Difference between revisions of "Monoterpene nitrate scheme"
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== Mechanism == | == Mechanism == | ||
− | |||
=== Species === | === Species === | ||
+ | The following table lists the '''new''' species included in the mechanism, their name in Browne et al. (2014), and whether they are treated as transported tracers: | ||
+ | |||
{| border="1" cellspacing="0" cellpadding="5" | {| border="1" cellspacing="0" cellpadding="5" | ||
|-bgcolor="#cccccc" | |-bgcolor="#cccccc" | ||
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|APIO2 ||APIP || No || RO2 from API | |APIO2 ||APIP || No || RO2 from API | ||
|- | |- | ||
− | |LIM ||LIM || Yes || limonene & other | + | |LIM ||LIM || Yes || limonene & other cyclic terpenes with two double bonds |
|- | |- | ||
|LIMO2 ||LIMP || No || RO2 from LIM | |LIMO2 ||LIMP || No || RO2 from LIM | ||
Line 29: | Line 30: | ||
|OLND ||TOLND || No || NO3-alkene adduct that primarily decomposes; from monoterpenes only here | |OLND ||TOLND || No || NO3-alkene adduct that primarily decomposes; from monoterpenes only here | ||
|- | |- | ||
− | |OLNN ||TOLNN || No || NO3-alkene adduct that primarily retains the NO3 | + | |OLNN ||TOLNN || No || NO3-alkene adduct that primarily retains the NO3 functional group; from monoterpenes only here |
|- | |- | ||
|MONITS ||TONIT || No || saturated first gen monoterpene organic nitrate | |MONITS ||TONIT || No || saturated first gen monoterpene organic nitrate | ||
Line 40: | Line 41: | ||
|} | |} | ||
+ | ===Kinetic reactions=== | ||
− | + | The following table lists the new kinetic reactions included in the monoterpene nitrate scheme: | |
− | The following table lists the new reactions included in the monoterpene nitrate scheme: | + | |
− | |||
{| border="1" cellspacing="0" cellpadding="5" | {| border="1" cellspacing="0" cellpadding="5" | ||
|-bgcolor="#cccccc" | |-bgcolor="#cccccc" | ||
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| APIO2 + NO || 0.82HO2 + 0.82NO2 + 0.23HCHO+ 0.43 RCHO + 0.11 ACET + 0.44MEK + 0.07 HCOOH + 0.12MONITS + 0.06MONITU || 4.00E-12 | | APIO2 + NO || 0.82HO2 + 0.82NO2 + 0.23HCHO+ 0.43 RCHO + 0.11 ACET + 0.44MEK + 0.07 HCOOH + 0.12MONITS + 0.06MONITU || 4.00E-12 | ||
|- | |- | ||
− | | APIO2 + HO2 || PIP ||1.50E-11 | + | | APIO2 + HO2 || PIP || 1.50E-11 |
|- | |- | ||
| APIO2 + MO2 || HO2 + 0.75HCHO + 0.25 MOH + 0.25 ROH + 0.75RCHO + 0.75MEK || 3.56E-14*exp(708/T) | | APIO2 + MO2 || HO2 + 0.75HCHO + 0.25 MOH + 0.25 ROH + 0.75RCHO + 0.75MEK || 3.56E-14*exp(708/T) | ||
Line 65: | Line 65: | ||
| API + O3 || 0.85OH + 0.1HO2 + 0.62 KO2 + 0.14 CO + 0.02 H2O2 + 0.65RCHO + 0.53MEK || 5.0E-16*exp(-530/T) | | API + O3 || 0.85OH + 0.1HO2 + 0.62 KO2 + 0.14 CO + 0.02 H2O2 + 0.65RCHO + 0.53MEK || 5.0E-16*exp(-530/T) | ||
|- | |- | ||
− | | API + NO3 || 0.1OLNN + 0.9 OLND || 1. | + | | API + NO3 || 0.1OLNN + 0.9 OLND || 8.33E-13*exp(490/T) |
+ | |- | ||
+ | | LIM + OH || LIMO2 || 4.20E-11*exp(401/T) | ||
+ | |- | ||
+ | | LIMO2 + NO || 0.686HO2 + 0.78NO2 + 0.22MONITU + 0.289 PRPE + 0.231HCHO + 0.491RCHO + 0.058HAC + 0.289MEK || 4.00E-12 | ||
+ | |- | ||
+ | | LIMO2 + HO2 || PIP ||1.50E-11 | ||
+ | |- | ||
+ | | LIMO2 + MO2 || HO2 + 0.192 PRPE + 1.04 HCHO + 0.308 MACR + 0.25 MOH + 0.25 ROH || 3.56E-14*exp(708/T) | ||
