Difference between revisions of "Caltech isoprene scheme"

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|1||ATOOH +OH=ATO2  +H2O ||2.66E-12exp(200/T) ||FP2009,New ||Rate uses MP+OH
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|1||ATOOH +OH=ATO2  +H2O ||2.66E-12exp(200/T) ||? ||Rate uses MP+OH
 
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|2||ATOOH +OH=MGLY  +OH    +H2O ||1.14E-12exp(200/T)||FP2009,New ||Rate uses MP+OH
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|2||ATOOH +OH=MGLY  +OH    +H2O ||1.14E-12exp(200/T)||? ||Rate uses MP+OH
 
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|3||RIO2 + NO = 0.883NO2 + 0.783HO2 + 0.660CH2O + 0.400MVK + 0.260MACR + 0.070ISOPND + 0.047ISOPNB + 0.123HC5 + 0.100DIBOO ||2.7E-12 exp(350/T)||FP2009ACP ||HNO3 channel deleted since nitrate is treated explicitly;paulothn2009;neglect methylfuran formation (increase the yield of other products)
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|3||RIO2 + NO = 0.883NO2 + 0.783HO2 + 0.660CH2O + 0.400MVK + 0.260MACR + 0.070ISOPND + 0.047ISOPNB + 0.123HC5 + 0.100DIBOO ||2.7E-12 exp(350/T)||Paulot 2009a ||HNO3 channel deleted since nitrate is treated explicitly;paulothn2009;neglect methylfuran formation (increase the yield of other products)
 
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|4||VRO2 + NO = 0.88NO2 + 0.35HO2 + 0.35CH2O + 0.53MCO3 + 0.53GLYC + 0.35MGLY + 0.12MVKN ||2.7E-12 exp(350/T)||replace old one ||
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|4||VRO2 + NO = 0.88NO2 + 0.35HO2 + 0.35CH2O + 0.53MCO3 + 0.53GLYC + 0.35MGLY + 0.12MVKN ||2.7E-12 exp(350/T)||Paulot 2009a||?
 
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|5||MRO2 + NO = 0.850NO2 + 0.850HO2 + 0.122MGLY + 0.728HAC + 0.728CO + 0.122CH2O + 0.150MACRN ||2.7E-12 exp(350/T)||replace old one ||This is modified based on Chuong et al. (2004).It was equally yield for MGLY and HAC in Paulot 2009 ACP, according to Peeters decomposition scheme.
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|5||MRO2 + NO = 0.85NO2 + 0.85HO2 + 0.122MGLY + 0.728HAC + 0.728CO + 0.122CH2O + 0.15MACRN ||2.7E-12 exp(350/T)||Paulot 2009a||This is modified based on Chuong et al. (2004).It was equally yield for MGLY and HAC in Paulot 2009 ACP, according to Peeters decomposition scheme.
 
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|6||MAN2+NO = 1.5NO2+0.5CH2O+0.5MGLY+0.5PROPNN+0.5CO+0.5OH      ||2.7E-1 exp(350/T) || ||Tyndall ETO2+NO
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|6||MAN2+NO = 1.5NO2 + 0.5CH2O + 0.5MGLY + 0.5PROPNN + 0.5CO + 0.5OH      ||2.7E-12 exp(350/T) || ||Tyndall ETO2+NO
 
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|7||ATO2 +HO2 =0.15MCO3  +0.15OH +0.15CH2O  +0.85ATOOH          ||8.60E-13 exp(700/T) || ||Tyndall, Dillon et al. (ACP 2008) cycling 15% reduce the recyling by 5% compared to previous version to be fully consistent with Dillon et al.
 
|7||ATO2 +HO2 =0.15MCO3  +0.15OH +0.15CH2O  +0.85ATOOH          ||8.60E-13 exp(700/T) || ||Tyndall, Dillon et al. (ACP 2008) cycling 15% reduce the recyling by 5% compared to previous version to be fully consistent with Dillon et al.

Revision as of 23:03, 3 February 2013

NOTE: This page is for documentation of new isoprene chemistry to be included in v9-02.

'Previous page of description can be found here New isoprene scheme prelim.

Implementation of the Paulot isoprene scheme

A full reference of all reactions used can be found in this document.

Species

New species added

Species Formula Note
MAOPO2 CH2OH-CHOO*CH3C(O)OOH Peroxy radical from MAOP (addition on the double bond)
ISOPNB C5H9NO4 Isoprene nitrate Beta
ISOPND C5H9NO4 Isoprene nitrate Delta
HC5 C55H8O2 Hydroxycarbonyl with 5C
DIBOO Dibble peroxy radical
MF3 Methyl furan but I didn’t use it
HC5OO Peroxy radical from HC5 (old IAO2?)
DHMOB C5H8O4 See Paulot et al., ACP (2009)
MOBA 5C acid from isoprene
MOBAOO RO2 from MOBA
ISOPNBO2 RO2 from ISOPND
ISOPNDO2 RO2 from ISOPND
PROPNN Propanone nitrate
ETHLN Ethanal nitrate
DHB Dihydroxybutanone (but removed)
MACRN Nitrate from MVK
MVKN Nitrate from MACR
PYAC Pyruvic acid
IEPOX Isoprene epoxide
IEPOXOO RO2 from IEPOX
PYPAN Pyruvic acid PAN
PYPO2 RO2 associated with PYPAN
ATOOH ATO2 peroxide
DRYPMNN Dry deposition for the different species
DRYALPH
DRYLIMO
DRYISOPND
DRYISOPNB
DRYRIP
DRYIEPOX
DRYMACRN
DRYMVKN
DRYPROPNN
DRYHCOOH
DRYACTA
DRYPYPAN

