scholarly journals Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

2010 ◽  
Vol 10 (14) ◽  
pp. 6969-6991 ◽  
Author(s):  
R. Volkamer ◽  
P. Sheehy ◽  
L. T. Molina ◽  
M. J. Molina
Keyword(s):  
Mexico City ◽  
Oxidative Capacity ◽  
Chemical Mechanism ◽  
Oh Radicals ◽  
Small Contribution ◽  
Radical Chain ◽  
Chain Reactions ◽  
Time Profiles ◽  
Concentration Time ◽  
Radical Production

Abstract. A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time-resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; the MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10–25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: Oxygenated VOC other than HCHO about 33%; HCHO and O3 photolysis each about 20%; O3/alkene reactions and HONO photolysis each about 12%, other sources <3%. Nitryl chloride photolysis could potentially contribute ~15% additional radicals, while NO2* + water makes – if any – a very small contribution (~2%). The peak radical production of ~7.5 107 molec cm−3 s−1 is found already at 10:00 a.m., i.e., more than 2.5 h before solar noon. O3/alkene reactions are indirectly responsible for ~33% of these radicals. Our measurements and analysis comprise a database that enables testing of the representation of radical sources and radical chain reactions in photochemical models. Since the photochemical processing of pollutants in the MCMA is radical limited, our analysis identifies the drivers for ozone and SOA formation. We conclude that reductions in VOC emissions provide an efficient opportunity to reduce peak concentrations of these secondary pollutants, because (1) about 70% of radical production is linked to VOC precursors; (2) lowering the VOC/NOx ratio has the further benefit of reducing the radical re-cycling efficiency from radical chain reactions (chemical amplification of radical sources); (3) a positive feedback is identified: lowering the rate of radical production from organic precursors also reduces that from inorganic precursors, like ozone, as pollution export from the MCMA caps the amount of ozone that accumulates at a lower rate inside the MCMA. Continued VOC reductions will in the future result in decreasing peak concentrations of ozone and SOA in the MCMA.

scholarly journals Oxidative capacity of the Mexico City atmosphere – Part 1: A radical source perspective

2007 ◽  
Vol 7 (2) ◽  
pp. 5365-5412 ◽  
Author(s):  
R. Volkamer ◽  
P. M. Sheehy ◽  
L. T. Molina ◽  
M. J. Molina
Keyword(s):  
Mexico City ◽  
Near Field ◽  
Oxidative Capacity ◽  
Chemical Mechanism ◽  
Oh Radicals ◽  
Time Resolved ◽  
Time Profiles ◽  
Concentration Time ◽  
Radical Production ◽  
Photolysis Frequencies

Abstract. A detailed analysis of OH, HO2 and RO2 radical sources is presented for the near field photochemical regime inside the Mexico City Metropolitan Area (MCMA). During spring of 2003 (MCMA-2003 field campaign) an extensive set of measurements was collected to quantify time resolved ROx (sum of OH, HO2, RO2) radical production rates from day- and nighttime radical sources. The Master Chemical Mechanism (MCMv3.1) was constrained by measurements of (1) concentration time-profiles of photosensitive radical precursors, i.e., nitrous acid (HONO), formaldehyde (HCHO), ozone (O3), glyoxal (CHOCHO), and other oxygenated volatile organic compounds (OVOCs); (2) respective photolysis-frequencies (J-values); (3) concentration time-profiles of alkanes, alkenes, and aromatic VOCs (103 compound are treated) and oxidants, i.e., OH- and NO3 radicals, O3; and (4) NO, NO2, meteorological and other parameters. The ROx production rate was calculated directly from these observations; MCM was used to estimate further ROx production from unconstrained sources, and express overall ROx production as OH-equivalents (i.e., taking into account the propagation efficiencies of RO2 and HO2 radicals into OH radicals). Daytime radical production is found to be about 10-25 times higher than at night; it does not track the abundance of sunlight. 12-h average daytime contributions of individual sources are: HCHO and O3 photolysis, each about 20%; O3/alkene reactions and HONO photolysis, each about 15%; unmeasured sources about 30%. While the direct contribution of O3/alkene reactions appears to be moderately small, source-apportionment of ambient HCHO and HONO identifies O3/alkene reactions as being largely responsible for jump-starting photochemistry about one hour after sunrise. The peak radical production is found to be higher than in any other urban influenced environment studied to date; further, differences exist in the timing of radical production. Our measurements and analysis comprise a database that enables testing of the representation of radical sources in photochemical models. Since the photochemical processing of pollutants is radical-limited in the MCMA, our analysis identifies the drivers for such processing. Three pathways are identified by which reductions in VOC emissions induce reductions in peak concentrations of secondary pollutants, such as O3 and secondary organic aerosol (SOA).

