StratosphericOzoneSystem
Comprehensive stratospheric ozone chemistry (Seinfeld & Pandis 2006, Chapter 5) — a monolithic 15-state ODE plus 5 algebraic family sums combining the Chapman mechanism, O(1D) photochemistry, the N2O NOx source, and the NOx / HOx / ClOx / BrOx catalytic ozone-destruction cycles. Migrated from GasChem.jl@8c12c048 src/StratosphericChemistry.jl:497. SI units throughout.
Description
Comprehensive stratospheric ozone chemistry (Seinfeld & Pandis 2006, Chapter 5) — a monolithic 15-state ODE plus 5 algebraic family sums combining the Chapman mechanism, O(1D) photochemistry, the N2O NOx source, and the NOx / HOx / ClOx / BrOx catalytic ozone-destruction cycles. Migrated from GasChem.jl@8c12c048 src/StratosphericChemistry.jl:497. SI units throughout.
Reference
_source_ref: GasChem.jl@8c12c048482b515fb8eb2110bf8ab4b4f4e71309:src/StratosphericChemistry.jl:497
Upstream StratosphericOzoneSystem is the comprehensive stratospheric ozone-chemistry component from Seinfeld & Pandis (2006) Chapter 5 — it combines the Chapman mechanism, O(1D) photochemistry, the N2O NOx source (Section 5.3.1), and the NOx / HOx / ClOx / BrOx catalytic ozone-destruction cycles into one model. Despite the upstream docstring phrase ‘combining all cycles’, the @component is a monolithic MTK System: it re-declares every constant, parameter and variable and writes all 20 equations inline, then returns System(eqs, t; name) — there is no couple() call and no sub-system composition. It therefore migrates as a single models.StratosphericOzoneSystem entry, the same file shape as the sibling single-cycle migrations (chapman.esm, nox_cycle.esm, hox_cycle.esm, clox_cycle.esm, brox_cycle.esm).
Structure: 40 upstream @constants and 14 upstream @parameters are all encoded as type: parameter with their upstream defaults (the rig-wide convention for @constants migration, matching the sibling stratospheric files). 15 ODE state variables (O, O1D, O3, N2O, NO, NO2, OH, HO2, Cl, ClO, HCl, ClONO2, Br, BrO, HOBr) and 5 algebraic family variables (Ox, NOx, HOx, ClOx, BrOx) are encoded as type: state. The 20 equations (15 ODEs + 5 algebraic family sums) reproduce the upstream structural invariant length(equations(sys)) == 20 asserted by the upstream ‘Comprehensive System Structure’ test (StratosphericChemistry_test.jl:94-130).
Rate-coefficient handling: the upstream rate coefficients (k2 power-law (T_ref/T)^2.4, k4 and the Arrhenius coefficients k_NO_O3 … k_Br_O3, the termolecular k_ClO_NO2_M power-law (T_ref/T)^3.4, the weighted O(1D) quenching k_O1D_M, and the temperature-independent rate constants k_O1D_H2O_c / k_O1D_CH4_c / k_N2O_O1D_NO_c / k_N2O_O1D_N2_c / k_BrO_O_c / k_BrO_ClO_c / k_BrO_HO2_c) and the derived concentrations O2_conc = O2_mixM, CH4_conc = CH4_mixM, H2O_conc = H2O_mix*M are local Julia bindings, not MTK state. They are inlined verbatim into each equation right-hand side — bit-equivalent to writing the equations with the helper bindings, and keeping them out of the symbolic state preserves the upstream length(unknowns(sys)) count. This is the same inlining convention used by chapman.esm.
The parameter N2O_mix (3.0e-7) is declared in the upstream @parameters block but is not referenced by any equation or rate coefficient — it is vestigial (the N2O state default 9.3e16 m^-3, which equals N2O_mix*M at the default M=3.1e23, is set directly on the state rather than derived from this parameter). It is preserved here as a type: parameter for fidelity to the upstream parameter block.
Chemistry: odd oxygen (Ox = O + O3) is produced by O2 photolysis and destroyed by the O + O3 reaction and by the four catalytic cycles (NO/NO2, OH/HO2, Cl/ClO, Br/BrO), each of which cycles a radical pair without net consumption of the catalyst. O(1D), produced by the O3 -> O(1D) photolysis sub-channel and by N2O photolysis, is quenched by air (M) back to O(3P) and reacts with H2O and CH4 to make the OH that seeds HOx. N2O is the sole NOx source via N2O + O(1D) -> 2 NO (Section 5.3.1) and has no source term, so it decays monotonically. The HCl and ClONO2 reservoirs sequester reactive chlorine; HOBr buffers reactive bromine.
Units: SI throughout (number densities in m^-3, rate coefficients in m^3/s or m^6/s, photolysis rates in s^-1, temperature in K), converted from the Seinfeld & Pandis CGS values via cm^3/molec/s x 1e-6 -> m^3/s for bimolecular coefficients and cm^6/molec^2/s x 1e-12 -> m^6/s for the three-body coefficients. No CGS<->SI conversion at parse or runtime.
Tolerance rationale (model-level rel=1e-6): the expected values pinned in the tests below are references from the canonical ESS Python runner earthsci_ast.simulation.simulate(rtol=1e-10, atol=1e-12, cse=False) — the exact settings the inline-test gate uses — so reference/gate cross-integrator drift is zero by construction; rel=1e-6 is the spec section 6.6.4 default and matches the sibling stratospheric files. The initial_conditions_t0 test overrides to rel=1e-10 / abs=1e-14 (t=0 has no integration drift). The nighttime_photolysis_off test adds an abs=1e-6 floor for radical species that decay below the integrator’s atol=1e-12 floor once their photochemical sources are switched off.
Upstream test reproduction: the upstream comprehensive-system tests are ‘Comprehensive System Structure’ (20-equation / state-name structural check, reproduced by the shape of the variables and equations blocks), ‘Comprehensive System Integration’ (1-hour positivity, reproduced and tightened by comprehensive_integration_1hour), ‘N2O Destruction in Comprehensive System’ (reproduced and tightened by n2o_destruction_1day), and ‘N2O as NOx Source’ (reproduced and tightened by n2o_as_nox_source). The remaining tests (short-term transients, chemical-family tracking, temperature and density perturbations, dark chemistry) extend coverage beyond the upstream suite.
Stiffness declaration: this document declares the top-level solver block solver.stiffness = “high” (esm-spec 2.2), and its declared esm version is 1.1.0 for that reason alone – the solver block arrives at 1.1.0 and a 1.0.0 document carrying one is rejected with solver_version_too_old. The comprehensive stratospheric system is the stiffest document in this directory, because it carries the whole span of Chapter 5 chemistry at once: O(1D) is quenched by air at k_O1D_M * M = 9.99e6 1/s at the default T = 227 K and M = 3.1e23 m^-3, a lifetime of 1.0e-7 s; O(3P) relaxes on 1/(k2 * O2 * M) = 0.042 s; and N2O, the sole NOx source, is removed by j_N2O = 5e-8 1/s, a 2.0e7 s (0.63 yr) lifetime with no source term at all. Fourteen orders of magnitude of chemical timescale sit inside one 20-equation system, and n2o_destruction_1day integrates it over an 86400 s window. Measured through EarthSciAST.run_inline_tests in one warm Julia session: without the declaration the non-stiff default hands back every one of the file’s 176 assertions as an error, solver retcode MaxIters, after 1217.0 s – 20.3 minutes; with it the binding picks Rosenbrock23 and all 176 pass in 118.4 s – 68.6 s on a repeat, once the specialization for this system is compiled.
What the stiff pick costs in accuracy, stated plainly: under Rosenbrock23 at the runner’s default integration tolerances, 174 of the 176 assertions compare against a non-zero expected value (the other two pin O and O(1D) at exactly 0.0 and are judged on the absolute floor), and 173 of those 174 land within 1.1e-7 relative of the stored reference values – the worst of them being Br at t = 1 s in default_short_term_100s (26196331783.22968 against a recorded 26196334555.6556, 1.06e-7 relative, 9.4 times inside the rel=1e-6 bound). The exception is NO at t = 3600 s in nighttime_photolysis_off: Rosenbrock23 gives 4.170514861316075e-05 m^-3 against a recorded 4.1705393178305094e-05 m^-3, which is 5.86e-6 relative – outside the model-level rel=1e-6 – and it passes only because that test also declares abs=1e-6, against which the 2.45e-10 m^-3 absolute difference is four orders of magnitude inside the bound. That is not a tolerance being abused: with every photolysis rate switched off, NO has decayed from 1e15 m^-3 to 4e-5 m^-3 over the hour, so the assertion is pinning numerical dust four orders of magnitude below one molecule per cubic metre, and the 2.45e-10 m^-3 the two integrators disagree by is nearly ten orders below it. That is exactly what the abs=1e-6 floor on this test was added for. It is recorded here rather than left for the next reader to rediscover: the stiff pick is measurably less accurate than scipy LSODA on that one value, and the two Julia sessions that measured it agree with each other bit for bit.