Species emitted and deposited

Species emitted Species deposited
NO NO2
NO2 O3
CO PAN
ALK4 HNO3
ISOP CH2O
ACET N2O5
PRPE H2O2
C3H8 PMN
C2H6 PPN
MEK R4N2
ALD2
CH2O PMNN
HNO3 IEPOX
O3 RIP
ISOPND
ISOPNB
PROPNN
MACRN
MVKN
HCOOH
ACTA

Henry's law constant

Species Heff(moles L-1 atm-1 ) ΔH/R (K) Reference
HCOOH 167,000 (pH = 5) -6100 Ito et al., 2007
CH3COOH 11,400 (pH = 5) -6300 Ito et al., 2007
MOBA 23000 -6300 Ito et al., 2007
GLYC 41000 -4600 Ito et al., 2007
GLYX 360000 -7200 Schweitzer et al., 1998
MGLY 3700 -7500 Ito et al., 2007
δ-ISOPN (ISOPND) 17000 -9200 Ito et al., 2007
β-ISOPN (ISOPND) 17000 -9200 Ito et al., 2007
MACRN 17000 -9200 Ito et al., 2007
MVKN 17000 -9200 Ito et al., 2007
PROPNN 1000 0 R. Sander (NITROOXYACETONE)
RIP 1.7e6 0 Marais et al., 2012
IEPOX 1.3e8 0 Marais et al., 2012
MAP 840 (f0 =1, reactive) -5300 R. Sander
HNO3 210000 -8700

Species removed from standard chemistry

Species Formula Note
GCO3 HOCH2C(O)OO hydroxy peroxyacetyl radical
GLCO3 HCOHC(O)OO peroxyacyl from GLYX
GLP HCOHC(O)OOH peroxide from GLCO3
GLPAN HCOHC(O)OONO2 peroxyacylnitrate from GLCO3
GP HOCH2C(O)OOH peroxide from GCO3
GPAN HOCH2C(O)OONO2 peroxyacylnitrate from GCO3
ISN1 HOCH2C(OO)(CH3)CH(ONO2)CH2OH RO2 from ISN2
RIO1 HOCH2C(OO)(CH3)CH=CHOH RO2 from isoprene oxidation products
IAO2 HOCH2C(CH3)(OO)CH(OH)CHO RO2 from isoprene oxidation products
MVN2 O2NOCH2CH(OO)C(O)CH3 RO2 from MVK+NO3

Species Activated from standard chemistry

Species Formula Note
GLYX CHOCHO glyoxal
HCOOH HCOOH formic acid
IALD HOCH2C(CH3)=CHCHO hydroxy carbonyl alkenes from isoprene