+ | |- | ||
+ | | LIMO2 + MCO3 || 0.5 HO2 + 0.5 MO2 + 0.192PRPE + 0.385 HCHO + 0.308 MACR + 0.5 RCOOH || 7.40E-13*exp(765/T) | ||
+ | |- | ||
+ | | LIMO2 + NO3 || HO2 + NO2 + 0.385PRPE + 0.385HCHO + 0.615MACR || 1.20E-12 | ||
+ | |- | ||
+ | | LIM + O3 || 0.85OH + 0.10HO2 + 0.16 ETO2 + 0.42 KO2 + 0.02H2O2 + 0.14CO + 0.46PRPE + 0.04HCHO + 0.79MACR + 0.01HCOOH + 0.07 RCOOH || 2.95E-15*exp(-783/T) | ||
+ | |- | ||
+ | | LIM + NO3 || 0.5OLNN + 0.5OLND || 1.22E-11 | ||
+ | |- | ||
+ | | PIP + OH || 0.49OH + 0.44R4O2 + 0.08RCHO + 0.41MEK || 3.4E-12*exp(190/T) | ||
+ | |- | ||
+ | | OLNN + NO || HO2 + NO2 + MONITS || 4.00E-12 | ||
+ | |- | ||
+ | | OLND + NO || 2.0 NO2 + 0.287 HCHO + 1.24 RCHO + 0.464 MEK || 4.00E-12 | ||
+ | |- | ||
+ | | OLNN + HO2 || 0.7MONITS + 0.3MONITU || 1.66E-13*exp(1300/T) | ||
+ | |- | ||
+ | | OLND + HO2 || 0.7MONITS + 0.3MONITU || 1.66E-13*exp(1300/T) | ||
+ | |- | ||
+ | | OLNN + MO2 || 2.0 HO2 + HCHO + 0.7MONITS + 0.3MONITU || 1.60E-13*exp(708/T) | ||
+ | |- | ||
+ | | OLND + MO2 || 0.5 HO2 + 0.5 NO2 + 0.965 HCHO + 0.93 RCHO + 0.348 MEK + 0.25 MOH + 0.25 ROH + 0.35 MONITS + 0.15 MONITU || 9.68E-14*exp(708/T) | ||
+ | |- | ||
+ | | OLNN + MCO3 || HO2 + MO2 + 0.7 MONITS + 0.3 MONITU || 8.85*E-13exp(765/T) | ||
+ | |- | ||
+ | | OLND + MCO3 || 0.5MO2 + NO2 + 0.287 HCHO + 1.24 RCHO + 0.464 MEK + 0.5 RCOOH || 5.37E-13*exp(765/T) | ||
+ | |- | ||
+ | | OLNN + NO3 || HO2 + NO2 + 0.7 MONITS + 0.3 MONITU || 1.20E-12 | ||
+ | |- | ||
+ | | OLND + NO3 || 2.0NO2 + 0.287 HCHO + 1.24 RCHO + 0.464 MEK || 1.20E-12 | ||
+ | |- | ||
+ | | OLNN + OLNN || HO2 + 1.4 MONITS + 0.6 MONITU || 7.0E-14*exp(1000/T) | ||
+ | |- | ||
+ | | OLNN + OLND || 0.5 HO2 + 0.5 NO2 + 0.202HCHO + 0.64 RCHO + 0.149 MEK +1.05 MONITS + 0.45 MONITU || 4.25E-14*exp(1000/T) | ||
+ | |- | ||
+ | | OLND + OLND || NO2 + 0.504 HCHO + 1.21 RCHO + 0.285MEK + 0.7 MONITS + 0.3 MONITU || 2.96E-14*exp(1000/T) | ||
+ | |- | ||
+ | | MONITS + OH || HONIT || 4.80E-12 | ||
+ | |- | ||
+ | | MONITU + OH || HONIT || 7.29E-11 | ||
+ | |- | ||
+ | | MONITU + O3 || HONIT || 1.67E-16 | ||
+ | |- | ||
+ | | MONITU + NO3 || HONIT || 3.15E-13*exp(-448/T) | ||
+ | |- | ||
+ | | MONITS + NO3 || HONIT || 3.15E-13*exp(-448/T) | ||
+ | |- | ||
+ | | HONIT + OH || NO3 + HKET || same as HNO3+OH | ||
+ | |- | ||
+ | |} | ||
+ | |||
+ | ===Photolysis reactions=== | ||
+ | |||
+ | The following table lists the new photolysis reactions included in the monoterpene nitrate scheme: | ||
+ | |||
+ | {| border="1" cellspacing="0" cellpadding="5" | ||
+ | |-bgcolor="#cccccc" | ||
+ | ! width="70pt" |'''Species''' | ||
+ | ! width="150pt" |'''Products''' | ||
+ | ! width="150pt" |'''j-values''' | ||
+ | |- | ||
+ | | PIP || OH + HO2 + RCHO || j(H2O2) | ||
+ | |- | ||
+ | | MONITS || MEK + NO2 || j(ONIT1) | ||
+ | |- | ||
+ | | MONITU || RCHO + NO2 || j(ONIT1) | ||
|- | |- | ||
+ | | HONIT || HKET + NO2 || j(ONIT1) | ||
|} | |} | ||
Latest revision as of 00:48, 11 March 2016
This page documents the monoterpene nitrate mechanism used in Fisher et al., 2016 (under review in Atmospheric Chemistry and Physics). This is an experimental mechanism that has not yet been included in the standard GEOS-Chem simulation.