The other two bindings: Python integrates the file either way – 176/176 before and 176/176 after – so nothing in the Python gate ever said this document was stiff, which is the agreement-by-luck a three-binding sweep exists to stop relying on. What the declaration changes there is the method (LSODA to BDF), which costs 4.8 s -> 5.7 s and, on the same NO at t = 3600 s, moves the Python actual from 9.46e-8 to 1.46e-8 relative – closer to the recorded value, not further. No other Python actual moves by more than 1.7e-9 relative. The Rust binding parses and version-checks the block but does not map stiffness to an integrator, and its rows are identical before and after: 167 passes and the 9 assertions of n2o_as_nox_source erroring with diffsol’s Step size is too small at time = 3.53e-16, a pre-existing failure this declaration neither causes nor clears. As with components/gaschem/pollu.esm and components/gaschem/stratospheric/chapman.esm, the fact that this model needs an implicit method now lives in the document, where all three bindings read it, rather than in a per-file solver table in one gate._
Variables
| Name | Units | Default | Description |
|---|---|---|---|
O | m^-3 | 10000000000000.0 | Atomic oxygen O(3P) number density (1e7 molec/cm^3 x 1e6). |
O1D | m^-3 | 50000000.0 | Excited oxygen O(1D) number density (50 molec/cm^3 x 1e6). |
O3 | m^-3 | 3e+18 | Ozone number density (3e12 molec/cm^3 x 1e6). |
NO | m^-3 | 1000000000000000.0 | Nitric oxide number density (1e9 molec/cm^3 x 1e6). |
NO2 | m^-3 | 1000000000000000.0 | Nitrogen dioxide number density (1e9 molec/cm^3 x 1e6). |
OH | m^-3 | 1000000000000.0 | Hydroxyl radical number density (1e6 molec/cm^3 x 1e6). |
HO2 | m^-3 | 10000000000000.0 | Hydroperoxyl radical number density (1e7 molec/cm^3 x 1e6). |
Cl | m^-3 | 10000000000.0 | Chlorine atom number density (1e4 molec/cm^3 x 1e6). |
ClO | m^-3 | 10000000000000.0 | Chlorine monoxide number density (1e7 molec/cm^3 x 1e6). |
HCl | m^-3 | 1000000000000000.0 | Hydrogen chloride reservoir number density (1e9 molec/cm^3 x 1e6). |
ClONO2 | m^-3 | 1000000000000000.0 | Chlorine nitrate reservoir number density (1e9 molec/cm^3 x 1e6). |
Br | m^-3 | 100000000000.0 | Bromine atom number density (1e5 molec/cm^3 x 1e6). |
BrO | m^-3 | 1000000000000.0 | Bromine monoxide number density (1e6 molec/cm^3 x 1e6). |
HOBr | m^-3 | 1000000000000.0 | Hypobromous acid number density (1e6 molec/cm^3 x 1e6). |
N2O | m^-3 | 9.3e+16 | Nitrous oxide number density (~300 ppb at 30 km). |
Parameters
| Name | Units | Default | Description |
|---|---|---|---|
T_ref | K | 300.0 | Reference temperature for power-law rate coefficients. |
k2_A | m^6/s | 6e-46 | Pre-factor: O + O2 + M -> O3 + M (6e-34 cm^6/molec^2/s x 1e-12, Table B.2). |
k4_A | m^3/s | 8e-18 | Pre-factor: O + O3 -> 2O2 (8e-12 cm^3/molec/s x 1e-6, Table B.1). |
C_k4 | K | -2060.0 | exp(C/T) activation temperature: O + O3. |
k_O1D_O2_A | m^3/s | 3.2e-17 | Pre-factor: O(1D) + O2 quenching (3.2e-11 cm^3/molec/s x 1e-6, Page 143). |
C_O1D_O2 | K | 70.0 | exp(C/T) activation temperature: O(1D) + O2. |
k_O1D_N2_A | m^3/s | 1.8e-17 | Pre-factor: O(1D) + N2 quenching (1.8e-11 cm^3/molec/s x 1e-6, Page 143). |
C_O1D_N2 | K | 110.0 | exp(C/T) activation temperature: O(1D) + N2. |
k_O1D_H2O_c | m^3/s | 2.2e-16 | O(1D) + H2O -> 2OH rate (2.2e-10 cm^3/molec/s x 1e-6, Page 156). |
k_O1D_CH4_c | m^3/s | 1.5e-16 | O(1D) + CH4 -> OH + CH3 rate (1.5e-10 cm^3/molec/s x 1e-6, Page 156). |
k_N2O_O1D_NO_c | m^3/s | 6.7e-17 | N2O + O(1D) -> NO + NO rate (6.7e-11 cm^3/molec/s x 1e-6, Page 151). |
k_N2O_O1D_N2_c | m^3/s | 4.9e-17 | N2O + O(1D) -> N2 + O2 rate (4.9e-11 cm^3/molec/s x 1e-6, Page 151). |
k_NO_O3_A | m^3/s | 3e-18 | Pre-factor: NO + O3 (3e-12 cm^3/molec/s x 1e-6, Page 154). |
C_NO_O3 | K | -1500.0 | exp(C/T) activation temperature: NO + O3. |
k_NO2_O_A | m^3/s | 5.6e-18 | Pre-factor: NO2 + O (5.6e-12 cm^3/molec/s x 1e-6, Page 154). |
C_NO2_O | K | 180.0 | exp(C/T) activation temperature: NO2 + O. |
k_OH_O3_A | m^3/s | 1.7e-18 | Pre-factor: OH + O3 (1.7e-12 cm^3/molec/s x 1e-6, Page 161). |
C_OH_O3 | K | -940.0 | exp(C/T) activation temperature: OH + O3. |
k_HO2_O3_A | m^3/s | 1e-20 | Pre-factor: HO2 + O3 (1e-14 cm^3/molec/s x 1e-6, Table B.1). |
C_HO2_O3 | K | -490.0 | exp(C/T) activation temperature: HO2 + O3. |
k_HO2_O_A | m^3/s | 3e-17 | Pre-factor: HO2 + O (3e-11 cm^3/molec/s x 1e-6, Page 161). |
C_HO2_O | K | 200.0 | exp(C/T) activation temperature: HO2 + O. |
k_HO2_NO_A | m^3/s | 3.5e-18 | Pre-factor: HO2 + NO (3.5e-12 cm^3/molec/s x 1e-6, Page 158). |
C_HO2_NO | K | 250.0 | exp(C/T) activation temperature: HO2 + NO. |
k_Cl_O3_A | m^3/s | 2.3e-17 | Pre-factor: Cl + O3 (2.3e-11 cm^3/molec/s x 1e-6, Page 162). |
C_Cl_O3 | K | -200.0 | exp(C/T) activation temperature: Cl + O3. |
k_ClO_O_A | m^3/s | 3e-17 | Pre-factor: ClO + O (3e-11 cm^3/molec/s x 1e-6, Page 162). |
C_ClO_O | K | 70.0 | exp(C/T) activation temperature: ClO + O. |
k_ClO_NO_A | m^3/s | 6.4e-18 | Pre-factor: ClO + NO (6.4e-12 cm^3/molec/s x 1e-6, Page 163). |
C_ClO_NO | K | 290.0 | exp(C/T) activation temperature: ClO + NO. |
k_Cl_CH4_A | m^3/s | 9.6e-18 | Pre-factor: Cl + CH4 (9.6e-12 cm^3/molec/s x 1e-6, Table B.1). |
C_Cl_CH4 | K | -1360.0 | exp(C/T) activation temperature: Cl + CH4. |
k_OH_HCl_A | m^3/s | 2.6e-18 | Pre-factor: OH + HCl (2.6e-12 cm^3/molec/s x 1e-6, Page 168). |
C_OH_HCl | K | -350.0 | exp(C/T) activation temperature: OH + HCl. |
k_ClO_NO2_M_A | m^6/s | 1.8e-43 | Pre-factor: ClO + NO2 + M -> ClONO2 (1.8e-31 cm^6/molec^2/s x 1e-12, Page 165). |
k_Br_O3_A | m^3/s | 1.7e-17 | Pre-factor: Br + O3 (1.7e-11 cm^3/molec/s x 1e-6, Table B.1). |
C_Br_O3 | K | -800.0 | exp(C/T) activation temperature: Br + O3. |
k_BrO_O_c | m^3/s | 5e-17 | BrO + O -> Br + O2 rate (5e-11 cm^3/molec/s x 1e-6). |
k_BrO_ClO_c | m^3/s | 2e-18 | BrO + ClO -> Br + Cl + O2 rate (2e-12 cm^3/molec/s x 1e-6). |
k_BrO_HO2_c | m^3/s | 4e-17 | BrO + HO2 -> HOBr + O2 rate (4e-11 cm^3/molec/s x 1e-6). |
j_O2 | s^-1 | 1e-10 | O2 photolysis rate. |
j_O3 | s^-1 | 0.001 | O3 photolysis rate (total, both O(3P) and O(1D) channels). |
j_O3_O1D | s^-1 | 0.0005 | O3 -> O(1D) photolysis rate (the O(1D)-producing sub-channel). |
j_NO2 | s^-1 | 0.01 | NO2 photolysis rate. |
j_ClONO2 | s^-1 | 0.0001 | ClONO2 photolysis rate. |
j_HOBr | s^-1 | 0.001 | HOBr photolysis rate. |
j_N2O | s^-1 | 5e-08 | N2O photolysis rate (Section 5.3.1). |
T | K | 227.0 | Temperature (Page 145 mid-stratosphere reference, ~30 km). |
M | m^-3 | 3.1e+23 | Air number density at 30 km (3.1e17 molec/cm^3 x 1e6). |
O2_mix | 1 | 0.21 | O2 mixing ratio in air (dimensionless). |
N2_mix | 1 | 0.79 | N2 mixing ratio in air (dimensionless). |
CH4_mix | 1 | 1.6e-06 | CH4 mixing ratio in air (dimensionless). |
H2O_mix | 1 | 5e-06 | H2O mixing ratio in air (dimensionless). |
N2O_mix | 1 | 3e-07 | N2O mixing ratio (~300 ppb, Section 5.3.1, dimensionless). Declared upstream; vestigial — the N2O state default 9.3e16 m^-3 (= N2O_mix x M) is set directly rather than derived from this parameter at runtime. |
Observed
| Name | Units | Default | Description |
|---|---|---|---|
Ox | m^-3 | Odd oxygen family: algebraic sum Ox ~ O + O3. | |
NOx | m^-3 | Reactive nitrogen family: algebraic sum NOx ~ NO + NO2. | |
HOx | m^-3 | Hydrogen radical family: algebraic sum HOx ~ OH + HO2. | |
ClOx | m^-3 | Reactive chlorine family: algebraic sum ClOx ~ Cl + ClO. | |
BrOx | m^-3 | Reactive bromine family: algebraic sum BrOx ~ Br + BrO. |
Observed expressions
$$ Ox = O + O3 $$Odd oxygen family: algebraic sum Ox ~ O + O3.
