural isomers. Available low energy ionisation methods are reviewed and an example given of the additional structural information which can be extracted by measuring mass spectra at both low and high ionisation energies, hence greatly enhancing the selectivity of the technique.

Insights into the Formation and Evolution of Individual Compounds in the Particulate Phase during Aromatic Photo-Oxidation.

Secondary organic aerosol (SOA) is well-known to have adverse effects on air quality and human health. However, the dynamic mechanisms occurring during SOA formation and evolution are poorly understood. The time-resolved SOA composition formed during the photo-oxidation of three aromatic compounds, methyl chavicol, toluene and 4-methyl catechol, were investigated at the European Photoreactor. SOA was collected using a particle into liquid sampler and analyzed offline using state-of-the-art mass spectrometry to produce temporal profiles of individual photo-oxidation products. In the photo-oxidation of methyl chavicol, 70 individual compounds were characterized and three distinctive temporal profile shapes were observed. The calculated mass fraction (Ci,aer/COA) of the individual SOA compounds showed either a linear trend (increasing/decreasing) or exponential decay with time. Substituted nitrophenols showed an exponential decay, with the nitro-group on the aromatic ring found to control the formation and loss of these species in the aerosol phase. Nitrophenols from both methyl chavicol and toluene photo-oxidation experiments showed a strong relationship with the NO2/NO (ppbv/ppbv) ratio and were observed during initial SOA growth. The location of the nitrophenol aromatic substitutions was found to be critically important, with the nitrophenol in the photo-oxidation of 4-methyl catechol not partitioning into the aerosol phase until irradiation had stopped; highlighting the importance of studying SOA formation and evolution at a molecular level.

Urinary metabolites of polycyclic aromatic hydrocarbons in Saudi Arabian schoolchildren in relation to sources of exposure.

Polycyclic aromatic hydrocarbons contain a number of known carcinogenic compounds, and urinary biomarkers have been widely used as a measure of exposure but quantitative relationships with exposure variables have proved elusive. This study aimed to quantify the relationship between exposures to phenanthrene and pyrene from atmospheric and dietary sources with the excretion of 1-hydroxypyrene and hydroxyphenanthrenes in urine as biomarkers of exposure. The study population consisted of 204 male schoolchildren attending three schools in different parts of Jeddah, Saudi Arabia who provided urine samples on each of three consecutive days. Outdoor air measurements of polycyclic aromatic hydrocarbons were made at the schools and the children provided information on diet, exposure to environmental tobacco smoke and incense, and various lifestyle factors through a questionnaire. Mixed models with random effects for subjects nested within site were fitted in order to examine the relationship between exposure variables and urinary PAH metabolites. A unit increase (1 ng m(-3)) in ambient pyrene (particulate plus gaseous phase) was associated with a 3.5% (95% CI: 1.01%, 5.13%) increase in urinary 1-hydroxypyrene concentration. A unit increase in ambient phenanthrene was associated with a 1.01% (95% CI: 0.03%, 2.02%) increase in total hydroxyphenanthrene concentrations. Consumption of chargrilled food increased the 1-hydroxypyrene and hydroxyphenanthrene concentrations by 24% (95% CI: 11%, 37%) and 17% (95% CI: 8%, 26%) respectively. We did not find evidence of association for environmental tobacco smoke exposure or incense burning. It is concluded that both respiratory exposure and consumption of chargrilled food are considerable sources of PAH exposure in this population as reflected by concentrations of urinary biomarkers.

Kinetics of stabilised Criegee intermediates derived from alkene ozonolysis: reactions with SO2, H2O and decomposition under boundary layer conditions.