scholarly journals Oxidative capacity of the Mexico City atmosphere – Part 2: A RO<sub>x</sub> radical cycling perspective

2010 ◽  
Vol 10 (14) ◽  
pp. 6993-7008 ◽  
Author(s):  
P. M. Sheehy ◽  
R. Volkamer ◽  
L. T. Molina ◽  
M. J. Molina
Keyword(s):  
Chain Length ◽  
Mexico City ◽  
Oxidative Capacity ◽  
Early Morning ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Vapor Concentration ◽  
Oh Radicals ◽  
Radical Initiation ◽  
Very High

Abstract. A box model using measurements from the Mexico City Metropolitan Area study in the spring of 2003 (MCMA-2003) is presented to study oxidative capacity (our ability to predict OH radicals) and ROx (ROx=OH+HO2+RO2+RO) radical cycling in a polluted (i.e., very high NOx=NO+NO2) atmosphere. Model simulations were performed using the Master Chemical Mechanism (MCMv3.1) constrained with 10 min averaged measurements of major radical sources (i.e., HCHO, HONO, O3, CHOCHO, etc.), radical sink precursors (i.e., NO, NO2, SO2, CO, and 102 volatile organic compounds (VOC)), meteorological parameters (temperature, pressure, water vapor concentration, dilution), and photolysis frequencies. Modeled HOx (=OH+HO2) concentrations compare favorably with measured concentrations for most of the day; however, the model under-predicts the concentrations of radicals in the early morning. This "missing reactivity" is highest during peak photochemical activity, and is least visible in a direct comparison of HOx radical concentrations. We conclude that the most likely scenario to reconcile model predictions with observations is the existence of a currently unidentified additional source for RO2 radicals, in combination with an additional sink for HO2 radicals that does not form OH. The true uncertainty due to "missing reactivity" is apparent in parameters like chain length. We present a first attempt to calculate chain length rigorously i.e., we define two parameters that account for atmospheric complexity, and are based on (1) radical initiation, n(OH), and (2) radical termination, ω. We find very high values of n(OH) in the early morning are incompatible with our current understanding of ROx termination routes. We also observe missing reactivity in the rate of ozone production (P(O3)). For example, the integral amount of ozone produced could be under-predicted by a factor of two. We argue that this uncertainty is partly accounted for in lumped chemical codes that are optimized to predict ozone concentrations; however, these codes do not reflect the true uncertainty in oxidative capacity that is relevant to other aspects of air quality management, such as the formation of secondary organic aerosol (SOA). Our analysis highlights that apart from uncertainties in emissions, and meteorology, there is an additional major uncertainty in chemical mechanisms that affects our ability to predict ozone and SOA formation with confidence.

scholarly journals Use of filter radiometer measurements to derive local photolysis rates and for future monitoring network application

2020 ◽  
Author(s):  
Hannah L. Walker ◽  
Mathew R. Heal ◽  
Christine F. Braban ◽  
Mhairi Coyle ◽  
Sarah R. Leeson ◽  
...  
Keyword(s):  
Computational Cost ◽  
Monitoring Network ◽  
Atmospheric Model ◽  
Early Morning ◽  
Oh Radicals ◽  
Visible Radiation ◽  
Radical Chain ◽  
Chain Reactions ◽  
Radical Production ◽  
Filter Radiometer