$$ NOx = NO + NO2 $$Reactive nitrogen family: algebraic sum NOx ~ NO + NO2.
$$ HOx = OH + HO2 $$Hydrogen radical family: algebraic sum HOx ~ OH + HO2.
$$ ClOx = Cl + ClO $$Reactive chlorine family: algebraic sum ClOx ~ Cl + ClO.
$$ BrOx = Br + BrO $$Reactive bromine family: algebraic sum BrOx ~ Br + BrO.
Equations
$$ \mathrm{D}\left(O\right) = 2.0 \cdot j_{O2} \cdot O2_{mix} \cdot M + \left(j_{O3} + \left(-1.0\right) \cdot j_{O3\,O1D}\right) \cdot O3 + \left(O2_{mix} \cdot k_{O1D\,O2\,A} \cdot e^{\frac{C_{O1D\,O2}}{T}} + N2_{mix} \cdot k_{O1D\,N2\,A} \cdot e^{\frac{C_{O1D\,N2}}{T}}\right) \cdot O1D \cdot M + j_{NO2} \cdot NO2 + \left(-1.0\right) \cdot k2_{A} \cdot \frac{T_{ref}}{T}^{2.4} \cdot O \cdot O2_{mix} \cdot M \cdot M + \left(-1.0\right) \cdot k4_{A} \cdot e^{\frac{C_{k4}}{T}} \cdot O \cdot O3 + \left(-1.0\right) \cdot k_{NO2\,O\,A} \cdot e^{\frac{C_{NO2\,O}}{T}} \cdot NO2 \cdot O + \left(-1.0\right) \cdot k_{ClO\,O\,A} \cdot e^{\frac{C_{ClO\,O}}{T}} \cdot ClO \cdot O + \left(-1.0\right) \cdot k_{BrO\,O\,c} \cdot BrO \cdot O + \left(-1.0\right) \cdot k_{HO2\,O\,A} \cdot e^{\frac{C_{HO2\,O}}{T}} \cdot HO2 \cdot O $$ $$ \mathrm{D}\left(O1D\right) = j_{O3\,O1D} \cdot O3 + j_{N2O} \cdot N2O + \left(-1.0\right) \cdot \left(O2_{mix} \cdot k_{O1D\,O2\,A} \cdot e^{\frac{C_{O1D\,O2}}{T}} + N2_{mix} \cdot k_{O1D\,N2\,A} \cdot e^{\frac{C_{O1D\,N2}}{T}}\right) \cdot O1D \cdot M + \left(-1.0\right) \cdot k_{O1D\,H2O\,c} \cdot O1D \cdot H2O_{mix} \cdot M + \left(-1.0\right) \cdot k_{O1D\,CH4\,c} \cdot O1D \cdot CH4_{mix} \cdot M + \left(-1.0\right) \cdot k_{N2O\,O1D\,NO\,c} \cdot O1D \cdot N2O + \left(-1.0\right) \cdot k_{N2O\,O1D\,N2\,c} \cdot O1D \cdot N2O $$ $$ \mathrm{D}\left(O3\right) = k2_{A} \cdot \frac{T_{ref}}{T}^{2.4} \cdot O \cdot O2_{mix} \cdot M \cdot M + \left(-1.0\right) \cdot j_{O3} \cdot O3 + \left(-1.0\right) \cdot k4_{A} \cdot e^{\frac{C_{k4}}{T}} \cdot O \cdot O3 + \left(-1.0\right) \cdot k_{NO\,O3\,A} \cdot e^{\frac{C_{NO\,O3}}{T}} \cdot NO \cdot O3 + \left(-1.0\right) \cdot k_{OH\,O3\,A} \cdot e^{\frac{C_{OH\,O3}}{T}} \cdot OH \cdot O3 + \left(-1.0\right) \cdot k_{HO2\,O3\,A} \cdot e^{\frac{C_{HO2\,O3}}{T}} \cdot HO2 \cdot O3 + \left(-1.0\right) \cdot k_{Cl\,O3\,A} \cdot e^{\frac{C_{Cl\,O3}}{T}} \cdot Cl \cdot O3 + \left(-1.0\right) \cdot k_{Br\,O3\,A} \cdot e^{\frac{C_{Br\,O3}}{T}} \cdot Br \cdot O3 $$ $$ \mathrm{D}\left(N2O\right) = \left(-1.0\right) \cdot j_{N2O} \cdot N2O + \left(-1.0\right) \cdot k_{N2O\,O1D\,NO\,c} \cdot O1D \cdot N2O + \left(-1.0\right) \cdot k_{N2O\,O1D\,N2\,c} \cdot O1D \cdot N2O $$ $$ \mathrm{D}\left(NO\right) = 2.0 \cdot k_{N2O\,O1D\,NO\,c} \cdot O1D \cdot N2O + j_{NO2} \cdot NO2 + k_{NO2\,O\,A} \cdot e^{\frac{C_{NO2\,O}}{T}} \cdot NO2 \cdot O + \left(-1.0\right) \cdot k_{NO\,O3\,A} \cdot e^{\frac{C_{NO\,O3}}{T}} \cdot NO \cdot O3 + \left(-1.0\right) \cdot k_{ClO\,NO\,A} \cdot e^{\frac{C_{ClO\,NO}}{T}} \cdot ClO \cdot NO + \left(-1.0\right) \cdot k_{HO2\,NO\,A} \cdot e^{\frac{C_{HO2\,NO}}{T}} \cdot HO2 \cdot NO $$ $$ \mathrm{D}\left(NO2\right) = k_{NO\,O3\,A} \cdot e^{\frac{C_{NO\,O3}}{T}} \cdot NO \cdot O3 + k_{HO2\,NO\,A} \cdot e^{\frac{C_{HO2\,NO}}{T}} \cdot HO2 \cdot NO + k_{ClO\,NO\,A} \cdot e^{\frac{C_{ClO\,NO}}{T}} \cdot ClO \cdot NO + \left(-1.0\right) \cdot j_{NO2} \cdot NO2 + \left(-1.0\right) \cdot k_{NO2\,O\,A} \cdot e^{\frac{C_{NO2\,O}}{T}} \cdot NO2 \cdot O + \left(-1.0\right) \cdot k_{ClO\,NO2\,M\,A} \cdot \frac{T_{ref}}{T}^{3.4} \cdot ClO \cdot NO2 \cdot M $$ $$ \mathrm{D}\left(OH\right) = 2.0 \cdot k_{O1D\,H2O\,c} \cdot O1D \cdot H2O_{mix} \cdot M + k_{O1D\,CH4\,c} \cdot O1D \cdot CH4_{mix} \cdot M + k_{HO2\,O\,A} \cdot e^{\frac{C_{HO2\,O}}{T}} \cdot HO2 \cdot O + k_{HO2\,O3\,A} \cdot e^{\frac{C_{HO2\,O3}}{T}} \cdot HO2 \cdot O3 + k_{HO2\,NO\,A} \cdot e^{\frac{C_{HO2\,NO}}{T}} \cdot HO2 \cdot NO + j_{HOBr} \cdot HOBr + \left(-1.0\right) \cdot k_{OH\,O3\,A} \cdot e^{\frac{C_{OH\,O3}}{T}} \cdot OH \cdot O3 + \left(-1.0\right) \cdot k_{OH\,HCl\,A} \cdot e^{\frac{C_{OH\,HCl}}{T}} \cdot OH \cdot HCl $$ $$ \mathrm{D}\left(HO2\right) = k_{OH\,O3\,A} \cdot e^{\frac{C_{OH\,O3}}{T}} \cdot OH \cdot O3 + \left(-1.0\right) \cdot k_{HO2\,O\,A} \cdot e^{\frac{C_{HO2\,O}}{T}} \cdot HO2 \cdot O + \left(-1.0\right) \cdot k_{HO2\,O3\,A} \cdot e^{\frac{C_{HO2\,O3}}{T}} \cdot HO2 \cdot O3 + \left(-1.0\right) \cdot k_{HO2\,NO\,A} \cdot e^{\frac{C_{HO2\,NO}}{T}} \cdot HO2 \cdot NO + \left(-1.0\right) \cdot k_{BrO\,HO2\,c} \cdot BrO \cdot HO2 $$ $$ \mathrm{D}\left(Cl\right) = k_{ClO\,O\,A} \cdot e^{\frac{C_{ClO\,O}}{T}} \cdot ClO \cdot O + k_{ClO\,NO\,A} \cdot e^{\frac{C_{ClO\,NO}}{T}} \cdot ClO \cdot NO + k_{OH\,HCl\,A} \cdot e^{\frac{C_{OH\,HCl}}{T}} \cdot OH \cdot HCl + j_{ClONO2} \cdot ClONO2 + k_{BrO\,ClO\,c} \cdot BrO \cdot ClO + \left(-1.0\right) \cdot k_{Cl\,O3\,A} \cdot e^{\frac{C_{Cl\,O3}}{T}} \cdot Cl \cdot O3 + \left(-1.0\right) \cdot k_{Cl\,CH4\,A} \cdot e^{\frac{C_{Cl\,CH4}}{T}} \cdot Cl \cdot CH4_{mix} \cdot M $$ $$ \mathrm{D}\left(ClO\right) = k_{Cl\,O3\,A} \cdot e^{\frac{C_{Cl\,O3}}{T}} \cdot Cl \cdot O3 + \left(-1.0\right) \cdot k_{ClO\,O\,A} \cdot e^{\frac{C_{ClO\,O}}{T}} \cdot ClO \cdot O + \left(-1.0\right) \cdot k_{ClO\,NO\,A} \cdot e^{\frac{C_{ClO\,NO}}{T}} \cdot ClO \cdot NO + \left(-1.0\right) \cdot k_{BrO\,ClO\,c} \cdot BrO \cdot ClO + \left(-1.0\right) \cdot k_{ClO\,NO2\,M\,A} \cdot \frac{T_{ref}}{T}^{3.4} \cdot ClO \cdot NO2 \cdot M $$ $$ \mathrm{D}\left(HCl\right) = k_{Cl\,CH4\,A} \cdot e^{\frac{C_{Cl\,CH4}}{T}} \cdot Cl \cdot CH4_{mix} \cdot M + \left(-1.0\right) \cdot k_{OH\,HCl\,A} \cdot e^{\frac{C_{OH\,HCl}}{T}} \cdot OH \cdot HCl $$ $$ \mathrm{D}\left(ClONO2\right) = k_{ClO\,NO2\,M\,A} \cdot \frac{T_{ref}}{T}^{3.4} \cdot ClO \cdot NO2 \cdot M + \left(-1.0\right) \cdot j_{ClONO2} \cdot ClONO2 $$ $$ \mathrm{D}\left(Br\right) = k_{BrO\,O\,c} \cdot BrO \cdot O + k_{BrO\,ClO\,c} \cdot BrO \cdot ClO + j_{HOBr} \cdot HOBr + \left(-1.0\right) \cdot k_{Br\,O3\,A} \cdot e^{\frac{C_{Br\,O3}}{T}} \cdot Br \cdot O3 $$ $$ \mathrm{D}\left(BrO\right) = k_{Br\,O3\,A} \cdot e^{\frac{C_{Br\,O3}}{T}} \cdot Br \cdot O3 + \left(-1.0\right) \cdot k_{BrO\,O\,c} \cdot BrO \cdot O + \left(-1.0\right) \cdot k_{BrO\,ClO\,c} \cdot BrO \cdot ClO + \left(-1.0\right) \cdot k_{BrO\,HO2\,c} \cdot BrO \cdot HO2 $$ $$ \mathrm{D}\left(HOBr\right) = k_{BrO\,HO2\,c} \cdot BrO \cdot HO2 + \left(-1.0\right) \cdot j_{HOBr} \cdot HOBr $$Analyses