The removal of SO2 in the presence of alkene-ozone systems has been studied for ethene, cis-but-2-ene, trans-but-2-ene and 2,3-dimethyl-but-2-ene, as a function of humidity, under atmospheric boundary layer conditions. The SO2 removal displays a clear dependence on relative humidity for all four alkene-ozone systems confirming a significant reaction for stabilised Criegee intermediates (SCI) with H2O. The observed SO2 removal kinetics are consistent with relative rate constants, k(SCI + H2O)/k(SCI + SO2), of 3.3 (±1.1) × 10(-5) for CH2OO, 26 (±10) × 10(-5) for CH3CHOO derived from cis-but-2-ene, 33 (±10) × 10(-5) for CH3CHOO derived from trans-but-2-ene, and 8.7 (±2.5) × 10(-5) for (CH3)2COO derived from 2,3-dimethyl-but-2-ene. The relative rate constants for k(SCI decomposition)/k(SCI + SO2) are -2.3 (±3.5) × 10(11) cm(-3) for CH2OO, 13 (±43) × 10(11) cm(-3) for CH3CHOO derived from cis-but-2-ene, -14 (±31) × 10(11) cm(-3) for CH3CHOO derived from trans-but-2-ene and 63 (±14) × 10(11) cm(-3) for (CH3)2COO. Uncertainties are ±2σ and represent combined systematic and precision components. These values are derived following the approximation that a single SCI is present for each system; a more comprehensive interpretation, explicitly considering the differing reactivity for syn- and anti-SCI conformers, is also presented. This yields values of 3.5 (±3.1) × 10(-4) for k(SCI + H2O)/k(SCI + SO2) of anti-CH3CHOO and 1.2 (±1.1) × 10(13) for k(SCI decomposition)/k(SCI + SO2) of syn-CH3CHOO. The reaction of the water dimer with CH2OO is also considered, with a derived value for k(CH2OO + (H2O)2)/k(CH2OO + SO2) of 1.4 (±1.8) × 10(-2). The observed SO2 removal rate constants, which technically represent upper limits, are consistent with decomposition being a significant, structure dependent, sink in the atmosphere for syn-SCI.

Polycyclic aromatic hydrocarbons, brachial artery distensibility and blood pressure among children residing near an oil refinery.

BACKGROUND: Polycyclic aromatic hydrocarbons (PAH) are produced by the burning and processing of fuel oils, and have been associated with oxidant stress, insulin resistance and hypertension in adults. Few studies have examined whether adolescents are susceptible to cardiovascular effects of PAHs. OBJECTIVE: To study associations of PAH exposure with blood pressure (BP) and brachial artery distensibility (BAD), an early marker of arterial wall stiffness, in young boys attending three schools in Jeddah, Saudi Arabia in varying proximity to an oil refinery. METHODS: Air samples collected from the three schools were analyzed for PAHs. PAH metabolites (total hydroxyphenanthrenes and 1-hydroxypyrene) were measured in urine samples from 184 adolescent males, in whom anthropometrics, heart rate, pulse pressure, brachial artery distensibility and blood pressure were measured. Descriptive, bivariate and multivariable analyses were performed to assess relationships of school location and urinary PAH metabolites with cardiovascular measures. RESULTS: Total suspended matter was significantly higher (444 ± 143 µg/m(3)) at the school near the refinery compared to a school located near a ring road (395 ± 65 µg/m(3)) and a school located away from vehicle traffic (232 ± 137 µg/m(3)), as were PAHs. Systolic (0.47 S D units, p = 0.006) and diastolic (0.53 SD units, p < 0.001) BP Z-scores were highest at the school near the refinery, with a 4.36-fold increase in prehypertension (p = 0.001), controlling for confounders. No differences in pulse pressure, BAD and heart rate were noted in relationship to school location. Urinary total hydroxyphenanthrenes and 1-hydroxypyrene were not associated with cardiovascular outcomes. CONCLUSIONS: Proximity to an oil refinery in Saudi Arabia is associated with prehypertension and increases in PAH and particulate matter exposures. Further study including insulin resistance measurements, better control for confounding, and longitudinal measurement is indicated.

Receptor modelling study of polycyclic aromatic hydrocarbons in Jeddah, Saudi Arabia.

