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When organics and inorganics share the same aerosol

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SOAS thermodynamics match MARGA ammonium–sulfate data if models mix phases carefully and nonvolatile-cation emissions are revised.

Source

Coupling of organic and inorganic aerosol systems and the effect on gas-particle partitioning in the southeastern US

Pye HOT, Zuend A, Fry JL, et al. · Atmospheric chemistry and physics · 2018

doi.org/10.5194/acp-18-357-2018Read the full paper ↗31 citationscc by

Study at a glance

Design
Computational / modelling — CMAQ 5.2 and thermodynamic box models evaluated against SOAS inorganic/organic observations
N
Model–observation comparison for June–July 2013 SOAS; not a primary sample N
Population
Southeastern US aerosol thermodynamics during SOAS at Centreville and domain monitors
Outcome
Ammonium–sulfate partitioning and organic gas–particle bias under phase-mixing assumptions

Structured fields used in claim comparison tables when every cited study has a complete layer.

What they did

Authors ran CMAQ 5.2 at 12 km for June–July 2013 and ISORROPIA/AIOMFAC box models against SEARCH, CSN, AMS, MARGA, and SV-TAG during SOAS at Centreville.

What they found

CMAQ mean ammonium/2×sulfate is 0.73 versus CSN 0.67. MARGA ratios ~0.8–0.9 agree with equilibrium models; AMS/CSN look too ammonium-poor. Mixing organics with inorganics can raise pH but is not the main model-evaluation problem. Organic Fp bias falls if vapor pressures drop by 4.2.

The limits

What it doesn't show

AMS nitrate includes organonitrates so inorganic nitrate was zeroed; 50% of 2-methyltetrols may be dimers; cation emissions remain uncertain by about a factor of three.

Key terms

ISORROPIA
Inorganic aerosol thermodynamic model used in CMAQ.
AIOMFAC
Activity-coefficient model for organic–inorganic liquid mixtures.
Phase separation
Organic and aqueous inorganic liquids occupying distinct particle phases.
RN/2S
Molar ammonium divided by twice total sulfate.
MARGA
Monitor for Aerosols and Gases in Ambient air measuring PM2.5 ions.

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CMAQ mean RN/2S vs CSN:

Common questions

Which observations match thermodynamics?

MARGA, not AMS or CSN ammonium/sulfate.

CMAQ domain RN/2S?

0.73 versus CSN 0.67.

Do organics mixing fix inorganic bias?

They can change pH but are likely not the main issue.

Organic vapor-pressure tweak?

EVAPORATION Psat cut by 4.2 reduces bias.

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