Contents
Basis of the Implementation
This chemistry is largely based on the scheme developed by Browne et al. (2014) for use in WRF-Chem, which was built on the RACM2 scheme developed by Goliff et al. (2013).
Mechanism
Species
The following table lists the new species included in the mechanism, their name in Browne et al. (2014), and whether they are treated as transported tracers:
Species | Browne Species | Transported Tracer? | Note |
---|---|---|---|
API | API | Yes | alpha-pinene & other cyclic terpenes with one double bond |
APIO2 | APIP | No | RO2 from API |
LIM | LIM | Yes | limonene & other cyclic terpenes with two double bonds |
LIMO2 | LIMP | No | RO2 from LIM |
PIP | OP2 | No | peroxides from API & LIM |
OLND | TOLND | No | NO3-alkene adduct that primarily decomposes; from monoterpenes only here |
OLNN | TOLNN | No | NO3-alkene adduct that primarily retains the NO3 functional group; from monoterpenes only here |
MONITS | TONIT | No | saturated first gen monoterpene organic nitrate |
MONITU | UTONIT | No | unsaturated first gen monoterpene organic nitrate |
MONIT | n/a | Yes | first generation monoterpene organic nitrate tracer combines species MONIT=MONITU+MONITS (like ISOPN, MMN) |
HONIT | HONIT | No | 2nd gen monoterpene nitrate |
Kinetic reactions
The following table lists the new kinetic reactions included in the monoterpene nitrate scheme:
Reactants | Products | Rate Constant |
---|---|---|
API + OH | APIO2 | 1.21E-11*exp(440/T) |
APIO2 + NO | 0.82HO2 + 0.82NO2 + 0.23HCHO+ 0.43 RCHO + 0.11 ACET + 0.44MEK + 0.07 HCOOH + 0.12MONITS + 0.06MONITU | 4.00E-12 |
APIO2 + HO2 | PIP | 1.50E-11 |
APIO2 + MO2 | HO2 + 0.75HCHO + 0.25 MOH + 0.25 ROH + 0.75RCHO + 0.75MEK | 3.56E-14*exp(708/T) |
APIO2 + MCO3 | 0.5 HO2 + 0.5 MO2 + RCHO + MEK + RCOOH | 7.40E-13*exp(765/T) |
APIO2 + NO3 | HO2 + NO2 + RCHO + MEK | 1.20E-12 |
API + O3 | 0.85OH + 0.1HO2 + 0.62 KO2 + 0.14 CO + 0.02 H2O2 + 0.65RCHO + 0.53MEK | 5.0E-16*exp(-530/T) |
API + NO3 | 0.1OLNN + 0.9 OLND | 8.33E-13*exp(490/T) |
LIM + OH | LIMO2 | 4.20E-11*exp(401/T) |
LIMO2 + NO | 0.686HO2 + 0.78NO2 + 0.22MONITU + 0.289 PRPE + 0.231HCHO + 0.491RCHO + 0.058HAC + 0.289MEK | 4.00E-12 |
LIMO2 + HO2 | PIP | 1.50E-11 |
LIMO2 + MO2 | HO2 + 0.192 PRPE + 1.04 HCHO + 0.308 MACR + 0.25 MOH + 0.25 ROH | 3.56E-14*exp(708/T) |
LIMO2 + MCO3 | 0.5 HO2 + 0.5 MO2 + 0.192PRPE + 0.385 HCHO + 0.308 MACR + 0.5 RCOOH | 7.40E-13*exp(765/T) |
LIMO2 + NO3 | HO2 + NO2 + 0.385PRPE + 0.385HCHO + 0.615MACR | 1.20E-12 |
LIM + O3 | 0.85OH + 0.10HO2 + 0.16 ETO2 + 0.42 KO2 + 0.02H2O2 + 0.14CO + 0.46PRPE + 0.04HCHO + 0.79MACR + 0.01HCOOH + 0.07 RCOOH | 2.95E-15*exp(-783/T) |
LIM + NO3 | 0.5OLNN + 0.5OLND | 1.22E-11 |
PIP + OH | 0.49OH + 0.44R4O2 + 0.08RCHO + 0.41MEK | 3.4E-12*exp(190/T) |