Measurements of 14 polycyclic aromatic hydrocarbons (PAH) have been made in Jeddah, Saudi Arabia, with a view to establishing the concentrations in this major city, and quantifying the contributions of major sources. Particulate and vapour forms have been sampled and analysed separately. The concentrations are compared to measurements from other sites in the Middle Eastern region and are towards the lower end of the range, being far lower than concentrations reported from Riyadh (Saudi Arabia), Assiut (Egypt) and Tehran (Iran) but broadly similar to those measured in Damascus (Syria) and higher than those measured in Kuwait. The partitioning between vapour and particle phases is similar to that in data from Egypt and China, but with many compounds showing a higher particle-associated percentage than in Birmingham (UK) possibly reflecting a higher concentration of airborne particulate matter in the former countries. Concentrations in Jeddah were significantly higher at a site close to the oil refinery and a site close to a major ring road than at a suburban site to the north of the city. Application of positive matrix factorisation to the pooled data elicited three factors accounting respectively for 17%, 33% and 50% of the measured sum of PAH and these are interpreted as arising from gasoline vehicles, industrial sources, particularly the oil refinery, and to diesel/fuel oil combustion.

Radical product yields from the ozonolysis of short chain alkenes under atmospheric boundary layer conditions.

The gas-phase reaction of ozone with unsaturated volatile organic compounds (VOCs), alkenes, is an important source of the critical atmospheric oxidant OH, especially at night when other photolytic radical initiation routes cannot occur. Alkene ozonolysis is also known to directly form HO2 radicals, which may be readily converted to OH through reaction with NO, but whose formation is poorly understood. We report a study of the radical (OH, HO2, and RO2) production from a series of small alkenes (propene, 1-butene, cis-2-butene, trans-2-butene, 2-methylpropene, 2,3-dimethyl-2-butene (tetramethyl ethene, TME), and isoprene). Experiments were performed in the European Photoreactor (EUPHORE) atmospheric simulation chamber, with OH and HO2 levels directly measured by laser-induced fluorescence (LIF) and HO2 + ΣRO2 levels measured by peroxy-radical chemical amplification (PERCA). OH yields were found to be in good agreement with the majority of previous studies performed under comparable conditions (atmospheric pressure, long time scales) using tracer and scavenger approaches. HO2 yields ranged from 4% (trans-2-butene) to 34% (2-methylpropene), lower than previous experimental determinations. Increasing humidity further reduced the HO2 yields obtained, by typically 50% for an RH increase from 0.5 to 30%, suggesting that HOx production from alkene ozonolysis may be lower than current models suggest under (humid) ambient atmospheric boundary layer conditions. The mechanistic origin of the OH and HO2 production observed is discussed in the context of previous experimental and theoretical studies.

Epicardial adipose tissue thickness as a predictor of impaired microvascular function in patients with non-obstructive coronary artery disease.

OBJECTIVE: To determine if increased epicardial adipose tissue (EAT) measured by cardiac CT could be associated with impaired myocardial flow reserve (MFR) in patients with non-obstructive coronary artery disease (CAD). BACKGROUND: Studies have shown that EAT volume is related to epicardial obstructive CAD, myocardial ischemia and major adverse cardiac events. However, the association between EAT with coronary microvascular dysfunction and impaired MFR has not been well clarified. METHODS: Consecutive patients who underwent Rb-82 positron emission tomography (PET), coronary artery calcium (CAC) scoring and non-invasive coronary computed tomography angiography (CCTA) were screened. PET scans were analysed for standard myocardial perfusion (MPI) and MFR. CCTA results were analysed and only patients with non-obstructive CAD (<50% luminal diameter stenosis) were included. EAT thickness and volumes were measured from CT scans. RESULTS: Of 137 patients without obstructive CAD by CCTA and with normal Rb-82 PET relative MPI, 26 (19.0%) patients had impaired MFR < 2 and 87 (64%) patients had CAC. EAT(thickness), EAT(volume) and CAC values were higher in patients with impaired MFR < 2 than those with normal MFR ≥ 2 (6.7 ± 1.6 mm vs 4.4 ± 1.0 mm, P < .0001; 119.0 ± 25.3 cm(3) vs 105.8 ± 30.5 cm(3), P < .04 and 508.9 ± 554.3 vs 167.8 ± 253.9, P < .0001, respectively). However, EAT(thickness) had a stronger negative correlation with MFR than EAT(volume) and CAC (r = -0.78 vs r = -0.25 and ρ = -0.32, P < .0001). With multivariable logistic regression analysis, only EAT(thickness) was independently associated with impaired MFR (OR 20.7, 95% CI 4.9-87.9, P < .0001). Importantly, the receiver-operator characteristic (ROC) curves demonstrated a superior performance of EAT(thickness) vs EAT(volume) and EAT(thickness) vs CAC in detecting impaired MFR (AUC: 0.945 vs 0.625, difference between AUC: 0.319, P < .0001; AUC: 0.945 vs 0.710, difference between AUC: 0.235, P < .0006, respectively). On ROC curve analysis, an EAT(thickness) cut-off value > 5.6 mm was optimal in detecting impaired MFR with a sensitivity and specificity of 81% and 92%, respectively. CONCLUSIONS: Increased EAT appears to be associated with impaired MFR. This parameter may help improve detection of patients at risk of microvascular dysfunction.