Reactions

New reactions

No Reaction Rate Constant Reference Note
1 ATOOH +OH=ATO2 +H2O 2.66E-12exp(200/T) ? Rate uses MP+OH
2 ATOOH +OH=MGLY +OH +H2O 1.14E-12exp(200/T) ? Rate uses MP+OH
3 RIO2 + NO = 0.883NO2 + 0.783HO2 + 0.660CH2O + 0.400MVK + 0.260MACR + 0.070ISOPND + 0.047ISOPNB + 0.123HC5 + 0.100DIBOO 2.7E-12 exp(350/T) Paulot 2009a HNO3 channel deleted since nitrate is treated explicitly;paulothn2009;neglect methylfuran formation (increase the yield of other products)
4 VRO2 + NO = 0.88NO2 + 0.35HO2 + 0.35CH2O + 0.53MCO3 + 0.53GLYC + 0.35MGLY + 0.12MVKN 2.7E-12 exp(350/T) Paulot 2009a ?
5 MRO2 + NO = 0.85NO2 + 0.85HO2 + 0.122MGLY + 0.728HAC + 0.728CO + 0.122CH2O + 0.15MACRN 2.7E-12 exp(350/T) Paulot 2009a This is modified based on Chuong et al. (2004).It was equally yield for MGLY and HAC in Paulot 2009 ACP, according to Peeters decomposition scheme.
6 MAN2+NO = 1.5NO2 + 0.5CH2O + 0.5MGLY + 0.5PROPNN + 0.5CO + 0.5OH 2.7E-12 exp(350/T) Tyndall ETO2+NO
7 ATO2 +HO2 =0.15MCO3 +0.15OH +0.15CH2O +0.85ATOOH 8.60E-13 exp(700/T) Tyndall, Dillon et al. (ACP 2008) cycling 15% reduce the recyling by 5% compared to previous version to be fully consistent with Dillon et al.
8 KO2+HO2 =OH +ALD2 +MCO3 7.40E-13 exp(700/T) replace old one
9 RIO2 +HO2=0.880RIP+0.120OH +0.047MACR +0.073MVK +0.120HO2+0.120CH2O 7.40E-13 exp(700/T) replace old one
10 VRO2 + HO2 = 0.100VRP + 0.680OH + 0.578GLYC + 0.578MCO3 + 0.187MEK + 0.102HO2 + 0.102CH2O + 0.102MGLY + 0.033RCHO 7.40E-13 exp(700/T) replace old one crounse2010
11 MRO2 +HO2 = 0.020MRP + 0.980OH + 0.980HO2 + 0.294CH2O + 0.686HAC + 0.294MGLY + 0.686CO 7.40E-13 exp(700/T) crounse2010
12 MAN2+HO2 =0.5PROPNN+0.5CO+0.5HO2+0.5MGLY+0.5CH2O+0.5NO2+OH 7.40E-13 exp(700/T)
13 INO2 +HO2 =0.5INPN +0.5ISOPND+0.5OH +0.5HO2 7.40E-13 exp(700/T)
14 RIO2+MO2=1.100HO2+1.220CH2O+0.280MVK+0.180MACR+0.300HC5+0.240MOH+0.240ROH 8.37E-14
15 RIO2 +RIO2 =1.280HO2+0.920CH2O +0.560MVK+0.360MACR+0.480ROH+0.500HC5 1.54E-13 FP2009,New
16 HC5OO + MO2 = 0.50HO2 + 0.33CO + 0.09H2 + 0.18HAC + 0.13GLYC + 0.29MGLY + 0.25MEK + 0.95CH2O + 0.25MOH + 0.25ROH + 0.5HO2 8.37E-14 FP2009 Tyndall MO2+MO2 Atkinson97 RO2+RO2 replace old one HC5OO=old IAO2
17 MRO2 + MO2 = 0.595HAC+0.255MGLY+0.595CO+1.255CH2O+1.700HO2+0.150ROH 8.37E-14
18 MAN2 + MO2 = 0.375PROPNN +0.375CO +0.375HO2+0.375MGLY +0.375CH2O +0.375NO2 +0.250CH2O +0.250R4N2 8.37E-14
19 INO2+MO2 = 0.55NO2+0.40HO2+0.425R4N2+0.025NO2+0.05MACR + 0.08CH2O+0.03MVK+0.25RCHO+0.75CH2O+0.25MOH+0.25ROH+0.5HO2 8.37E-14
20 RCO3 + HO2 = 0.410RP + 0.150RCOOH + 0.150O3 + 0.440OH + 0.440ETO2 4.3E-13exp(1040/T)
21 MAO3 + HO2 = 0.870OH +0.030O3 + 0.435CH2O + 0.435MO2 + 0.1MAOP + 0.030RCOOH + 0.283HAC + 0.152ATO2 + 0.870CO2 + 0.435CO 4.3E-13exp(1040/T)
22 PMN + OH = 1.000PMNO2 3.20E-11
23 PMNO2 + NO = 0.6CO2 + 0.6HAC + 0.6NO3 + 0.4CH2O + 0.4HO2 + 0.4PYPAN + 0.900NO2 K* (1-YN) where YN isreturned from fyrno3.f; K=2.7E-12 exp(350/T) (Xcarbn=4.0E00) FP2009,New J. Orlando, AE 2002
24 PMNO2 + NO=PMNN K* YN where YN is returned from fyrno3.f ; K=2.7E-12 exp(350/T) (Xcarbn=4.0E00) FP2009,New
25 PMNO2 + HO2 = 0.6CO2 + 0.6HAC + 0.6NO3 + 0.4CH2O + 0.4HO2 + 0.4PYPAN + 0.5R4P + 0.5OH 7.4E-13exp(700/T) FP2009,New
26 PYPO2 + NO2 + M = PYPAN LPL: 9.0E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6 FP2009,New same as RCO3+NO2 = PPN
27 PYPAN =PYPO2 +NO2 9.0E-29exp(14000/T) FP2009,New follow PPN
28 PYPO2 +NO = CO2+MCO3 +NO2 2.7E-12 exp(350/T) FP2009,New
29 PYPO2 +HO2 = CO2+MCO3 +OH 7.40E-13 exp(700/T) FP2009,New
30 GLYC + OH = 0.850CH2O +0.260CO2 + 0.580CO + 0.260OH + 0.740HO2 + 0.155GLYX FRAC=1-11.0729*exp(-1/73T) Rate=8.00E-12*FRAC FP2009,New Butkovskaya 2006 companion paper and Paulot 2009
31 GLYC + OH= HCOOH + 0.190OH +0.190CO + 0.810CO2 + 0.810HO2 FRAC=1-11.0729*exp(-1/73T) Rate=8.00E-12*(1-FRAC) FP2009,New Butkovskaya 2006 companion paper and Paulot 2009
32 GLYX+OH = HO2+2CO 3.1E-12exp(340/T) IUPAC2008 JMAO