Abstract. Production of hydroxyl (OH) radicals is frequently dominated by the photolysis of tropospheric ozone (O3). However, photolysis of nocturnal radical reservoirs, such as nitrous acid (HONO) and nitryl chloride (ClNO2), also produces radicals (OH and Cl atoms) that contribute to the oxidising capacity of the local atmosphere, and initiate many radical-chain reactions that lead to the formation of harmful secondary pollutants. Photolysis of nitric acid (HNO3) is also a minor radical production mechanism. In this paper, locally representative photolysis rate constants (j-values) for these molecules are shown to be critical for quantifying and understanding the rate of radical production in a local atmosphere. The first long-term 4-π filter radiometer dataset in the UK (21 November 2018–20 November 2019) available for direct atmospheric model validation is reported. Measurements were made at Auchencorth Moss, a Scottish rural background site, and j(NO2) is used to generate a measurement-driven adjustment factor (MDAF) for calculated j-values that accounts for local changes in meteorological variables without significantly increasing computational cost. Modelled clear-sky j-values and actinic flux for Auchencorth Moss were generated using the Tropospheric Ultraviolet and Visible radiation model (TUV; v.5.3.1). Applying the MDAF metric resulted in the calculated photolytic production rate of OH radicals, from all sources considered, being ~40 % lower over the year. Photolysis of HONO resulted in an increased rate of OH production compared to that from O3 in low-light conditions, such as sunrise and sunset (Solar Zenith Angle > 80°). Hydroxyl radical production from HONO photolysis exceeded that from O3 consistently throughout the day during the winter and autumn (by a factor of 5 and 2.1, respectively). Radical production rates from HONO and ClNO2 reached maximum values during the early morning hours of summer (06:00–09:00 UTC), with OH produced at a rate of 1.06 × 106 OH radicals cm−3 s−1, and Cl radicals at 3.20 × 104 Cl radicals cm−3 s−1, with the MDAF metric applied. This first application of the MDAF j-values demonstrates an efficient measurement and computational approach to improve modelling of the local atmospheric photochemistry that drives NO2, O3 and PM pollution levels. The incorporation of local radiation measurements in measurement networks, and the consequent greater spatial resolution of locally-relevant photolysis coefficients in model photolysis parameterisations, will improve the accuracy of assessment of air pollution and policy-intervention impacts.

scholarly journals Oxidative capacity of the Mexico City atmosphere – Part 2: A RO<sub>x</sub> radical cycling perspective

2008 ◽  
Vol 8 (2) ◽  
pp. 5359-5412 ◽  
Author(s):  
P. M. Sheehy ◽  
R. Volkamer ◽  
L. T. Molina ◽  
M. J. Molina
Keyword(s):  
Mexico City ◽  
Oxidative Capacity ◽  
Early Morning ◽  
Photochemical Activity ◽  
Chemical Mechanism ◽  
Ozone Production ◽  
Vapor Concentration ◽  
Photolysis Frequencies ◽  
Pressure Water ◽  
Major Chemical

Abstract. A box model using measurements from the Mexico City Metropolitan Area study in the spring of 2003 (MCMA-2003) is presented to study ROx (ROx=OH+HO2+RO2+RO) radical cycling in the troposphere. Model simulations were performed with the Master Chemical Mechanism (MCMv3.1) constrained with 10 min averaged measurements of major radical sources (i.e., HCHO, HONO, O3, CHOCHO, etc.), radical sink precursors (i.e., NO, NO2, SO2, CO, and 102 volatile organic compounds VOC), meteorological parameters (temperature, pressure, water vapor concentration, dilution), and photolysis frequencies. Modeled HOx concentrations compare favorably with measured concentrations for most of the day; however, the model under-predicts the concentrations of radicals in the early morning. This "missing reactivity" is highest during peak photochemical activity, and is least visible in a direct comparison of HOx radical concentrations. The true uncertainty due to "missing reactivity" is apparent in parameters like chain length, and ozone production (P(O3)). For example, the integral amount of ozone produced could be under-predicted by a factor of two. Our analysis highlights that apart from uncertainties in emissions, and meteorology, there is an additional major chemical uncertainty in current models.

Nitrate and chloride formation in chloramination

1994 ◽  
Vol 30 (9) ◽  
pp. 101-110
Author(s):  
V. Diyamandoglu
Keyword(s):  
Kinetic Model ◽  
Analytical Method ◽  
Kinetic Data ◽  
Experimental Results ◽  
Mass Balances ◽  
Time Profiles ◽  
Slow Decay ◽  
Concentration Time ◽  
End Products ◽  
Chlorine Residuals

