Engineering topics

Madronich, Sasha

Publications and source records attributed to Madronich, Sasha.

9 records

DOE OSTI2023

Inferring the photolysis rate of NO 2 in the stratosphere based on satellite observations

NO and NO 2 (NO x ) play major roles in both tropospheric and stratospheric chemistry. This paper provides a novel method to obtain a global and accurate photolysis rate for NO 2 based on satellite data. The photolysis rate J(NO 2 ) dominates the daytime diurnal variation of NO x photochemistry. Here the spatial variation of J(NO 2 ) at 50–90°S in December from 20–40km is obtained using data from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) experiment. Because NO and NO 2 rapidly exchange with one another in the daytime, J(NO 2 ) can be attained assuming steady state, and the results are shown to be consistent with model results. The J(NO 2 ) value decreases as the solar zenith angle increases and has a weak altitude dependence. A key finding is that satellite-derived J(NO 2 ) increases in the polar regions, in good agreement with model predictions, due to the effects of ice and snow on surface albedo. Thus, the method presented here provides an observation-based check on the role of albedo in driving polar photochemistry.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2021

Three-Dimensional Modeling of the Explicit Chemistry of Organic Aerosols: Formation, Removal, and Comparison with Observations

The major goals of the project were to further our understanding of the formation of secondary organic aerosols (SOA) from major anthropogenic and biogenic precursors, and to evaluate the GECKO-A chemistry model in the context of three DOE-led field campaigns (GoAmazon, BBOP, and HI-SCALE) with the long-term objective of improving the treatment of organic gases and particles in three-dimensional regional and global models. The three field campaigns were selected to evaluate and improve specific aspects of GECKO-A: (i) GoAmazon to help quantify interactions of biogenic and anthropogenic emissions; (ii) BBOP to predict the UV-visible absorption properties of biomass burning aerosols (brown carbon) from explicit molecular properties; and (iii) HI-SCALE to evaluate new model components that include aqueous (cloud) processing of organic gases and aerosols.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Exploration of oxidative chemistry and secondary organic aerosol formation in the Amazon during the wet season: explicit modeling of the Manaus urban plume with GECKO-A

The GoAmazon 2014/5 field campaign took place in Manaus, Brazil, and allowed the investigation of the interaction between background-level biogenic air masses and anthropogenic plumes. We present in this work a box model built to simulate the impact of urban chemistry on biogenic secondary organic aerosol (SOA) formation and composition. An organic chemistry mechanism is generated with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate the explicit oxidation of biogenic and anthropogenic compounds. A parameterization is also included to account for the reactive uptake of isoprene oxidation products on aqueous particles. The biogenic emissions estimated from existing emission inventories had to be reduced to match measurements. The model is able to reproduce ozone and NO x for clean and polluted situations. The explicit model is able to reproduce background case SOA mass concentrations but does not capture the enhancement observed in the urban plume. The oxidation of biogenic compounds is the major contributor to SOA mass. A volatility basis set (VBS) parameterization applied to the same cases obtains better results than GECKO-A for predicting SOA mass in the box model. The explicit mechanism may be missing SOA-formation processes related to the oxidation of monoterpenes that could be implicitly accounted for in the VBS parameterization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2018

Response of Surface Ultraviolet and Visible Radiation to Stratospheric SO 2 Injections

Climate modification by stratospheric SO 2 injections, to form sulfate aerosols, may alter the spectral and angular distributions of the solar ultraviolet and visible radiation that reach the Earth’s surface, with potential consequences to environmental photobiology and photochemistry. We used modeling results from the CESM1(WACCM) stratospheric aerosol geoengineering large ensemble (GLENS) project, following the RCP8.5 emission scenario, and one geoengineering experiment with SO 2 injections in the stratosphere, designed to keep surface temperatures at 2020 levels. Zonally and monthly averaged vertical profiles of O 3 , SO 2 , and sulfate aerosols, at 30 N and 70 N, served as input into a radiative transfer model, to compute biologically active irradiances for DNA damage ( i DNA ), UV index (UVI), photosynthetically active radiation (PAR), and two key tropospheric photodissociation coefficients ( j O1D for O 3 + hν (λ < 330 nm) → O( 1 D) + O 2 ; and j NO2 for NO 2 + hν (λ < 420 nm) → O( 3 P) + NO). We show that the geoengineering scenario is accompanied by substantial reductions in UV radiation. For example, comparing March 2080 to March 2020, i DNA decreased by 25% to 29% in the subtropics (30 N) and by 26% to 33% in the polar regions (70 N); UVI decreased by 19% to 20% at 30 N and 23% to 26% at 70 N; and j O1D decreased by 22% to 24% at 30 N and 35% to 40% at 70 N, with comparable contributions from sulfate scattering and stratospheric O 3 recovery. Different responses were found for processes that depend on longer UV and visible wavelengths, as these are minimally affected by ozone; PAR and j NO2 were only slightly lower (9–12%) at 30 N, but much lower at 70 N (35–40%). Similar reductions were estimated for other months (June, September, and December). Large increases in the PAR diffuse-direct ratio occurred in agreement with previous studies. Absorption by SO 2 gas had a small (~1%) effect on j O1D , i DNA , and UVI, and no effect on j NO2 and PAR.