33 MACR + OH = 0.53MAO3 +0.47MRO2 8.0E-12exp(380/T) FP2009,ACP MAO3(=MCO3 in the paper); MRO2(=MACROO in the paper)
34 HAC+OH=MGLY +HO2 FRAC=1-23.7*exp(1/60T) Rate=2.15E-12exp(305/T)*FRAC replace old one Butkovskaya JPC A (a,b)2006 and Paulot 2009
35 HAC+OH=0.500HCOOH + OH +0.5ACTA +0.5CO2 + 0.5CO + 0.5MO2 FRAC=1-23.7*exp(1/60T) Rate=2.15E-12exp(305/T)*(1-FRAC) replace old one Butkovskaya JPC A (a,b)2006 and Paulot 2009
36 INPN+OH=1.0OH+1.0NO2+1.0MEK 1.9E-11exp(390/T) two reactions because of the double bond (rate is from RIP +OH)
37 INPN+OH=0.36INO2+0.64R4N2+0.64OH 5.18E-12exp(200/T) abstraction of the H of the hydroperoxide
38 PRPN+OH=0.209PRN1+0.791OH+0.791PROPNN 8.78E-12exp(200/T)
39 ETP+OH=0.64OH+0.36ETO2+0.60ALD2 5.18E-12exp(200/T)
40 RA3P+OH=0.64OH+0.36A3O2+0.64RCHO 5.18E-12exp(200/T)
41 RB3P+OH=0.791OH+0.209B3O2+0.791ACET 8.78E-12exp(200/T)
42 R4P+OH=0.791OH+0.209R4O2+0.791RCHO 8.78E-12exp(200/T)
43 RP+OH=RCO3 6.13E-13exp(200/T) same as MAP+OH
44 PP+OH=0.791OH+0.209PO2+0.791RCHO 8.78E-12exp(200/T)
45 RIP+OH=0.387RIO2+0.613OH+0.613HC5 4.75E-12exp(200/T)
46 RIP + OH = OH + IEPOX 1.9E-11exp(390/T) FP2009, Science the yield of IEPOX is > 70% assumed to be 100%
47 IEPOX + OH = IEPOXOO 5.78e-11exp(-400/T) FP2009, Science
48 IEPOXOO + HO2 = 0.725HAC + 0.275GLYC + 0.275GLYX + 0.275MGLY + 1.125OH + 0.825HO2 + 0.200CO2 + 0.375CH2O + 0.074HCOOH + 0.251CO 7.4E-13exp(700/T) FP2009, Science unconstrained use HO2 reaction
49 IEPOXOO +NO=0.725HAC+0.275GLYC+0.275GLYX +0.275MGLY +0.125OH +0.825HO2+0.200CO2+0.375CH2O +0.074HCOOH +0.251CO +NO2 2.7E-12exp(350/T) FP: No peroxide was observed
50 IAP+OH =0.654OH+0.654DHMOB+0.346HC5OO 5.31E-12 exp(200/T)
51 VRP+OH=0.791OH+0.791MEK+0.209VRO2 8.78E-12exp(200/T)
52 MRP+OH=MRO2 1.84E-12exp(200/T)
53 MRP+OH=CO2+HAC+OH 4.40E-12exp(380/T)
54 MAOP + OH = MAO3 6.13E-13exp(200/T) same as MAP+OH
55 MAOP+OH=MAOPO2 3.60E-12exp(380/T)
56 MCO3+MAOPO2=1.0HAC+2.0CO2+OH+MO2 1.68E-12exp(500/T)
57 MCO3+MAOPO2=1.0ACTA+1.0MEK 1.87E-13 exp(500/T)
58 MAOPO2+MO2=0.7HAC +0.7CO2+0.7OH+1.0CH2O+0.7HO2+0.3ROH 8.37E-14
59 MAOPO2+MAOPO2=2.0HAC+2.0CO2+2.0OH 8.37E-14
60 MAOPO2+HO2=1.0HAC+1.0CO2+2.0OH 7.4E-13exp(700/T)
61 MAOPO2+NO=1.0HAC+1.0CO2+1.0OH+1.0NO2 K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00)
62 MAOPO2+NO=1.000HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) Not treated explicitly
63 OH+MAP=1.0MCO3 6.13E-13exp(200/T) From J. Orlando (unpublished results), how confident is this temperature dependence?
64 HC5+O3 = 0.6MGLY + 0.1OH + 0.12CH2O + 0.28GLYC + 0.3O3 + 0.4CO + 0.2H2 + 0.2HAC + 0.2HCOOH 6.16E-15 exp(-1814/T) HC5=old IALD??
65 R4O2+MCO3 = MO2 +0.32ACET+0.19MEK+0.27HO2+0.32ALD2+0.13RCHO+0.05A3O2+0.18B3O2+0.32ETO2 1.68E-12 exp(500/T)
66 ATO2+MCO3 = MCO3 +CH2O +MO2 1.68E-12 exp(500/T) IUPAC06
67 RIO2 + MCO3 = 0.887HO2 + 0.747CH2O + 0.453MVK + 0.294MACR + 0.140HC5 + 0.113DIBOO + CO2 + MO2 1.68E-12 exp(500/T) Follow RIO2+NO without the yield of nitrate and NO2 and then rescale it.
68 HC5OO +MCO3=0.216GLYX +0.234MGLY+0.234GLYC+0.216HAC +0.29DHMOB+0.17MOBA+0.09RCHO+HO2+0.09CO+MO2 1.68E-12 exp(500/T) HC5OO=old IAO2, this radical channel use the same as HC5OO+NO without NO2 yield.
69 VRO2+MCO3=0.4HO2+0.4CH2O+0.6MCO3+0.6GLYC+0.4MGLY+1.0MO2 1.68E-12 exp(500/T) this radical channel use the same as VRO2+NO without NO2 and MVKN yield. And carbon balance.
70 MRO2 +MCO3 =0.850HO2 +0.143MGLY+0.857HAC +0.857CO+0.143CH2O +1.0MO2 1.68E-12 exp(500/T) this radical channel use the same as MRO2+NO without NO2 and MACRN yield.
71 MAN2+MCO3 = MO2 +.5NO2+.5CH2O+.5MGLY+.5PROPNN+.5CO+.5HO2 1.68E-12 exp(500/T)
72 ATO2 +MCO3 =MGLY+ACTA 1.87E-13exp(500/T) IUPAC06 replace MEK with MGLY
73 HC5OO+MCO3 = MEK +ACTA 1.87E-13 exp(500/T)
74 ISOPNB+O3=0.610MVKN +0.390MACRN +0.270OH +CH2O 1.06E-16 Lockwood et al., 2010 ACP
75 ISOPND+O3=0.500PROPNN+0.500ETHLN +0.270OH +0.500GLYC+0.500HAC 5.3E-17 Lockwood et al., 2010 ACP
76 HC5+OH=HC5OO 3.35E-11exp(380/T) FP2009,ACP
