75 research outputs found

    Simultaneous, in situ measurements of OH, HO_2, O_3, and H_2O: A test of modeled stratospheric HO_x chemistry

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    Simultaneous, in situ measurements of OH, HO_2, H_2O, and O_3 from 37–23 km are reported. The partitioning between OH and HO_2 and the total HO_x concentration are compared with expected steady-state values. The ratio of HO_2 to OH varies from less than 2 at 36 km to more than 3 at 25 km; in the lower stratosphere this ratio is nearly a factor of two less than predicted. The data are used to calculate HO_x production and loss rates. The measured HOx mixing ratio is consistent with production dominated by the reaction of O(1D) with H_2O, and loss controlled by NO_y below 28 km and HO_x above 30 km. The steady-state concentration of H_2O_2 is inferred from the measured HO_2 concentration and calculated photolysis rate. The maximum H_2O_2 mixing ratio (at 33 km) is predicted to be less than 0.2 ppb

    JNO\u3csub\u3e2\u3c/sub\u3e at high solar zenith angles in the lower stratosphere

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    In situ measurements of NO, NO2, O3, HO2, C1O, pressure, and temperature have been made at high solar zenith angles (SZA, 70° - 93°) in the lower stratosphere. These measurements are used to derive the photolysis rate of NO2, JNO2, using a time-dependent method. The resultant JNO2 values and the results of a multiple-scattering actinic flux model show a linear relationship throughout the SZA range. The difference of the two sets of JNO2 values of about 11% suggests that the model scattering calculation is very accurate at high SZA conditions near sunrise and sunset

    Evaluation of Clinical Risk Factors to Predict High On-Treatment Platelet Reactivity and Outcome in Patients with Stable Coronary Artery Disease (PREDICT-STABLE)

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    Objectives This study was designed to identify the multivariate effect of clinical risk factors on high on-treatment platelet reactivity (HPR) and 12 months major adverse events (MACE) under treatment with aspirin and clopidogrel in patients undergoing non-urgent percutaneous coronary intervention (PCI). Methods 739 consecutive patients with stable coronary artery disease (CAD) undergoing PCI were recruited. On-treatment platelet aggregation was tested by light transmittance aggregometry. Clinical risk factors and MACE during one-year follow-up were recorded. An independent population of 591 patients served as validation cohort. Results Degree of on-treatment platelet aggregation was influenced by different clinical risk factors. In multivariate regression analysis older age, diabetes mellitus, elevated BMI, renal function and left ventricular ejection fraction were independent predictors of HPR. After weighing these variables according to their estimates in multivariate regression model, we developed a score to predict HPR in stable CAD patients undergoing elective PCI (PREDICT-STABLE Score, ranging 0-9). Patients with a high score were significantly more likely to develop MACE within one year of follow-up, 3.4% (score 0-3), 6.3% (score 4-6) and 10.3% (score 7-9); odds ratio 3.23, P=0.02 for score 7-9 vs. 0-3. This association was confirmed in the validation cohort. Conclusions Variability of on-treatment platelet function and associated outcome is mainly influenced by clinical risk variables. Identification of high risk patients (e.g. with high PREDICT-STABLE score) might help to identify risk groups that benefit from more intensified antiplatelet regimen. Additional clinical risk factor assessment rather than isolated platelet function-guided approaches should be investigated in future to evaluate personalized antiplatelet therapy in stable CAD-patients

    Quantitative constraints on the atmospheric chemistry of nitrogen oxides: An analysis along chemical coordinates

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    In situ observations Of NO_2, NO, NO_y, ClONO_2, OH, O_3, aerosol surface area, spectrally resolved solar radiation, pressure and temperature obtained from the ER-2 aircraft during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) experiments are used to examine the factors controlling the fast photochemistry connecting NO and NO_2 and the slower chemistry connecting NO_x and HNO_3. Our analysis uses “chemical coordinates” to examine gradients of the difference between a model and precisely calibrated measurements to provide a quantitative assessment of the accuracy of current photochemical models. The NO/NO_2 analysis suggests that reducing the activation energy for the NO+O_3 reaction by 1.7 kJ/mol will improve model representation of the temperature dependence of the NO/NO_2 ratio in the range 215–235 K. The NO_x/HNO_3 analysis shows that systematic errors in the relative rate coefficients used to describe NO_x loss by the reaction OH + NO_2 → HNO_3 and by the reaction set NO_2 + O_3 → NO_3; NO_2 + NO_3 → N_(2)O_5; N_(2)O_5 + H_(2)O → 2HNO_3 are in error by +8.4% (+30/−45%) (OH+NO_2 too fast) in models using the Jet Propulsion Laboratory 1997 recommendations [DeMore et al., 1997]. Models that use recommendations for OH+NO2 and OH+HNO_3 based on reanalysis of recent and past laboratory measurements are in error by 1.2% (+30/−45%) (OH+NO_2 too slow). The +30%/−45% error limit reflects systematic uncertainties, while the statistical uncertainty is 0.65%. This analysis also shows that the POLARIS observations only modestly constrain the relative rates of the major NO_x production reactions HNO3 + OH → H_(2)O + NO_3 and HNO_3 + hν → OH + NO_2. Even under the assumption that all other aspects of the model are perfect, the POLARIS observations only constrain the rate coefficient for OH+HNO_3 to a range of 65% around the currently recommended value