42 ENGINEERING↗

DOE OSTI2015

FDATMOS16 non-linear partitioning and organic volatility distributions in urban aerosols

Gas-to-particle partitioning of organic aerosols (OA) is represented in most models by Raoult’s law, and depends on the existing mass of particles into which organic gases can dissolve. This raises the possibility of non-linear response of particle-phase OA to the emissions of precursor volatile organic compounds (VOCs) that contribute to this partitioning mass. Implications for air quality management are evident: A strong non-linear dependence would suggest that reductions in VOC emission would have a more-than-proportionate benefit in lowering ambient OA concentrations. Chamber measurements on simple VOC mixtures generally confirm the non-linear scaling between OA and VOCs, usually stated as a mass-dependence of the measured OA yields. However, for realistic ambient conditions including urban settings, no single component dominates the composition of the organic particles, and deviations from linearity are presumed to be small. Here we re-examine the linearity question using volatility spectra from several sources: (1) chamber studies of selected aerosols, (2) volatility inferred for aerosols sampled in two megacities, Mexico City and Paris, and (3) an explicit chemistry model (GECKO-A). These few available volatility distributions suggest that urban OA may be only slightly super-linear, with most values of the sensitivity exponent in the range 1.1-1.3, also substantially lower than seen in chambers for some specific aerosols. Furthermore, the rather low values suggest that OA concentrations in megacities are not an inevitable convergence of non-linear effects, but can be addressed (much like in smaller urban areas) by proportionate reductions in emissions.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2015

Modeling the Explicit Chemistry of Anthropogenic and Biogenic Organic Aerosols

The atmospheric burden of Secondary Organic Aerosols (SOA) remains one of the most important yet uncertain aspects of the radiative forcing of climate. This grant focused on improving our quantitative understanding of SOA formation and evolution, by developing, applying, and improving a highly detailed model of atmospheric organic chemistry, the Generation of Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) model. Eleven (11) publications have resulted from this grant.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Atmospheric Amines and Ammonia Measured with a Chemical Ionization Mass Spectrometer (CIMS)

We report ambient measurements of amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a Southeastern U.S. forest in Alabama and a moderately polluted Midwestern site during the summer. In the Alabama forest, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected on a daily basis. C3-amines and ammonia showed similar diurnal trends and temperature and wind direction dependences, and were not associated with transported CO and SO2 plumes. Consistent with temperature dependences, amine and ammonia in the gas and aerosol phases showed opposite diurnal trends, indicating gas-to-particle partitioning of amines and ammonia. Temperature dependences also imply reversible processes of amines and ammonia evaporation from soil surfaces in daytime and deposition of amines and ammonia to soil surfaces at nighttime. Various amines (C1-C6) at the pptv level were observed in the transported biomass burning plumes, showing that biomass burning can be a substantial source of amines in the Southeast U.S. At the moderately polluted Kent site, higher concentrations of amines (C1-C6, from pptv to tens of pptv) and ammonia (up to 6 ppbv) were detected. Diurnal variations of C1- to C3-amines and ammonia were correlated with the ambient temperature. C4- to C6-amines showed abrupt increases during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Lower amine concentrations at the rural forested site highlight the importance of constraining anthropogenic sources of amines.

You, Y.↗

NASA NTRS2000

Global Analysis of the Effects of Dust on the Photodissociation Rates

Aerosols scatter and absorb UV radiation and consequently either enhance or reduce the actinic fluxes and photolysis rates. Mineral dust particles are known to absorb UV radiation, but the impact on the photolysis rates is complicated by the optical properties dependency on the particle size, composition and wavelength. The high spatial and temporal variabilities of the dust size distribution add difficulties to the global analysis. The Georgia Tech/Goddard Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) model has been used to simulate several years of the global distribution of mineral dust in the troposphere. The optical parameters (extinction efficiency, single scattering albedo and asymmetry parameter) of the seven particle sizes (from 0.1 to 5 microns), transported by the model, have been inserted in the Tropospheric Ultraviolet-Visible (TUV) radiation model version 4. The photodissociation rates of J(N02) and J(03 to O(1D)) have been calculated with TUV-4 with and without dust particles on the global scale. The effects of dust on J(N02) and J(03) will be analyzed with an emphasis on the difference between major dust sources in Africa and Asia.

Ginoux, Paul↗

NASA NTRS1991

Ultraviolet radiation changes

A major consequence of ozone depletion is an increase in solar ultraviolet (UV) radiation received at the Earth's surface. This chapter discusses advances that were made since the previous assessment (World Meteorological Organization (WMO)) to our understanding of UV radiation. The impacts of these changes in UV on the biosphere are not included, because they are discussed in the effects assessment.

Mckenzie, Richard L.↗