77 HC5OO + NO = NO2 + 0.216GLYX + 0.234MGLY + 0.234GLYC + 0.216HAC + 0.290DHMOB + 0.170MOBA + 0.090RCHO + HO2 + 0.090CO K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00)
78 HC5OO +NO=HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00)
79 HC5OO +HO2 =0.1IAP+0.9OH +0.9MGLY +0.9GLYC +0.9HO2 7.4E-13exp(700/T) 90% recycling, no experimental data. Somewhat based upon the high recycling rate observed for MVK/MACR
80 ISOPND+OH=ISOPNDO2 2.64E-11exp(380/T) FP2009,ACP
81 ISOPNB+OH=ISOPNBO2 3.61E-12exp(380/T) FP2009,ACP
82 ISOPNDO2 + NO = 0.070MACRN + 0.310HCOOH + 0.440HAC + 0.130ETHLN + 0.650CH2O + 1.340NO2 + 0.150GLYC + 0.310NO3 + 0.150PROPNN + 0.340MEK + 0.350HO2 K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) FP2009,ACP
83 ISOPNDO2+NO=HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) Nitrates from ISOPND could not be observed in this experiment
84 ISOPNDO2 + HO2 = 0.035MACRN + 0.155HCOOH + 0.22HAC + 0.065ETHLN + 0.325CH2O + 0.170NO2 + 0.075GLYC + 0.155NO3 + 0.075PROPNN + 0.170MEK + 0.175HO2 + 0.5OH + 0.5ISNP 7.4E-13exp(700/T) Assume 50% recycling from HO2+RO2 (no experimental data - check Ng et al. for better estimates)
85 ISOPNBO2 + NO = 0.6GLYC + 0.6HAC + 0.4CH2O + 1.6NO2 + 0.26MACRN + 0.4HO2 + 0.14MVKN K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) FP2009,ACP
86 ISOPNBO2 + NO = HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) Nitrates from ISOPND could not be observed in this experiment
87 ISOPNBO2 + HO2 = 0.3GLYC + 0.3HAC + 0.2CH2O + 0.13MACRN + 0.07MVKN + 0.3NO2 + 0.2HO2 + 0.5OH + 0.5ISNP 7.4E-13exp(700/T) Assume 50% recycling from HO2+RO2 (no experimental data - check Ng et al. for better estimates)
88 ISNP+OH=0.612OH+0.612R4N1++0.193ISOPNBO2+0.193ISOPNDO2 4.75E-12exp(200/T) replace the old ISNP+OH
89 MVKN+OH=0.650HCOOH+NO3+0.650MGLY+0.350CH2O+0.350PYAC 1.5E-12exp(380/T) FP2009,ACP
90 MACRN + OH = 1.0MACRNO2 1.39E-11exp(380/T)
91 MACRNO2 + NO = 0.08ACTA + 0.08CH2O + 0.15NO3 + 0.07HCOOH + 0.070MGLY + 0.850HAC + 0.85NO2 + 0.93CO2 + 1.0NO2 2.7E-12exp(350/T) no nitrate yield (acyl)
92 MACRNO2 + HO2 = 0.08ACTA + 0.08CH2O + 0.15NO3 + 0.07HCOOH + 0.07MGLY + 0.85HAC + 0.85NO2 + 0.93CO2 + 1.0OH 7.4E-13exp(700/T) Assume 100% recycling. No experiment data. Inferred from the very high recycling observed for MAO2+HO2
93 MACRNO2 + NO2=1.0PMNN LPL: 9.00E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6
94 PMNN =1.000MACRNO2 +1.000NO2 9e-29*exp(14000/T)
95 DHMOB + OH = 1.5CO + 1.0HO2 + 0.5HAC + 0.5MEK 2.52E-11exp(410/T)
96 DIBOO +NO=HO2+NO2+0.520GLYC +0.520MGLY +0.480HAC+0.480GLYX K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) Dibble, 2004 Note that the yield of DIBOO Is likely overestimate (~30%)
97 DIBOO +NO=HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00)
98 DIBOO+HO2=HO2+OH +0.520GLYC+0.520MGLY+0.480HAC+0.480GLYX 7.4E-13exp(700/T) Assume 100% recycling. No experimental data. Somewhat derived from the high recycling in MVK/MACR
99 MOBA +OH=MOBAOO 2.79E-11exp(380/T)
100 MOBAOO+NO=RCHO+CO2+HO2+NO2 K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00)
101 MOBAOO+NO=HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00)
102 MOBAOO+HO2=0.500OH+0.500HO2+0.500RCHO+0.500CO2+0.500R4P 7.4E-13exp(700/T) FP2009,ACP No experimental constraint. Assume 50% recycling and go to R4P for the peroxide channel to avoid carrying another peroxide
103 MOBA +O3=OH +HO2+CO2+MEK 2.00E-17 FP2009,ACP Weak constraint on the rate constant - no constraint on the products
104 ETHLN +OH=CH2O +CO2+NO2 1.00E-11
105 PROPNN+OH=NO2+MGLY 1.00E-15 FP2009,ACP IUPAC says < 1e-12;Experiment suggests it is slower than than 1e-13-1e-15
Photolysis RIP = OH + HO2 + 0.710CH2O + 0.425MVK + 0.285MACR + 0.29HC5
Photolysis MACRN=NO2+HAC+MGLY+0.500CH2O+HO2+0.500CO
Photolysis MVKN=GLYC +NO2+MCO3
Photolysis ISOPNB=HC5+NO2+HO2
Photolysis ISOPND=HC5+NO2+HO2
Photolysis PROPNN=CH2O +NO2+CO +MO2
Photolysis ATOOH=OH +CH2O +MCO3
Photolysis PYPAN=0.300NO3+0.700NO2+MCO3 +CO2
Photolysis PYPAN=NO3++MCO3 +CO2