default_run_1hour
One-hour integration under the S&P Chapter 5 mid-stratosphere defaults (T=227 K, M=3.1e23 m^-3, ~30 km). Shows the coupled evolution of the ozone reservoir and the NOx / HOx / ClOx / BrOx catalytic radical pools that destroy it.
Time span: 0.0 → 3600.0
temperature_sensitivity_sweep
Stratospheric temperature sweep over 200-280 K (cold polar vortex to warm sub-tropical mid-stratosphere). Each temperature drives an independent one-hour integration; the plots show the t=3600 s ozone and ClO against T, surfacing the net effect of the temperature-dependent rate coefficients on the catalytic balance.
Time span: 0.0 → 3600.0
Swept over: T
altitude_density_sweep
Air-density sweep across the stratospheric range, mimicking altitude: M from 1e22 m^-3 (~60 km) to 3e24 m^-3 (~20 km). Each density drives an independent one-hour integration; the plot shows the t=3600 s ozone against M, illustrating how the M-dependent three-body production competes with the bimolecular catalytic sinks.
Time span: 0.0 → 3600.0
Swept over: M
Raw .esm
Raw .esm JSON (this component)
{
"reference": {
"notes": "source_ref: GasChem.jl@8c12c048482b515fb8eb2110bf8ab4b4f4e71309:src/StratosphericChemistry.jl:497\n\nUpstream `StratosphericOzoneSystem` is the comprehensive stratospheric ozone-chemistry component from Seinfeld & Pandis (2006) Chapter 5 — it combines the Chapman mechanism, O(1D) photochemistry, the N2O NOx source (Section 5.3.1), and the NOx / HOx / ClOx / BrOx catalytic ozone-destruction cycles into one model. Despite the upstream docstring phrase 'combining all cycles', the `@component` is a *monolithic* MTK `System`: it re-declares every constant, parameter and variable and writes all 20 equations inline, then returns `System(eqs, t; name)` — there is no `couple()` call and no sub-system composition. It therefore migrates as a single `models.StratosphericOzoneSystem` entry, the same file shape as the sibling single-cycle migrations (chapman.esm, nox_cycle.esm, hox_cycle.esm, clox_cycle.esm, brox_cycle.esm).\n\nStructure: 40 upstream `@constants` and 14 upstream `@parameters` are all encoded as `type: parameter` with their upstream defaults (the rig-wide convention for `@constants` migration, matching the sibling stratospheric files). 15 ODE state variables (O, O1D, O3, N2O, NO, NO2, OH, HO2, Cl, ClO, HCl, ClONO2, Br, BrO, HOBr) and 5 algebraic family variables (Ox, NOx, HOx, ClOx, BrOx) are encoded as `type: state`. The 20 `equations` (15 ODEs + 5 algebraic family sums) reproduce the upstream structural invariant `length(equations(sys)) == 20` asserted by the upstream 'Comprehensive System Structure' test (StratosphericChemistry_test.jl:94-130).\n\nRate-coefficient handling: the upstream rate coefficients (k2 power-law (T_ref/T)^2.4, k4 and the Arrhenius coefficients k_NO_O3 ... k_Br_O3, the termolecular k_ClO_NO2_M power-law (T_ref/T)^3.4, the weighted O(1D) quenching k_O1D_M, and the temperature-independent rate constants k_O1D_H2O_c / k_O1D_CH4_c / k_N2O_O1D_NO_c / k_N2O_O1D_N2_c / k_BrO_O_c / k_BrO_ClO_c / k_BrO_HO2_c) and the derived concentrations O2_conc = O2_mix*M, CH4_conc = CH4_mix*M, H2O_conc = H2O_mix*M are local Julia bindings, not MTK state. They are inlined verbatim into each equation right-hand side — bit-equivalent to writing the equations with the helper bindings, and keeping them out of the symbolic state preserves the upstream `length(unknowns(sys))` count. This is the same inlining convention used by chapman.esm.\n\nThe parameter `N2O_mix` (3.0e-7) is declared in the upstream `@parameters` block but is not referenced by any equation or rate coefficient — it is vestigial (the N2O state default 9.3e16 m^-3, which equals N2O_mix*M at the default M=3.1e23, is set directly on the state rather than derived from this parameter). It is preserved here as a `type: parameter` for fidelity to the upstream parameter block.\n\nChemistry: odd oxygen (Ox = O + O3) is produced by O2 photolysis and destroyed by the O + O3 reaction and by the four catalytic cycles (NO/NO2, OH/HO2, Cl/ClO, Br/BrO), each of which cycles a radical pair without net consumption of the catalyst. O(1D), produced by the O3 -> O(1D) photolysis sub-channel and by N2O photolysis, is quenched by air (M) back to O(3P) and reacts with H2O and CH4 to make the OH that seeds HOx. N2O is the sole NOx source via N2O + O(1D) -> 2 NO (Section 5.3.1) and has no source term, so it decays monotonically. The HCl and ClONO2 reservoirs sequester reactive chlorine; HOBr buffers reactive bromine.\n\nUnits: SI throughout (number densities in m^-3, rate coefficients in m^3/s or m^6/s, photolysis rates in s^-1, temperature in K), converted from the Seinfeld & Pandis CGS values via cm^3/molec/s x 1e-6 -> m^3/s for bimolecular coefficients and cm^6/molec^2/s x 1e-12 -> m^6/s for the three-body coefficients. No CGS<->SI conversion at parse or runtime.\n\nTolerance rationale (model-level rel=1e-6): the expected values pinned in the tests below are references from the canonical ESS Python runner `earthsci_ast.simulation.simulate(rtol=1e-10, atol=1e-12, cse=False)` — the exact settings the inline-test gate uses — so reference/gate cross-integrator drift is zero by construction; rel=1e-6 is the spec section 6.6.4 default and matches the sibling stratospheric files. The `initial_conditions_t0` test overrides to rel=1e-10 / abs=1e-14 (t=0 has no integration drift). The `nighttime_photolysis_off` test adds an abs=1e-6 floor for radical species that decay below the integrator's atol=1e-12 floor once their photochemical sources are switched off.