Three regimes for sulfate-nitrate-ammonium aerosol formation

Total sulfate [S(VI] = [H2SO4(aq)] + [HSO4-] + [SO42-]

Total ammonia [N(-III)] = [NH3(g)] + [NH3(aq)] + [NH4+] moles per m3 of air
Total nitrate [N(V)] = [HNO3(g)] + [HNO3(aq)] + [NO3-]

[N(-III)]  2[S(VI)]
SNA ratio =
[N(V)]
gas
aerosol

N(V)

N(V)
N(V)

gas
aerosol

N(-III)
gas

N(-III)
aerosol

2S(VI)
2S(VI)
2S(VI)

N(-III)

2[S(VI)] > [N(-III)] 2[S(VI)]+[N(V)] > [N(-III)] > 2[S(VI)] 2[S(VI)]+[N(V)] < [N(-III)]
PM2.5 controlled PM2.5 controlled PM2.5 controlled
by sulfate by ammonia by sulfate and nitrate
REGIME 1 REGIME 2 REGIME 3
SNA ratio < 0 0 < SNA ratio < 1 SNA ratio > 1
Control SO2 emission Control NH3 emission Control SO2 and NOx emission
 Ionic composition of precipitation (late 1980s)

Acid rain is caused by H2SO4 and HNO3 originating from SO2 and NOx…
and can be neutralized by NH3 and soil dust (e.g., CaCO3)
 Mean pH of precipitation, 1990: acid rain across eastern US

National Acid Deposition Program

Since 1990, SO2 emissions have decreased by 90% and NOx emissions by 60%;
pH is now above 5 everywhere
 Natural pH of rain
• Equilibrium with natural CO2 (280 ppmv) results in a rain pH of 5.7:


H2O
CO 2 ( g )   CO 2 •H 2O K H  3  102 M atm-1

 HCO3- +H + K1  9  107 M
CO 2 •H 2 O 


 CO32- +H +
HCO3- 
 K 2  7  1010 M

Electroneutrality equation: [H  ]  [OH  ]  [HCO3 ]  2[CO32 ]

We know that pH < 7 so [H+] >> [OH-], [HCO3-] >> [CO32-]

[H  ]  [HCO3 ]

[H + ]  ( K1 K H PCO2 )1/2  105.7 M

• This pH can be modified by natural acids (H2SO4, HNO3, RCOOH…) and
bases (NH3, CaCO3) e natural rain has a pH in range 5-7

“Acid rain” refers to rain with pH < 5 e damage to ecosystems

 Equilibrium constants

If we have a forward reaction A+ B→C+D (rate constant kf)

then we must have the backward reaction C + D → A + B (rate constant kb)

If the backward reaction is negligible then the forward reaction is said irreversible

If the backward reaction is significant then the forward reaction is said reversible.

If the backward reaction is fast then the species may be in equilibrium:

d [A ] [C][D] kf
A+B C+D  kb [C][D]  kf [ A ][B]  0   K
dt [ A ][B] kb equilibrium
constant
Ionic dissociation reactions in water are fast and best described by equilibrium constants:

A+ + B - [ A  ][B ]
AB K
[ AB]
 Dissolution in water and acid dissociation
Dissolution is a physical process, governed by the Henry’s law equilibrium constant KH

 X(aq )
X( g ) 

ratio of the equilibrium concentration of a
compound in solution to the equilibrium
concentration of that compound in the gas [X(aq )]
phase over that solution. KH  units of M atm-1
pX where M ≡ moles per liter of water

Acid (HA) dissolution and dissociation in water:


 HA(aq ) [HA( aq )]
HA( g ) 
 KH 
pHA K H K a pHA
[A ] 
-

[H + ][A - ] [H + ]

H  A
HA(aq) 

 
Ka 
[HA(aq )]

[A - ] K
pKa = -log(Ka)  +a  1 when pH  pK a
[HA(aq)] [H ]
Brown Carbon (BrC)
 Organic Aerosol is Ubiquitous in the Atmosphere
Northern hemisphere aerosol components
NO3 SO4

NH4
Organic

[Zhang et al., 2007]

Tropics and southern hemisphere aerosol components

(Urban) (Rural)
Southern Africa South America Southeast Asia South Asia Oceania
[IPCC, 2013]
Primary and secondary organic aerosol (POA and SOA)

atmospheric oxidation condensation secondary

VOC low-volatility products
organic aerosol
large functionalized molecules

VOCs VOCs VOCs

primary organic aerosol

(direct emission)

open fires fuel combustion vegetation

and industry
Two models for formation of secondary organic aerosol
Classical model for reversible uptake by pre-existing organic aerosol

GAS ORGANIC PHASE

semi-volatile semi-volatile
VOC
oxidation gas aerosol

Alternative model for irreversible uptake by aqueous aerosol

GAS AQUEOUS PHASE

water-soluble dissolved nonvolatile

VOC gas oxidation species
oxidation gas
complexation
oligomerization
 Classical SOA modeling as gas-aerosol equilibrium
of semivolatile products of VOC oxidation
VOC oxidation generates semi-volatile organic gases SOG:
VOC + oxidant → 1SOG1 + 2SOG2 + …

…which then partition between the gas and aerosol phase to produce SOA:

SOGi

SOAi
Organic aerosol phase
mass concentration Mo
Mo ≡ POA + ΣSOAi
Pathways for aqueous-phase SOA formation
AQUEOUS
Same mechanisms for PHASE
aqueous aerosol and GAS PHASE Hydration,
cloudwater, but dominant oligomerization,
ionization
processes differ Organic mass
Oxidants Oxygenated > Henry’s Law
(·OH, O3, HO2, VOCs
NO, NO3) Aldehydes
Emitted Radicals
VOCs Epoxides Henry’s Law (OH, HO2,
Glyoxal SO4-, HSO4) • Organic acids
Methylglyoxal • CO2
• Organosulfates
Nonradical
reactions
(NH4+, SO4-2,
HSO4-
• Organosulfates
• Light-absorbing

Faye McNeill
Elemental composition are present in very trace amount (constitute less
than 2 % of PM2.5 mass)
Enrichment Factor – is a qualitative method to determine the
emission of elements coming from natural or anthropogenic source