Removed reactions from standard chemistry

No Reaction Rate Constant Reference Note
1 RIO2 + NO = 0.90NO2 + 0.90HO2 + 0.34IALD + 0.34MVK + 0.22MACR + 0.56CH2O K=2.7E-12 exp(350/T) Atkinson 97&DBM(MCM 3.1)
2 RIO1+NO=NO2+IALD+HO2+0.75CH2O K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) Atkinson 97&DBM(MCM 3.1)
3 RIO1+NO = HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=5.00E00) Atkinson 97
4 IAO2+NO = 0.92HO2+0.61CO+0.17H2+0.33HAC+0.24GLYC +0.53MGLY+0.92NO2 +0.35CH2O+0.08HNO3 2.7E-12 exp(350/T) Tyndall ETO2+NO
5 ISN1+NO = 1.9NO2+0.95GLYC+0.95HAC +0.05HNO3+0.05NO2+0.05HO2 Paulson&Seinfeld 1992
6 VRO2+NO = NO2+0.28HO2+0.28CH2O+0.72MCO3+0.72GLYC+0.28MGLY K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) Atkinson 97
7 VRO2+NO = HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) Atkinson 97
8 MRO2 + NO = NO2 + HAC + CH2O + HO2 K* (1-YN) where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) Atkinson 97&DBM(MCM 3.1)
9 MRO2+NO = HNO3 K* YN where YN is returned from fyrno3.f K=2.7E-12 exp(350/T) (Xcarbn=4.00E00) Atkinson 97
10 MVN2+NO = 1.90NO2 +0.30HO2+0.30CH2O+0.60MCO3+0.60GLYC+0.30MGLY+0.10HNO3 2.7E-12 exp(350/T)
11 INO2+NO = 1.10NO2+0.80HO2+0.85HNO3+0.05NO2+0.10MACR+0.15CH2O+0.05MVK 2.7E-12 exp(350/T) Tyndall ETO2+NO
12 GLCO3+NO2 = GLPAN LPL: 9.00E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6 JPL02 Same as PPN
13 GLPAN = GLCO3+NO2 9e-29*exp(14000/T) JPL02 PPN
14 GCO3+NO2 = GPAN LPL: 9.00E-28(300/T)^8.9 HPL:7.70E-12(300/T)^0.2 Fc: 0.6 JPL02 Same as PPN
15 GPAN = GCO3+NO2N 9e-29*exp(14000/T) JPL02 PPN
16 GCO3+NO = NO2+HO2 +CH2O 6.70E-12 exp(340/T) IUPAC02 C2H5CO3+NO
17 GLCO3+NO = NO2+HO2+CO 6.70E-12 exp(340/T) IUPAC02 C2H5CO3+NO This reaction doesn't exist in the manual but is in the input The rate is from IUPAC2006 (or 2003), using the rate of CH3CH2C(O)O2+NO=C2H5C(O)O+NO2.
18 MAO3 + NO=MCO3 + CH2O + NO2 6.7E-12exp(340/T) IUPAC2006
19 ATO2+HO2 = MCO3 + MO2 8.60E-13 exp(700/T)
20 KO2+HO2 = MO2 + MGLY 7.40E-13 exp(700/T) Tyndall Tyndall forms CH3C(O)CH2OOH ,this must then split and go to MCO3+MO2, the products in chem..dat ??
21 RIO2+HO2 = RIP 7.40E-13 exp(700/T) Tyndall
22 RIO1+HO2 = RIP 7.40E-13 exp(700/T) Tyndall
23 IAO2 + HO2 = IAP 7.40E-13 exp(700/T) Tyndall
24 ISN1+HO2 = ISNP 7.40E-13 exp(700/T) Tyndall
25 VRO2+HO2 = VRP 7.40E-13 exp(700/T)
26 MRO2+HO2 = MRP 7.40E-13 exp(700/T)
27 MVN2 + HO2 = ISNP 7.40E-13 exp(700/T)
28 RIO2+MO2 = 0.42HO2 +0.35CH2O+0.2MVK +0.14MACR + 0.07RIO1 +0.06IALD+0.25MEK+0.75CH2O+0.25MOH+0.25ROH + 0.5HO2 8.37E-14 Tyndall MO2+MO2 Atkinson97 RO2+RO2
29 RIO1+MO2 = 0.50IALD+0.50HO2+0.38CH2O+0.25MEK+0.75CH2O+0.25MOH+0.25ROH+ 0.5HO2 8.37E-14 Tyndall MO2+MO2 Atkinson97 RO2+RO2
30 IAO2+MO2 = 0.50HO2+0.33CO+0.09H2+0.18HAC+0.13GLYC+0.29MGLY+0.25MEK+0.95CH2O+0.25MOH+0.25ROH+0.5HO2 8.37E-14 Tyndall MO2+MO2 Atkinson97 RO2+RO2
31 ISN1+MO2 = NO2+0.50GLYC+0.50HAC+0.25RCHO+0.75CH2O+0.25MOH+ 0.25ROH+0.50HO2 8.37E-14 Tyndall MO2+MO2 Atkinson97 RO2+RO2
32 RCO3+HO2=0.3RCOOH+0.3O3+ 0.7RP 4.30E-13 exp(1040/T)
33 GCO3 + HO2 = 0.71GP + 0.29O3 + 0.29CH2O 4.30E-13 exp(1040/T) DBM(MCM 3.1)
34 MAO3+HO2=0.3RCOOH+0.3O3 + 0.7MAOP 4.30E-13 exp(1040/T)
35 GLCO3+HO2=0.3RCOOH+0.3O3+0.7GLP 4.30E-13 exp(1040/T)
36 GLYC+OH =0.800GCO3+0.400CO+0.200H2+0.200HO2 1.00E-11 Atkinson 92,94
