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CMAQ Parameterizations of Cloud-Produced Secondary Organic Aerosol Ann Marie Carlton International Aerosol Modeling Algorithms Conference University of California, Davis December 6, 2007 SOA Formation Through Cloud Processing In-cloud chemistry Cloud evaporation SOA

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cmaq parameterizations of cloud produced secondary organic aerosol

CMAQ Parameterizations of Cloud-Produced Secondary Organic Aerosol

Ann Marie Carlton

International Aerosol Modeling Algorithms Conference

University of California, Davis

December 6, 2007

soa formation through cloud processing
SOA Formation Through Cloud Processing

In-cloud chemistry

Cloud evaporation

SOA

Reactive organic emissions

  • Gas phase organic emissions are oxidized (e.g., in the interstitial spaces of clouds) forming water-soluble organic gases.
  • Water-soluble gases partition into cloud droplets where they oxidize further, forming low volatility products.
  • These products remain in the particle phase upon cloud evaporation, contributing secondary organic aerosol (SOA).
slide3

Objective

  • Include “cloud processing” SOA pathway in 3-dimensional regional scale air quality simulations using CMAQ
  • Clouds provide a means of transporting constituents from the boundary layer to the free troposphere
    • More than 90% of cloud droplets evaporate

Motivation

  • CMAQ (and other models) under predict OC, in particular during the summer
    • The underprediction is greatest for aloft layers

Hypothesis

  • In-cloud chemistry explains, in part, the uderprediction aloft

Plausibility

geos chem oc predictions
GEOS-Chem OC Predictions

Heald et al., GRL (2005)

cmaq icartt oc comparisons

Aug. 14, 2004 - clouds

Aug. 11 – NYC plume

CMAQ & ICARTT OC comparisons

Aug. 3 – new england

CMAQ OC prediction

Aug. 15

transit to FL via Atlanta

Aug. 6

Ohio Valley power plants

ICARTT WSOC meas.

v4.6 SAPRC, AE4, 12km, eastern U.S.

transition from laboratory to regional scale modeling
Transition from laboratory to regional scale modeling
  • Sophisticated chemical mechanism not suitable for current CMAQ aqueous chemistry module (aqchem)
    • forward Euler solver for oxidation and bisection method for pH

(note linear convergence for bisection method)

cmaq aqueous chemistry map aqchem f

Molar conc. = initial amt. – amt. deposited (mol L-1)

bisection for pH, initial guesses between 0.01 – 10

liquid conc. (mol L-1) SO4, HSO4, SO3, HSO3, CO3, HCO3, OH, NH4, HCO2, NO3, Cl

Start iteration and bisection (3000 iterations)

Calc. final gas phase partial pressure of SO2, NH3, HNO3, HCOOH, CO2

liquid conc. (mol L-1) SO4, HSO4, SO3, HSO3, CO3, HCO3, OH, NH4, HCO2, NO3, Cl

Check for convergence

Check for convergence

Compute ionic strength and activity coefficient (Davies Eqn.)

Calculate liquid concentrations and final gas phase concs. of oxdidants

Cal. Min time step – check for large time step

Kinetic calcs

SIV oxidized < 0.05 of SIV oxidized since time 0, double DT

Don’t let DT > TAUCLD

1000 max. iterations

Compute wet depositions and phase concentrations for each species

TIME = TAUCLD (OR 1000 iterations)

CMAQ Aqueous Chemistry Map(aqchem.F)
enhance representation of aqueous chemistry in cmaq
Enhance Representation of Aqueous Chemistry in CMAQ
  • Improve partitioning parameterization
  • Develop Rosenbrock Solver
    • Comparison with box model for chemical mechanism (Barth et al., 2003) using a Gear solver
    • Develop generalized solver for a mechanism that represents the same aqueous chemistry currently in CMAQ for benchmarking
  • Extend to include advanced organic chemistry
    • Laboratory based
    • Sensitive reactions determined in parcel model (Ervens et al. 2007)
enhancing cmaq aqueous chemistry

Gas-to-drop partitioning

Enhancing CMAQ Aqueous Chemistry

Current CMAQ parameterization

volatilization

sink reactions

aqueous production

accommodation

interfacial processes by Schwartz (1986)

reaction types

Partitioning:

Reaction Types

kd

  • Acid/Base Equilibrium: [HA] [H+] + [A-]

ka

  • Oxidation:
rosenbrock method
Rosenbrock Method

Where J is the Jacobian

complex and explicit chemistry balanced with cmaq implementation
Complex and Explicit Chemistry Balanced with CMAQ Implementation
  • Yield-based parameterization (similar to how ‘traditional’ SOA modeling began)
    • Calculated maximum yield for oxalic acid from lab data (0.02)
    • Assumed same yield for higher MW species
    • Assumed same yields for MGLY as for GLY
  • Altieri et al., (2007)
    • OM:OC for cloud produced aerosol ~2
    • MW for cloud produced aerosol ~177 g mol-1
in cloud soa production added to cmaq
2 chemical “reactions” added to aqchem

Parameterization is based on laboratory experiments

GLY and MGLY react with OH to make non-reactive species “AORGCJ”

Reacting species (GLY, MGLY, OH) decrease

C...CALCULATE IN-CLOUD SOA PRODUCTION

C...Calculate GLY oxidation due to OH

DGLYDT = -1.0 * (RGLY3 ) * GLYL * OHL

C...Calculate MGLY oxidation due to OH

DMGLYDT = -1.0 * (RMGLY3) * MGLYL * OHL

C…Calculate AORGC Production

DORGC = DORGC - ( ( 0.04 * DGLYDT * DTW( 0 ) )

& + ( 0.04 * DMGLYDT * DTW( 0 ) ) )

In-cloud SOA production added to CMAQ
cmaq model testing
CMAQ Model Testing
  • 12km simulation for August 2004
  • CMAQ V4.6, SAPRC, AE4
  • 12km simulations, 14 vertical layers up to 100mb
  • Meterology
    • MM5 v3.6.3, with data nudging
    • Pleim-Xu land surface scheme, Reisner 2 microphysics, Kain-Fritsch cumulus parameterization, RRTM radiation parameterization
  • Emissions
    • 2001 inventory updated: point source emissions from base inventory by observed CEM data and Mobile 6 emission model
    • Biogenic emissions estimated using BEIS 3.13
august 14 2004 icartt cloud experiment

urban plume

o– OC prediction including SOAcld

o – OC prediction without SOAcld

-o- WSOC measurements

Solid line is aircraft altitude; secondary y-axis

Where CMAQ did not predict a cloud encountered by the NOAA-P3: predicted OC did not differ between simulations and both predictions for this time period were biased low.

Concentration (mgC/m3)

Altitude (m)

Time (UTC)

August 14, 2004 ICARTT Cloud Experiment
aug 14 cloud experiment vertical profile
Aug. 14 cloud experimentVertical Profile

Vertical profile:

comparison of CMAQ-predicted OC and PILS WSOC measurements

ICARTT

PILS WSOC meas.

Base CMAQ

CMAQ w/ AORGC

aug 14 cloud experiment
Aug. 14 cloud experiment

r2=0.74

x = CMAQ with cloud-produced SOA, o = base CMAQ OC prediction

fraction of total soa that is cloud produced

Layer 6 (cloud base height)

Fraction of Total SOA that is Cloud–Produced

Heald et al., (2006) – variability in OC measurements not predicted well

findings and implications
Findings and Implications
  • We expect SOA to form in aerosol water and cloud droplets
  • We expect this pathway to contribute SOA regionally and globally
  • SOA aloft has implications for long range transport and climate
  • Model performance enhanced for OC prediction when SOA cloud processing pathway is included – particularly aloft
    • Long range pollution transport
    • Global climate
future directions
Future Directions
  • Include Ervens et al. (2007) yield parameterization
  • Test this process for different seasons and locations
    • Full U.S., also in winter
  • Incorporate more explicit chemistry into CMAQ with a Rosenbrock solver
  • Find balance between more explicit chemistry and computational efficiency
  • Compare with other data sets
    • TexAQS; Speciated rain or cloud data; deposition measurements
acknowledgements
Acknowledgements
  • Gerald Gipson, Shawn Roselle, Rohit Mathur
  • Charles Chang
  • Barbara Ervens, Katye Altieri, Barbara Turpin, Sybil Sietzinger
  • Rodney Weber
disclaimer
Disclaimer

The research presented here was performed under the Memorandum of Understanding between the U.S. Environmental Protection Agency (EPA) and the U.S. Department of Commerce’s National Oceanic and Atmospheric Administration (NOAA) and under agreement number DW13921548. This work constitutes a contribution to the NOAA Air Quality Program, it does not necessarily reflect the views or policies of NOAA or EPA.