    Inorganic chlorine partitioning in the summer lower stratosphere: Modeled and measured [ClONO_2]/[HCl] during POLARIS

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    We examine inorganic chlorine (Cl_y,) partitioning in the summer lower stratosphere using in situ ER-2 aircraft observations made during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) campaign. New steady state and numerical models estimate [ClONO_2]/[HCl] using currently accepted photochemistry. These models are tightly constrained by observations with OH (parameterized as a function of solar zenith angle) substituting for modeled HO_2 chemistry. We find that inorganic chlorine photochemistry alone overestimates observed [ClONO_2]/[HCl] by approximately 55–60% at mid and high latitudes. On the basis of POLARIS studies of the inorganic chlorine budget, [ClO]/[ClONO_2], and an intercomparison with balloon observations, the most direct explanation for the model-measurement discrepancy in Cl_y, partitioning is an error in the reactions, rate constants, and measured species concentrations linking HCl and ClO (simulated [ClO]/[HCl] too high) in combination with a possible systematic error in the ER-2 ClONO_2 measurement (too low). The high precision of our simulation (±15% 1σ for [ClONO_2]/[HCl], which is compared with observations) increases confidence in the observations, photolysis calculations, and laboratory rate constants. These results, along with other findings, should lead to improvements in both the accuracy and precision of stratospheric photochemical models

    A comparison of observations and model simulations of NO\u3csub\u3ex\u3c/sub\u3e/NO\u3csub\u3ey\u3c/sub\u3e in the lower stratosphere

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    Extensive airborne measurements of the reactive nitrogen reservoir (NOy) and its component nitric oxide (NO) have been made in the lower stratosphere. Box model simulations that are constrained by observations of radical and long-lived species and which include heterogeneous chemistry systematically underpredict the NOx (= NO + NO2) to NOy ratio. The model agreement is substantially improved if newly measured rate coefficients for the OH + NO2 and OH + HNO3 reactions are used. When included in 2-D models, the new rate coefficients significantly increase the calculated ozone loss due to NOx and modestly change the calculated ozone abundances in the lower stratosphere. Ozone changes associated with the emissions of a fleet of supersonic aircraft are also altered. Copyright 1999 by the American Geophysical Union

    Comparison of modeled and observed values of NO_2 and JNO_2 during the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) mission

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    Stratospheric measurements of NO, NO_(2), O_(3), ClO, and HO_(2) were made during spring, early summer, and late summer in the Arctic region during 1997 as part of the Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) field campaign. In the sunlit atmosphere, NO_(2) and NO are in steady state through NO2 photolysis and reactions involving O_(3), ClO, BrO, and HO_(2). By combining observations of O_(3), ClO, and HO_(2), observed and modeled values of the NO_(2) photolysis rate coefficient (JNO_(2)), and model estimates of BrO, several comparisons are made between steady state and measured values of both NO_(2) and JNO_(2). An apparent seasonal dependence in discrepancies between calculated and measured values was found; however, a source for this dependence could not be identified. Overall, the mean linear fits in the various comparisons show agreement within 19%, well within the combined uncertainties (±50 to 70%). These results suggest that photochemistry controlling the NO_(2)/NO abundance ratio is well represented throughout much of the sunlit lower stratosphere. A reduction in the uncertainty of laboratory determinations of the rate coefficient of NO + O_(3) → NO_(2) + O_(2) would aid future analyses of these or similar atmospheric observations

    Ozone destruction and production rates between spring and autumn in the Arctic stratosphere

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    In situ measurements of radical and long-lived species were made in the lower Arctic stratosphere (18 to 20 km) between spring and early autumn in 1997. The measurements include O_3, ClO, OH, HO_2, NO, NO_2, N_(2)O, CO, and overhead O_3. A photochemical box model constrained by these and other observations is used to compute the diurnally averaged destruction and production rates of O3 in this region. The rates show a strong dependence on solar exposure and ambient O_3. Total destruction rates, which reach 19%/month in summer, reveal the predominant role of NO_x and HO_x catalytic cycles throughout the period. Production of O_3 is significant only in midsummer air parcels. A comparison of observed O_3 changes with destruction rates and transport effects indicates the predominant role of destruction in spring and an increased role of transport by early autumn

    Observations of large reductions in the NO/NO_y ratio near the mid-latitude tropopause and the role of heterogeneous chemistry

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    During the 1993 NASA Stratospheric Photochemistry, Aerosols and Dynamics Expedition (SPADE), anomalously low nitric oxide (NO) was found in a distinct sunlit layer located above the mid-latitude tropopause. The presence of a significant amount of reactive nitrogen (NO_y) in the layer implies the systematic removal of NO, which is without precedent in stratospheric in situ observations. Large increases in measured chlorine monoxide (ClO) and the hydroperoxyl radical (HO_2) also were observed in the layer. Heterogeneous reaction rate constants of chlorine nitrate (ClONO_2) with hydrogen chloride (HCl) and H_2O to form nitric acid (HNO_3) on sulfate aerosol are enhanced in the NO removal layer by local increases in H_2O and aerosol surface area. The associated conversion of NO_x (= NO + NO_2) to HNO_3 is the most likely cause of the observed low NO and NO_x/NO_y values and high ClO values
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