37 MACR + OH = 0.57MAO3 + 0.43MRO2 8.0E-12exp(380/T) IUPAC06 JMAO,DBM(MCM3.1)
38 HAC+OH = MGLY+HO2 3E-012 IUPAC06
39 GCO3+MO2 = 2CH2O +2HO2 1.68E-12 exp(500/T) T dep & B.R.Tyndall K298Villenave 98
40 GLCO3+MO2 = CH2O +2HO2+CO 1.68E-12 exp(500/T) T dep & B.R.Tyndall K298Villenave 98
41 GCO3+MO2 = RCOOH + CH2O 1.87E-13 exp(500/T) T dep & B.R.Tyndall K298Villenave 98
42 PP + OH = PO2 3.80E-12 exp(200/T) DBM(MCM 3.1)
43 GP + OH = GCO3 3.80E-12 exp(200/T) DBM(MCM 3.1)
44 GLP+OH = 0.50OH+0.50GLCO3+0.50CO 3.80E-12 exp(200/T) JPL97,MP+OH
45 RIP + OH = 0.509IALD + 0.509OH + 0.491RIO2 3.80E-12 exp(200/T) DBM,lumping from MCM3.1
46 IAP + OH = IAO2 3.80E-12 exp(200/T) DBM(MCM 3.1)
47 ISNP+OH = 0.50OH+0.50RCHO+0.50NO2+0.50ISN1 3.80E-12 exp(200/T) JPL97,MP+OH
48 VRP+OH = 0.50OH+0.50RCHO+0.50VRO2 3.80E-12 exp(200/T) JPL97,MP+OH
49 MRP + OH = MRO2 3.80E-12 exp(200/T) DBM(MCM 3.1)
50 MAOP + OH = MAO3 DBM(MCM 3.1)
51 MNO3+OH =CH2O+NOMNO32 8.0E-13exp(-1000/T) JPL06
52 IALD+OH = 0.44IAO2 +0.41MAO3+0.15HO2 3.70E-11 Paulson &Seinfeld, 92
53 IALD+O3 = 0.60MGLY+0.10OH+0.12CH2O+0.28GLYC+0.30O3+0.40CO+0.20H2+0.20HAC+0.20HCOOH 6.16E-15 exp(-1814/T) Paulson &Seinfeld, 92 MCO3+NO,MCO3,HO2,RCO3,GCO3,MAO3,GLCO3 rates are used for other radicals.
54 R4O2+MCO3 = MO2 +0.32ACET+0.19MEK+0.18MO2+0.27HO2+0.32ALD2+0.13RCHO+0.05A3O2+0.18B3O2+0.32ETO2 1.68E-12 exp(500/T) T dep & B.R.Tyndall K298Villenave 98
55 RIO2+MCO3 = MO2+0.864HO2+0.690CH2O +0.402MVK+0.288MACR+0.136RIO1+0.127IALD 1.68E-12 exp(500/T)
56 RIO1+MCO3 = MO2 +IALD+HO2+0.75CH2O 1.68E-12 exp(500/T)
57 IAO2+MCO3 = MO2 +HO2+0.65CO+0.18H2+0.36HAC+0.26GLYC+0.58MGLY+0.4CH2O 1.68E-12 exp(500/T)
58 ISN1+MCO3 = MO2+NO2+GLYC+HAC 1.68E-12 exp(500/T)
59 ATO2+MCO3 = MEK +ACTA 1.87E-13 exp(500/T)
60 KO2+MCO3 = MEK + ACTA 1.87E-13 exp(500/T)
61 RIO1+MCO3 = MEK +ACTA 1.87E-13 exp(500/T)
62 IAO2+MCO3 = MEK+ ACTA 1.87E-13 exp(500/T)
63 VRO2+MCO3 = MEK +ACTA 1.87E-13 exp(500/T)
64 MRO2+MCO3 = MEK +ACTA 1.87E-13 exp(500/T)
65 R4N1+MCO3 = RCHO +ACTA + NO2 1.87E-13 exp(500/T)
66 ISN1+MCO3 = RCHO +ACTA + NO2 1.87E-13 exp(500/T)
67 MVN2+MCO3 = RCHO +ACTA + NO2 1.87E-13 exp(500/T)
68 MAN2+MCO3 = RCHO +ACTA + NO2 1.87E-13 exp(500/T)
69 INO2+MCO3 = RCHO +ACTA + NO2 1.87E-13 exp(500/T)
70 PRN1 + MCO3 = RCHO +ACTA + NO2 1.87E-13 exp(500/T)
71 GCO3+MCO3 = MO2 + HO2+ CH2O 2.50E-12 exp(500/T) Tyndall,MCO3+MCO3
72 MONX=3.000CH2O 1.07E-5
73 GLCO3+MCO3 = MO2+ HO2+ CO 2.50E-12 exp(500/T) Tyndall,MCO3+MCO3
74 MVN2+MO2 = NO2+0.50CH2O+0.25MCO3 +0.25MGLY+0.25HO2+0.25RCHO+0.75CH2O+0.25MOH+0.25ROH+0.50HO2 8.37E-14
75 MVN2+MCO3 = MO2 +NO2+CH2O+0.5MCO3+0.5MGLY+0.5HO2 1.68E-12 exp(500/T)
76 MVN2+MCO3 = RCHO +ACTA + NO2 1.87E-13 exp(500/T)
Photolysis MNO3 = CH2O + H2O + NO2 As in Wild et al., 2000.
Photolysis GP = OH + HO2 + CH2O Uses MP cross-section
Photolysis GLP = OH + HO2 + CO Uses MP cross-section
Photolysis PP = OH + HO2 + ALD2 + CH2O DBM(MCM 3.1)
Photolysis RIP = OH + HO2 + 0.627CH2O + 0.368MVK + 0.259MACR + 0.373IALD DBM(MCM3.1)
Photolysis VRP = OH + 0.3HO2 + 0.3CH2O + 0.7MCO3 + 0.7GLYC + 0.3MGLY DBM(MCM3.1)
Emission EMISSION=ALPH
Emission EMISSION=LIMO
  • MVN2 reactions are removed because we deactivate the source MVK+NO3.
  • MNO3 is removed because there is no source of MNO3 in the model.