\n\nUpstream test reproduction: the upstream comprehensive-system tests are 'Comprehensive System Structure' (20-equation / state-name structural check, reproduced by the shape of the variables and equations blocks), 'Comprehensive System Integration' (1-hour positivity, reproduced and tightened by `comprehensive_integration_1hour`), 'N2O Destruction in Comprehensive System' (reproduced and tightened by `n2o_destruction_1day`), and 'N2O as NOx Source' (reproduced and tightened by `n2o_as_nox_source`). The remaining tests (short-term transients, chemical-family tracking, temperature and density perturbations, dark chemistry) extend coverage beyond the upstream suite.\n\nStiffness declaration: this document declares the top-level solver block solver.stiffness = \"high\" (esm-spec 2.2), and its declared esm version is 1.1.0 for that reason alone -- the solver block arrives at 1.1.0 and a 1.0.0 document carrying one is rejected with `solver_version_too_old`. The comprehensive stratospheric system is the stiffest document in this directory, because it carries the whole span of Chapter 5 chemistry at once: O(1D) is quenched by air at k_O1D_M * M = 9.99e6 1/s at the default T = 227 K and M = 3.1e23 m^-3, a lifetime of 1.0e-7 s; O(3P) relaxes on 1/(k2 * O2 * M) = 0.042 s; and N2O, the sole NOx source, is removed by j_N2O = 5e-8 1/s, a 2.0e7 s (0.63 yr) lifetime with no source term at all. Fourteen orders of magnitude of chemical timescale sit inside one 20-equation system, and `n2o_destruction_1day` integrates it over an 86400 s window. Measured through EarthSciAST.run_inline_tests in one warm Julia session: without the declaration the non-stiff default hands back every one of the file's 176 assertions as an error, `solver retcode MaxIters`, after 1217.0 s -- 20.3 minutes; with it the binding picks Rosenbrock23 and all 176 pass in 118.4 s -- 68.6 s on a repeat, once the specialization for this system is compiled.\n\nWhat the stiff pick costs in accuracy, stated plainly: under Rosenbrock23 at the runner's default integration tolerances, 174 of the 176 assertions compare against a non-zero expected value (the other two pin O and O(1D) at exactly 0.0 and are judged on the absolute floor), and 173 of those 174 land within 1.1e-7 relative of the stored reference values -- the worst of them being Br at t = 1 s in `default_short_term_100s` (26196331783.22968 against a recorded 26196334555.6556, 1.06e-7 relative, 9.4 times inside the rel=1e-6 bound). The exception is NO at t = 3600 s in `nighttime_photolysis_off`: Rosenbrock23 gives 4.170514861316075e-05 m^-3 against a recorded 4.1705393178305094e-05 m^-3, which is 5.86e-6 relative -- outside the model-level rel=1e-6 -- and it passes only because that test also declares abs=1e-6, against which the 2.45e-10 m^-3 absolute difference is four orders of magnitude inside the bound. That is not a tolerance being abused: with every photolysis rate switched off, NO has decayed from 1e15 m^-3 to 4e-5 m^-3 over the hour, so the assertion is pinning numerical dust four orders of magnitude below one molecule per cubic metre, and the 2.45e-10 m^-3 the two integrators disagree by is nearly ten orders below it. That is exactly what the abs=1e-6 floor on this test was added for. It is recorded here rather than left for the next reader to rediscover: the stiff pick is measurably less accurate than scipy LSODA on that one value, and the two Julia sessions that measured it agree with each other bit for bit.\n\nThe other two bindings: Python integrates the file either way -- 176/176 before and 176/176 after -- so nothing in the Python gate ever said this document was stiff, which is the agreement-by-luck a three-binding sweep exists to stop relying on. What the declaration changes there is the method (LSODA to BDF), which costs 4.8 s -> 5.7 s and, on the same NO at t = 3600 s, moves the Python actual from 9.46e-8 to 1.46e-8 relative -- closer to the recorded value, not further. No other Python actual moves by more than 1.7e-9 relative. The Rust binding parses and version-checks the block but does not map stiffness to an integrator, and its rows are identical before and after: 167 passes and the 9 assertions of `n2o_as_nox_source` erroring with diffsol's `Step size is too small at time = 3.53e-16`, a pre-existing failure this declaration neither causes nor clears. As with components/gaschem/pollu.esm and components/gaschem/stratospheric/chapman.esm, the fact that this model needs an implicit method now lives in the document, where all three bindings read it, rather than in a per-file solver table in one gate."
},
"tolerance": {
"rel": 1e-06
},
"variables": {
"T_ref": {
"type": "parameter",
"units": "K",
"default": 300.0,
"description": "Reference temperature for power-law rate coefficients."
},
"k2_A": {
"type": "parameter",
"units": "m^6/s",
"default": 6e-46,
"description": "Pre-factor: O + O2 + M -> O3 + M (6e-34 cm^6/molec^2/s x 1e-12, Table B.2)."
},
"k4_A": {
"type": "parameter",
"units": "m^3/s",
"default": 8e-18,
"description": "Pre-factor: O + O3 -> 2O2 (8e-12 cm^3/molec/s x 1e-6, Table B.1)."
},
"C_k4": {
"type": "parameter",
"units": "K",
"default": -2060.0,
"description": "exp(C/T) activation temperature: O + O3."
},
"k_O1D_O2_A": {
"type": "parameter",
"units": "m^3/s",
"default": 3.2e-17,
"description": "Pre-factor: O(1D) + O2 quenching (3.2e-11 cm^3/molec/s x 1e-6, Page 143)."
},
"C_O1D_O2": {
"type": "parameter",
"units": "K",
"default": 70.0,
"description": "exp(C/T) activation temperature: O(1D) + O2."
},
"k_O1D_N2_A": {
"type": "parameter",
"units": "m^3/s",
"default": 1.8e-17,
"description": "Pre-factor: O(1D) + N2 quenching (1.8e-11 cm^3/molec/s x 1e-6, Page 143)."
},
"C_O1D_N2": {
"type": "parameter",
"units": "K",
"default": 110.0,
"description": "exp(C/T) activation temperature: O(1D) + N2."
},
"k_O1D_H2O_c": {
"type": "parameter",
"units": "m^3/s",
"default": 2.2e-16,
"description": "O(1D) + H2O -> 2OH rate (2.2e-10 cm^3/molec/s x 1e-6, Page 156)."
},
"k_O1D_CH4_c": {
"type": "parameter",
"units": "m^3/s",
"default": 1.5e-16,
"description": "O(1D) + CH4 -> OH + CH3 rate (1.5e-10 cm^3/molec/s x 1e-6, Page 156)."