The formation of nitrate and chloride as end-products of chloramination (combined chlorination) was investigated at pH ranging between 6.9 and 9.6 at 25°C. The experimental results comprised concentration-time profiles of combined chlorine residuals along with nitrate and chloride. Nitrite, if present, was always below the detectibility limit of the analytical method used (25 ppb). Mass balances on chlorine species depicted that chloride formed during the slow decay of combined chlorine residuals does not account for all the chlorine lost. This substantiates the formation of other reaction end-products which are yet to be identified. A kinetic model for chloramination is proposed based on the kinetic data obtained in this study.

scholarly journals Physiologically Based Pharmacokinetic Models of Probenecid and Furosemide to Predict Transporter Mediated Drug-Drug Interactions

2020 ◽  
Vol 37 (12) ◽  
Author(s):  
Hannah Britz ◽  
Nina Hanke ◽  
Mitchell E. Taub ◽  
Ting Wang ◽  
Bhagwat Prasad ◽  
...  
Keyword(s):  
Plasma Concentration ◽  
Organic Anion ◽  
Plasma Concentrations ◽  
Whole Body ◽  
Time Profiles ◽  
Pbpk Models ◽  
Physiologically Based Pharmacokinetic ◽  
Concentration Time ◽  
Anion Transporter ◽  
Physiologically Based

Abstract Purpose To provide whole-body physiologically based pharmacokinetic (PBPK) models of the potent clinical organic anion transporter (OAT) inhibitor probenecid and the clinical OAT victim drug furosemide for their application in transporter-based drug-drug interaction (DDI) modeling. Methods PBPK models of probenecid and furosemide were developed in PK-Sim®. Drug-dependent parameters and plasma concentration-time profiles following intravenous and oral probenecid and furosemide administration were gathered from literature and used for model development. For model evaluation, plasma concentration-time profiles, areas under the plasma concentration–time curve (AUC) and peak plasma concentrations (Cmax) were predicted and compared to observed data. In addition, the models were applied to predict the outcome of clinical DDI studies. Results The developed models accurately describe the reported plasma concentrations of 27 clinical probenecid studies and of 42 studies using furosemide. Furthermore, application of these models to predict the probenecid-furosemide and probenecid-rifampicin DDIs demonstrates their good performance, with 6/7 of the predicted DDI AUC ratios and 4/5 of the predicted DDI Cmax ratios within 1.25-fold of the observed values, and all predicted DDI AUC and Cmax ratios within 2.0-fold. Conclusions Whole-body PBPK models of probenecid and furosemide were built and evaluated, providing useful tools to support the investigation of transporter mediated DDIs.

ChemInform Abstract: Concise Syntheses of L-Selenomethionine and of L-Selenocystine Using Radical Chain Reactions.

ChemInform ◽  
1987 ◽  
Vol 18 (4) ◽  
Author(s):  
D. H. R. BARTON ◽  
D. BRIDON ◽  
Y. HERVE ◽  
P. POTIER ◽  
J. THIERRY ◽  
...  
Keyword(s):  
Radical Chain ◽  
Chain Reactions

scholarly journals The detection and inhibition of free radical chain reactions

1942 ◽  
Vol 180 (982) ◽  
pp. 237-256 ◽  
Keyword(s):  
Nitric Oxide ◽  
Free Radical ◽  
Chemical Analysis ◽  
Diethyl Ether ◽  
Pressure Increase ◽  
Stationary States ◽  
Decomposition Rates ◽  
Radical Chain ◽  
Chain Reactions ◽  
Limiting Values

Part I. Comparison of nitric oxide and propylene as inhibitors The reduction by propylene of the rate of pressure increase in the decomposition of propaldehyde at 550° has been shown by chemical analysis to represent a true inhibition of the reaction, and not to be due n an important degree to an induced polymerization of the propylene. With propaldehyde and with diethyl ether the limiting values to which the decomposition rates are reduced by nitric oxide and by propylene respectively are the same, although much more propylene is required to produce a given degree of inhibition. From this it is concluded that the limiting rates are more probably those of independent non-chain processes, than those characteristic of stationary states where the inhibitor starts and stops chains with equal efficiency.

Dithiocarbonate group transfer in radical chain reactions

1990 ◽  
Vol 31 (18) ◽  
pp. 2565-2568 ◽  
Author(s):  
Judith E. Forbes ◽  
Catherine Tailhan ◽  
Samir Z. Zard
Keyword(s):  
Radical Chain ◽  
Group Transfer ◽  
Chain Reactions
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