Update One - RO2+HO2 Reaction Rate

Update applied to all >C2 RO2 species reaction with HO2. These include, in the standard scheme, R4O2, R4N1, KO2, RIO2, RIO1, IAO2,ISN1, VRO2, MRO2, MVN2, MAN2, B3O2, INO2, PRN1, A3O2, PO2.

Old RO2+HO2 reaction rate: k = 7.40E-13*EXP(700/T)

New RO2+HO2 reaction rate: k = 2.91E-13*EXP(1300/T)[1-EXP(-0.245*n)], where n=no. of carbon atoms

Comparison of new and old RO2+HO2 reaction rates for C4 RO2 and C5 RO2:

Ro2 ho2 rate.jpg

Benchmarking for this update can be viewed at: (Benchmarking results for RO2+HO2 reaction)

Update Two - Transport of RIP

RIP = isoprene peroxide species formed at low-NOx (i.e. via the RO2+HO2 pathway)

This benchmark is done to understand the muted influence of the increased rate of the RO2+HO2 reaction on CH2O. Is this because the ultimate yield of CH2O is similar for all levels of NOx and RIP is not transported, leading to the realization of the ultimate yield of CH2O in the same grid box as its emission source?

Both schemes are run with initial concentrations of species set to zero. As RIP is added as an additional transported species this was viewed as the most effective way of comparing the two model runs.

Benchmarking for this update can be viewed at: (Benchmarking results for transporting RIP)

References

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  2. Crounse, J. D., Knap, H. C., Ørnsø, K. B., Jørgensen, S., Paulot, F., Kjaergaard, H. G., and Wennberg, P. O.: Atmospheric Fate of Methacrolein. 1. Peroxy Radical Isomerization Following Addition of OH and O2, The Journal of Physical Chemistry A, 116, 5756-5762, 10.1021/jp211560u, 2012.
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  6. Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479-1501, 2009a.
  7. Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kurten, A., St Clair, J. M., Seinfeld, J. H., and Wennberg, P. O.: Unexpected Epoxide Formation in the Gas-Phase Photooxidation of Isoprene, Science, 325, 730-733, 10.1126/science.1172910, 2009b.
  8. Peeters, J., Nguyen, T. L., and Vereecken, L.: HOx radical regeneration in the oxidation of isoprene, Phys. Chem. Chem. Phys., 11, 5935-5939, 10.1039/b908511d, 2009.
  9. Peeters, J., and Müller, J. F.: HOx radical regeneration in isoprene oxidation via peroxy radical isomerisations. II: experimental evidence and global impact, Phys. Chem. Chem. Phys., 12, 14227-14235, 10.1039/c0cp00811g, 2010.
  10. Xie, Y., Paulot, F., Carter, W. P. L., Nolte, C. G., Luecken, D. J., Hutzell, W. T., Wennberg, P. O., Cohen, R. C., and Pinder, R. W.: Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality, Atmos. Chem. Phys. Discuss., 12, 27173-27218, 10.5194/acpd-12-27173-2012, 2012.