},
"k_N2O_O1D_NO_c": {
"type": "parameter",
"units": "m^3/s",
"default": 6.7e-17,
"description": "N2O + O(1D) -> NO + NO rate (6.7e-11 cm^3/molec/s x 1e-6, Page 151)."
},
"k_N2O_O1D_N2_c": {
"type": "parameter",
"units": "m^3/s",
"default": 4.9e-17,
"description": "N2O + O(1D) -> N2 + O2 rate (4.9e-11 cm^3/molec/s x 1e-6, Page 151)."
},
"k_NO_O3_A": {
"type": "parameter",
"units": "m^3/s",
"default": 3e-18,
"description": "Pre-factor: NO + O3 (3e-12 cm^3/molec/s x 1e-6, Page 154)."
},
"C_NO_O3": {
"type": "parameter",
"units": "K",
"default": -1500.0,
"description": "exp(C/T) activation temperature: NO + O3."
},
"k_NO2_O_A": {
"type": "parameter",
"units": "m^3/s",
"default": 5.6e-18,
"description": "Pre-factor: NO2 + O (5.6e-12 cm^3/molec/s x 1e-6, Page 154)."
},
"C_NO2_O": {
"type": "parameter",
"units": "K",
"default": 180.0,
"description": "exp(C/T) activation temperature: NO2 + O."
},
"k_OH_O3_A": {
"type": "parameter",
"units": "m^3/s",
"default": 1.7e-18,
"description": "Pre-factor: OH + O3 (1.7e-12 cm^3/molec/s x 1e-6, Page 161)."
},
"C_OH_O3": {
"type": "parameter",
"units": "K",
"default": -940.0,
"description": "exp(C/T) activation temperature: OH + O3."
},
"k_HO2_O3_A": {
"type": "parameter",
"units": "m^3/s",
"default": 1e-20,
"description": "Pre-factor: HO2 + O3 (1e-14 cm^3/molec/s x 1e-6, Table B.1)."
},
"C_HO2_O3": {
"type": "parameter",
"units": "K",
"default": -490.0,
"description": "exp(C/T) activation temperature: HO2 + O3."
},
"k_HO2_O_A": {
"type": "parameter",
"units": "m^3/s",
"default": 3e-17,
"description": "Pre-factor: HO2 + O (3e-11 cm^3/molec/s x 1e-6, Page 161)."
},
"C_HO2_O": {
"type": "parameter",
"units": "K",
"default": 200.0,
"description": "exp(C/T) activation temperature: HO2 + O."
},
"k_HO2_NO_A": {
"type": "parameter",
"units": "m^3/s",
"default": 3.5e-18,
"description": "Pre-factor: HO2 + NO (3.5e-12 cm^3/molec/s x 1e-6, Page 158)."
},
"C_HO2_NO": {
"type": "parameter",
"units": "K",
"default": 250.0,
"description": "exp(C/T) activation temperature: HO2 + NO."
},
"k_Cl_O3_A": {
"type": "parameter",
"units": "m^3/s",
"default": 2.3e-17,
"description": "Pre-factor: Cl + O3 (2.3e-11 cm^3/molec/s x 1e-6, Page 162)."
},
"C_Cl_O3": {
"type": "parameter",
"units": "K",
"default": -200.0,
"description": "exp(C/T) activation temperature: Cl + O3."
},
"k_ClO_O_A": {
"type": "parameter",
"units": "m^3/s",
"default": 3e-17,
"description": "Pre-factor: ClO + O (3e-11 cm^3/molec/s x 1e-6, Page 162)."
},
"C_ClO_O": {
"type": "parameter",
"units": "K",
"default": 70.0,
"description": "exp(C/T) activation temperature: ClO + O."
},
"k_ClO_NO_A": {
"type": "parameter",
"units": "m^3/s",
"default": 6.4e-18,
"description": "Pre-factor: ClO + NO (6.4e-12 cm^3/molec/s x 1e-6, Page 163)."
},
"C_ClO_NO": {
"type": "parameter",
"units": "K",
"default": 290.0,
"description": "exp(C/T) activation temperature: ClO + NO."
},
"k_Cl_CH4_A": {
"type": "parameter",
"units": "m^3/s",
"default": 9.6e-18,
"description": "Pre-factor: Cl + CH4 (9.6e-12 cm^3/molec/s x 1e-6, Table B.1)."
},
"C_Cl_CH4": {
"type": "parameter",
"units": "K",
"default": -1360.0,
"description": "exp(C/T) activation temperature: Cl + CH4."
},
"k_OH_HCl_A": {
"type": "parameter",
"units": "m^3/s",
"default": 2.6e-18,
"description": "Pre-factor: OH + HCl (2.6e-12 cm^3/molec/s x 1e-6, Page 168)."
},
"C_OH_HCl": {
"type": "parameter",
"units": "K",
"default": -350.0,
"description": "exp(C/T) activation temperature: OH + HCl."
},
"k_ClO_NO2_M_A": {
"type": "parameter",
"units": "m^6/s",
"default": 1.8e-43,
"description": "Pre-factor: ClO + NO2 + M -> ClONO2 (1.8e-31 cm^6/molec^2/s x 1e-12, Page 165)."
},
"k_Br_O3_A": {
"type": "parameter",
"units": "m^3/s",
"default": 1.7e-17,
"description": "Pre-factor: Br + O3 (1.7e-11 cm^3/molec/s x 1e-6, Table B.1)."
},
"C_Br_O3": {
"type": "parameter",
"units": "K",
"default": -800.0,
"description": "exp(C/T) activation temperature: Br + O3."
},
"k_BrO_O_c": {
"type": "parameter",
"units": "m^3/s",
"default": 5e-17,
"description": "BrO + O -> Br + O2 rate (5e-11 cm^3/molec/s x 1e-6)."
},
"k_BrO_ClO_c": {
"type": "parameter",
"units": "m^3/s",
"default": 2e-18,
"description": "BrO + ClO -> Br + Cl + O2 rate (2e-12 cm^3/molec/s x 1e-6)."
},
"k_BrO_HO2_c": {
"type": "parameter",
"units": "m^3/s",
"default": 4e-17,
"description": "BrO + HO2 -> HOBr + O2 rate (4e-11 cm^3/molec/s x 1e-6)."
},
"j_O2": {
"type": "parameter",
"units": "s^-1",
"default": 1e-10,
"description": "O2 photolysis rate."
},
"j_O3": {
"type": "parameter",
"units": "s^-1",
"default": 0.001,
"description": "O3 photolysis rate (total, both O(3P) and O(1D) channels)."
},
"j_O3_O1D": {
"type": "parameter",
"units": "s^-1",
"default": 0.0005,
"description": "O3 -> O(1D) photolysis rate (the O(1D)-producing sub-channel)."
},
"j_NO2": {
"type": "parameter",
"units": "s^-1",
"default": 0.01,
"description": "NO2 photolysis rate."
},
"j_ClONO2": {
"type": "parameter",
"units": "s^-1",
"default": 0.0001,
"description": "ClONO2 photolysis rate."
},
"j_HOBr": {
"type": "parameter",
"units": "s^-1",
"default": 0.001,
"description": "HOBr photolysis rate."
},
"j_N2O": {
"type": "parameter",
"units": "s^-1",
"default": 5e-08,
"description": "N2O photolysis rate (Section 5.3.1)."
},
"T": {
"type": "parameter",
"units": "K",
"default": 227.0,
"description": "Temperature (Page 145 mid-stratosphere reference, ~30 km)."
},
"M": {
"type": "parameter",
"units": "m^-3",
"default": 3.1e+23,
"description": "Air number density at 30 km (3.1e17 molec/cm^3 x 1e6)."
},
"O2_mix": {
"type": "parameter",
"units": "1",
"default": 0.21,
"description": "O2 mixing ratio in air (dimensionless)."
},
"N2_mix": {
"type": "parameter",
"units": "1",
"default": 0.79,
"description": "N2 mixing ratio in air (dimensionless)."
},
"CH4_mix": {
"type": "parameter",
"units": "1",
"default": 1.6e-06,
"description": "CH4 mixing ratio in air (dimensionless)."
},
"H2O_mix": {
"type": "parameter",
"units": "1",
"default": 5e-06,
"description": "H2O mixing ratio in air (dimensionless)."
},
"N2O_mix": {
"type": "parameter",
"units": "1",
"default": 3e-07,
"description": "N2O mixing ratio (~300 ppb, Section 5.3.1, dimensionless). Declared upstream; vestigial — the N2O state default 9.3e16 m^-3 (= N2O_mix x M) is set directly rather than derived from this parameter at runtime."
},
"O": {
"type": "unknown",
"units": "m^-3",
"default": 10000000000000.0,
"description": "Atomic oxygen O(3P) number density (1e7 molec/cm^3 x 1e6)."
},
"O1D": {
"type": "unknown",
"units": "m^-3",
"default": 50000000.0,
"description": "Excited oxygen O(1D) number density (50 molec/cm^3 x 1e6)."