The A2B adenosine receptor promotes Th17 differentiation via stimulation of dendritic cell IL-6.

Adenosine is an endogenous metabolite produced during hypoxia or inflammation. Previously implicated as an anti-inflammatory mediator in CD4(+) T cell regulation, we report that adenosine acts via dendritic cell (DC) A(2B) adenosine receptor (A(2B)AR) to promote the development of Th17 cells. Mouse naive CD4(+) T cells cocultured with DCs in the presence of adenosine or the stable adenosine mimetic 5'-(N-ethylcarboximado) adenosine resulted in the differentiation of IL-17- and IL-22-secreting cells and elevation of mRNA that encode signature Th17-associated molecules, such as IL-23R and RORγt. The observed response was similar when DCs were generated from bone marrow or isolated from small intestine lamina propria. Experiments using adenosine receptor antagonists and cells from A(2B)AR(-/-) or A(2A)AR(-/-)/A(2B)AR(-/-) mice indicated that the DC A(2B)AR promoted the effect. IL-6, stimulated in a cAMP-independent manner, is an important mediator in this pathway. Hence, in addition to previously noted direct effects of adenosine receptors on regulatory T cell development and function, these data indicated that adenosine also acts indirectly to modulate CD4(+) T cell differentiation and suggested a mechanism for putative proinflammatory effects of A(2B)AR.

Total radical yields from tropospheric ethene ozonolysis.

The gas-phase reactions of ozone with alkenes can be significant sources of free radicals (OH, HO(2) and RO(2)) in the Earth's atmosphere. In this study the total radical production and degradation products from ethene ozonolysis have been measured, under conditions relevant to the troposphere, during a series of detailed simulation chamber experiments. Experiments were carried out in the European photoreactor EUPHORE (Valencia, Spain), utilising various instrumentation including a chemical-ionisation-reaction time-of-flight mass-spectrometer (CIR-TOF-MS) measuring volatile organic compounds/oxygenated volatile organic compounds (VOCs/OVOCs), a laser induced fluorescence (LIF) system for measuring HO(2) radical products and a peroxy radical chemical amplification (PERCA) instrument measuring HO(2) + ΣRO(2). The ethene + ozone reaction system was investigated with and without an OH radical scavenger, in order to suppress side reactions. Radical concentrations were measured under dry and humid conditions and interpreted through detailed chemical chamber box modelling, incorporating the Master Chemical Mechanism (MCMv3.1) degradation scheme for ethene, which was updated to include a more explicit representation of the ethene-ozone reaction mechanism.The rate coefficient for the ethene + ozone reaction was measured to be (1.45 ± 0.25) × 10(-18) cm(3) molecules(-1) s(-1) at 298 K, and a stabilised Criegee intermediate yield of 0.54 ± 0.12 was determined from excess CO scavenger experiments. An OH radical yield of 0.17 ± 0.09 was determined using a cyclohexane scavenger approach, by monitoring the formation of the OH-initiated cyclohexane oxidation products and HO(2). The results highlight the importance of knowing the [HO(2)] (particularly under alkene limited conditions and high [O(3)]) and scavenger chemistry when deriving radical yields. An averaged HO(2) yield of 0.27 ± 0.07 was determined by LIF/model fitting. The observed yields are interpreted in terms of branching ratios for each channel within the postulated ethene ozonolysis mechanism.