OLNN + NO | HO2 + NO2 + MONITS | 4.00E-12 |
OLND + NO | 2.0 NO2 + 0.287 HCHO + 1.24 RCHO + 0.464 MEK | 4.00E-12 |
OLNN + HO2 | 0.7MONITS + 0.3MONITU | 1.66E-13*exp(1300/T) |
OLND + HO2 | 0.7MONITS + 0.3MONITU | 1.66E-13*exp(1300/T) |
OLNN + MO2 | 2.0 HO2 + HCHO + 0.7MONITS + 0.3MONITU | 1.60E-13*exp(708/T) |
OLND + MO2 | 0.5 HO2 + 0.5 NO2 + 0.965 HCHO + 0.93 RCHO + 0.348 MEK + 0.25 MOH + 0.25 ROH + 0.35 MONITS + 0.15 MONITU | 9.68E-14*exp(708/T) |
OLNN + MCO3 | HO2 + MO2 + 0.7 MONITS + 0.3 MONITU | 8.85*E-13exp(765/T) |
OLND + MCO3 | 0.5MO2 + NO2 + 0.287 HCHO + 1.24 RCHO + 0.464 MEK + 0.5 RCOOH | 5.37E-13*exp(765/T) |
OLNN + NO3 | HO2 + NO2 + 0.7 MONITS + 0.3 MONITU | 1.20E-12 |
OLND + NO3 | 2.0NO2 + 0.287 HCHO + 1.24 RCHO + 0.464 MEK | 1.20E-12 |
OLNN + OLNN | HO2 + 1.4 MONITS + 0.6 MONITU | 7.0E-14*exp(1000/T) |
OLNN + OLND | 0.5 HO2 + 0.5 NO2 + 0.202HCHO + 0.64 RCHO + 0.149 MEK +1.05 MONITS + 0.45 MONITU | 4.25E-14*exp(1000/T) |
OLND + OLND | NO2 + 0.504 HCHO + 1.21 RCHO + 0.285MEK + 0.7 MONITS + 0.3 MONITU | 2.96E-14*exp(1000/T) |
MONITS + OH | HONIT | 4.80E-12 |
MONITU + OH | HONIT | 7.29E-11 |
MONITU + O3 | HONIT | 1.67E-16 |
MONITU + NO3 | HONIT | 3.15E-13*exp(-448/T) |
MONITS + NO3 | HONIT | 3.15E-13*exp(-448/T) |
HONIT + OH | NO3 + HKET | same as HNO3+OH |
Photolysis reactions
The following table lists the new photolysis reactions included in the monoterpene nitrate scheme:
Species | Products | j-values |
---|---|---|
PIP | OH + HO2 + RCHO | j(H2O2) |
MONITS | MEK + NO2 | j(ONIT1) |
MONITU | RCHO + NO2 | j(ONIT1) |
HONIT | HKET + NO2 | j(ONIT1) |
References
- Browne, E. C., Wooldridge, P. J., Min, K.-E., and Cohen, R. C.: On the role of monoterpene chemistry in the remote continental boundary layer, Atmospheric Chemistry and Physics, 14, 1225–1238, doi:10.5194/acp-14-1225-2014, http://dx.doi.org/10.5194/acp-14-1225-2014, 2014.
- Fisher, J.A., D.J. Jacob, K.R. Travis, P.S. Kim, E.A. Marais, C. Chan Miller, K. Yu, L. Zhu, R.M. Yantosca, M.P. Sulprizio, J. Mao, P.O. Wennberg, J.D. Crounse, A.P. Teng, T.B. Nguyen, J.M. St Clair, R.C. Cohen, P. Romer, B.A. Nault, P.J. Wooldridge, J.L. Jimenez, P. Campuzano-Jost, D.A. Day, P.B. Shepson, F. Xiong, D.R. Blake, A.H. Goldstein, P.K. Misztal, T.F. Hanisco, G.M. Wolfe, T.B. Ryerson, A. Wisthaler, T. Mikoviny: Organic nitrate chemistry and its implications for nitrogen budgets in an isoprene- and monoterpene-rich atmosphere: constraints from aircraft (SEAC4RS) and ground-based (SOAS) observations in the Southeast US, submitted to Atmospheric Chemistry & Physics, 2016.
- Goliff, W. S., Stockwell, W. R., and Lawson, C. V.: The regional atmospheric chemistry mechanism, version 2, Atmospheric Environment, 68, 174 – 185, http://dx.doi.org/10.1016/j.atmosenv.2012.11.038, 2013.