},
"O3": {
"type": "unknown",
"units": "m^-3",
"default": 3e+18,
"description": "Ozone number density (3e12 molec/cm^3 x 1e6)."
},
"NO": {
"type": "unknown",
"units": "m^-3",
"default": 1000000000000000.0,
"description": "Nitric oxide number density (1e9 molec/cm^3 x 1e6)."
},
"NO2": {
"type": "unknown",
"units": "m^-3",
"default": 1000000000000000.0,
"description": "Nitrogen dioxide number density (1e9 molec/cm^3 x 1e6)."
},
"OH": {
"type": "unknown",
"units": "m^-3",
"default": 1000000000000.0,
"description": "Hydroxyl radical number density (1e6 molec/cm^3 x 1e6)."
},
"HO2": {
"type": "unknown",
"units": "m^-3",
"default": 10000000000000.0,
"description": "Hydroperoxyl radical number density (1e7 molec/cm^3 x 1e6)."
},
"Cl": {
"type": "unknown",
"units": "m^-3",
"default": 10000000000.0,
"description": "Chlorine atom number density (1e4 molec/cm^3 x 1e6)."
},
"ClO": {
"type": "unknown",
"units": "m^-3",
"default": 10000000000000.0,
"description": "Chlorine monoxide number density (1e7 molec/cm^3 x 1e6)."
},
"HCl": {
"type": "unknown",
"units": "m^-3",
"default": 1000000000000000.0,
"description": "Hydrogen chloride reservoir number density (1e9 molec/cm^3 x 1e6)."
},
"ClONO2": {
"type": "unknown",
"units": "m^-3",
"default": 1000000000000000.0,
"description": "Chlorine nitrate reservoir number density (1e9 molec/cm^3 x 1e6)."
},
"Br": {
"type": "unknown",
"units": "m^-3",
"default": 100000000000.0,
"description": "Bromine atom number density (1e5 molec/cm^3 x 1e6)."
},
"BrO": {
"type": "unknown",
"units": "m^-3",
"default": 1000000000000.0,
"description": "Bromine monoxide number density (1e6 molec/cm^3 x 1e6)."
},
"HOBr": {
"type": "unknown",
"units": "m^-3",
"default": 1000000000000.0,
"description": "Hypobromous acid number density (1e6 molec/cm^3 x 1e6)."
},
"N2O": {
"type": "unknown",
"units": "m^-3",
"default": 9.3e+16,
"description": "Nitrous oxide number density (~300 ppb at 30 km)."
},
"Ox": {
"type": "unknown",
"units": "m^-3",
"description": "Odd oxygen family: algebraic sum Ox ~ O + O3."
},
"NOx": {
"type": "unknown",
"units": "m^-3",
"description": "Reactive nitrogen family: algebraic sum NOx ~ NO + NO2."
},
"HOx": {
"type": "unknown",
"units": "m^-3",
"description": "Hydrogen radical family: algebraic sum HOx ~ OH + HO2."
},
"ClOx": {
"type": "unknown",
"units": "m^-3",
"description": "Reactive chlorine family: algebraic sum ClOx ~ Cl + ClO."
},
"BrOx": {
"type": "unknown",
"units": "m^-3",
"description": "Reactive bromine family: algebraic sum BrOx ~ Br + BrO."
}
},
"equations": [
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"O"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
2.0,
"j_O2",
"O2_mix",
"M"
]
},
{
"op": "*",
"args": [
{
"op": "+",
"args": [
"j_O3",
{
"op": "*",
"args": [
-1.0,
"j_O3_O1D"
]
}
]
},
"O3"
]
},
{
"op": "*",
"args": [
{
"op": "+",
"args": [
{
"op": "*",
"args": [
"O2_mix",
"k_O1D_O2_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_O1D_O2",
"T"
]
}
]
}
]
},
{
"op": "*",
"args": [
"N2_mix",
"k_O1D_N2_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_O1D_N2",
"T"
]
}
]
}
]
}
]
},
"O1D",
"M"
]
},
{
"op": "*",
"args": [
"j_NO2",
"NO2"
]
},
{
"op": "*",
"args": [
-1.0,
"k2_A",
{
"op": "^",
"args": [
{
"op": "/",
"args": [
"T_ref",
"T"
]
},
2.4
]
},
"O",
"O2_mix",
"M",
"M"
]
},
{
"op": "*",
"args": [
-1.0,
"k4_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_k4",
"T"
]
}
]
},
"O",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_NO2_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_NO2_O",
"T"
]
}
]
},
"NO2",
"O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_ClO_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_ClO_O",
"T"
]
}
]
},
"ClO",
"O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_BrO_O_c",
"BrO",
"O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_HO2_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_O",
"T"
]
}
]
},
"HO2",
"O"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"O1D"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"j_O3_O1D",
"O3"
]
},
{
"op": "*",
"args": [
"j_N2O",
"N2O"
]
},
{
"op": "*",
"args": [
-1.0,
{
"op": "+",
"args": [
{
"op": "*",
"args": [
"O2_mix",
"k_O1D_O2_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_O1D_O2",
"T"
]
}
]
}
]
},
{
"op": "*",
"args": [
"N2_mix",
"k_O1D_N2_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_O1D_N2",
"T"
]
}
]
}
]
}
]
},
"O1D",
"M"
]
},
{
"op": "*",
"args": [
-1.0,
"k_O1D_H2O_c",
"O1D",
"H2O_mix",
"M"
]
},
{
"op": "*",
"args": [
-1.0,
"k_O1D_CH4_c",
"O1D",
"CH4_mix",
"M"
]
},
{
"op": "*",
"args": [
-1.0,
"k_N2O_O1D_NO_c",
"O1D",
"N2O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_N2O_O1D_N2_c",
"O1D",
"N2O"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"O3"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k2_A",
{
"op": "^",
"args": [
{
"op": "/",
"args": [
"T_ref",
"T"
]
},
2.4
]
},
"O",
"O2_mix",
"M",
"M"
]
},
{
"op": "*",
"args": [
-1.0,
"j_O3",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k4_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_k4",
"T"
]
}
]
},
"O",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_NO_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_NO_O3",
"T"
]
}
]
},
"NO",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_OH_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_OH_O3",
"T"
]
}
]
},
"OH",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_HO2_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_O3",
"T"
]
}
]
},
"HO2",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_Cl_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_Cl_O3",
"T"
]
}
]
},
"Cl",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_Br_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_Br_O3",
"T"
]
}
]
},
"Br",
"O3"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"N2O"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
-1.0,
"j_N2O",
"N2O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_N2O_O1D_NO_c",
"O1D",
"N2O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_N2O_O1D_N2_c",
"O1D",
"N2O"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"NO"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
2.0,
"k_N2O_O1D_NO_c",
"O1D",
"N2O"
]
},
{
"op": "*",
"args": [
"j_NO2",
"NO2"
]
},
{
"op": "*",
"args": [
"k_NO2_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_NO2_O",
"T"
]
}
]
},
"NO2",
"O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_NO_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_NO_O3",
"T"
]
}
]
},
"NO",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_ClO_NO_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_ClO_NO",
"T"
]
}
]
},
"ClO",
"NO"
]
},
{
"op": "*",
"args": [
-1.0,
"k_HO2_NO_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_NO",
"T"
]
}
]
},
"HO2",
"NO"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"NO2"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_NO_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_NO_O3",
"T"
]
}
]
},
"NO",
"O3"
]
},
{
"op": "*",
"args": [
"k_HO2_NO_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_NO",
"T"
]
}
]
},
"HO2",
"NO"
]
},
{
"op": "*",
"args": [
"k_ClO_NO_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_ClO_NO",
"T"
]
}
]
},
"ClO",
"NO"
]
},
{
"op": "*",
"args": [
-1.0,
"j_NO2",
"NO2"
]
},
{
"op": "*",
"args": [
-1.0,
"k_NO2_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_NO2_O",
"T"
]
}
]
},
"NO2",
"O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_ClO_NO2_M_A",
{
"op": "^",
"args": [
{
"op": "/",
"args": [
"T_ref",
"T"
]
},
3.4
]
},
"ClO",
"NO2",
"M"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"OH"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
2.0,
"k_O1D_H2O_c",
"O1D",
"H2O_mix",
"M"
]
},
{
"op": "*",
"args": [
"k_O1D_CH4_c",
"O1D",
"CH4_mix",
"M"
]
},
{
"op": "*",
"args": [
"k_HO2_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_O",
"T"
]
}
]
},
"HO2",
"O"
]
},
{
"op": "*",
"args": [
"k_HO2_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_O3",
"T"
]
}
]
},
"HO2",
"O3"
]
},
{
"op": "*",
"args": [
"k_HO2_NO_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_NO",
"T"
]
}
]
},
"HO2",
"NO"
]
},
{
"op": "*",
"args": [
"j_HOBr",
"HOBr"
]
},
{
"op": "*",
"args": [
-1.0,
"k_OH_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_OH_O3",
"T"
]
}
]
},
"OH",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_OH_HCl_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_OH_HCl",
"T"
]
}
]
},
"OH",
"HCl"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"HO2"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_OH_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_OH_O3",
"T"
]
}
]
},
"OH",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_HO2_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_O",
"T"
]
}
]
},
"HO2",
"O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_HO2_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_O3",
"T"
]
}
]
},
"HO2",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_HO2_NO_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_HO2_NO",
"T"
]
}
]
},
"HO2",
"NO"
]
},
{
"op": "*",
"args": [
-1.0,
"k_BrO_HO2_c",
"BrO",
"HO2"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"Cl"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_ClO_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_ClO_O",
"T"
]
}
]
},
"ClO",
"O"
]
},
{
"op": "*",
"args": [
"k_ClO_NO_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_ClO_NO",
"T"
]
}
]
},
"ClO",
"NO"
]
},
{
"op": "*",
"args": [
"k_OH_HCl_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_OH_HCl",
"T"
]
}
]
},
"OH",
"HCl"
]
},
{
"op": "*",
"args": [
"j_ClONO2",
"ClONO2"
]
},
{
"op": "*",
"args": [
"k_BrO_ClO_c",
"BrO",
"ClO"
]
},
{
"op": "*",
"args": [
-1.0,
"k_Cl_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_Cl_O3",
"T"
]
}
]
},
"Cl",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_Cl_CH4_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_Cl_CH4",
"T"
]
}
]
},
"Cl",
"CH4_mix",
"M"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"ClO"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_Cl_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_Cl_O3",
"T"
]
}
]
},
"Cl",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_ClO_O_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_ClO_O",
"T"
]
}
]
},
"ClO",
"O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_ClO_NO_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_ClO_NO",
"T"
]
}
]
},
"ClO",
"NO"
]
},
{
"op": "*",
"args": [
-1.0,
"k_BrO_ClO_c",
"BrO",
"ClO"
]
},
{
"op": "*",
"args": [
-1.0,
"k_ClO_NO2_M_A",
{
"op": "^",
"args": [
{
"op": "/",
"args": [
"T_ref",
"T"
]
},
3.4
]
},
"ClO",
"NO2",
"M"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"HCl"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_Cl_CH4_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_Cl_CH4",
"T"
]
}
]
},
"Cl",
"CH4_mix",
"M"
]
},
{
"op": "*",
"args": [
-1.0,
"k_OH_HCl_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_OH_HCl",
"T"
]
}
]
},
"OH",
"HCl"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"ClONO2"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_ClO_NO2_M_A",
{
"op": "^",
"args": [
{
"op": "/",
"args": [
"T_ref",
"T"
]
},
3.4
]
},
"ClO",
"NO2",
"M"
]
},
{
"op": "*",
"args": [
-1.0,
"j_ClONO2",
"ClONO2"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"Br"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_BrO_O_c",
"BrO",
"O"
]
},
{
"op": "*",
"args": [
"k_BrO_ClO_c",
"BrO",
"ClO"
]
},
{
"op": "*",
"args": [
"j_HOBr",
"HOBr"
]
},
{
"op": "*",
"args": [
-1.0,
"k_Br_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_Br_O3",
"T"
]
}
]
},
"Br",
"O3"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"BrO"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_Br_O3_A",
{
"op": "exp",
"args": [
{
"op": "/",
"args": [
"C_Br_O3",
"T"
]
}
]
},
"Br",
"O3"
]
},
{
"op": "*",
"args": [
-1.0,
"k_BrO_O_c",
"BrO",
"O"
]
},
{
"op": "*",
"args": [
-1.0,
"k_BrO_ClO_c",
"BrO",
"ClO"
]
},
{
"op": "*",
"args": [
-1.0,
"k_BrO_HO2_c",
"BrO",
"HO2"
]
}
]
}
},
{
"lhs": {
"op": "D",
"wrt": "t",
"args": [
"HOBr"
]
},
"rhs": {
"op": "+",
"args": [
{
"op": "*",
"args": [
"k_BrO_HO2_c",
"BrO",
"HO2"
]
},
{
"op": "*",
"args": [
-1.0,
"j_HOBr",
"HOBr"
]
}
]
}
},
{
"lhs": "Ox",
"rhs": {
"op": "+",
"args": [
"O",
"O3"
]
}
},
{
"lhs": "NOx",
"rhs": {
"op": "+",
"args": [
"NO",
"NO2"
]
}
},
{
"lhs": "HOx",
"rhs": {
"op": "+",
"args": [
"OH",
"HO2"
]
}
},
{
"lhs": "ClOx",
"rhs": {
"op": "+",
"args": [
"Cl",
"ClO"
]
}
},
{
"lhs": "BrOx",
"rhs": {
"op": "+",
"args": [
"Br",
"BrO"
]
}
}
],
"tests": [
{
"id": "initial_conditions_t0",
"description": "At t=0 the solver must return the declared species defaults exactly, and each algebraic family must equal the sum of its two members. Tolerance tightened to rel=1e-10 / abs=1e-14: t=0 carries no integration drift, only parser->Float64 conversion and the first-step identity evaluation of the initial state.",
"time_span": {
"start": 0.0,
"end": 1.0
},
"tolerance": {
"rel": 1e-10,
"abs": 1e-14
},
"assertions": [
{
"variable": "O",
"time": 0.0,
"expected": 9999999999999.998
},
{
"variable": "O1D",
"time": 0.0,
"expected": 49999999.99999999
},
{
"variable": "O3",
"time": 0.0,
"expected": 3e+18
},
{
"variable": "NO",
"time": 0.0,
"expected": 1000000000000000.0
},
{
"variable": "NO2",
"time": 0.0,
"expected": 1000000000000000.0
},
{
"variable": "OH",
"time": 0.0,
"expected": 1000000000000.0
},
{
"variable": "HO2",
"time": 0.0,
"expected": 10000000000000.0
},
{
"variable": "Cl",
"time": 0.0,
"expected": 10000000000.0
},
{
"variable": "ClO",
"time": 0.0,
"expected": 10000000000000.0
},
{
"variable": "HCl",
"time": 0.0,
"expected": 1000000000000000.0
},
{
"variable": "ClONO2",
"time": 0.0,
"expected": 1000000000000000.0
},
{
"variable": "Br",
"time": 0.0,
"expected": 100000000000.0
},
{
"variable": "BrO",
"time": 0.0,
"expected": 1000000000000.0
},
{
"variable": "HOBr",
"time": 0.0,
"expected": 1000000000000.0
},
{
"variable": "N2O",
"time": 0.0,
"expected": 9.3e+16
},
{
"variable": "Ox",
"time": 0.0,
"expected": 3.00001e+18
},
{
"variable": "NOx",
"time": 0.0,
"expected": 2000000000000000.0
},
{
"variable": "HOx",
"time": 0.0,
"expected": 11000000000000.0
},
{
"variable": "ClOx",
"time": 0.0,
"expected": 10010000000000.0
},
{
"variable": "BrOx",
"time": 0.0,
"expected": 1100000000000.0
}
]
},
{
"id": "comprehensive_integration_1hour",
"description": "Headline 1-hour integration under the S&P Chapter 5 mid-stratosphere defaults (T=227 K, M=3.1e23 m^-3, ~30 km). Reproduces and tightens the upstream 'Comprehensive System Integration' test (StratosphericChemistry_test.jl:529-544) — that test asserts only retcode=Success and positivity of O/O3/NO/NO2/N2O, this one pins the full multi-species trajectory at three times across the window.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"assertions": [
{
"variable": "O",
"time": 600.0,
"expected": 127947404705428.3
},
{
"variable": "O1D",
"time": 600.0,
"expected": 150320646.88713777
},
{
"variable": "O3",
"time": 600.0,
"expected": 3.0042330587316127e+18
},
{
"variable": "NO",
"time": 600.0,
"expected": 896973206846427.0
},
{
"variable": "NO2",
"time": 600.0,
"expected": 1100503668192925.9
},
{
"variable": "OH",
"time": 600.0,
"expected": 17011401343985.533
},
{
"variable": "HO2",
"time": 600.0,
"expected": 58529374818868.016
},
{
"variable": "Cl",
"time": 600.0,
"expected": 64709393914.47645
},
{
"variable": "ClO",
"time": 600.0,
"expected": 67751036044948.46
},
{
"variable": "HCl",
"time": 600.0,
"expected": 996863616124983.4
},
{
"variable": "ClONO2",
"time": 600.0,
"expected": 945330638436152.5
},
{
"variable": "Br",
"time": 600.0,
"expected": 4639173791.942083
},
{
"variable": "BrO",
"time": 600.0,
"expected": 882916816388.9995
},
{
"variable": "HOBr",
"time": 600.0,
"expected": 1212444009819.0583
},
{
"variable": "N2O",
"time": 600.0,
"expected": 9.299623775470997e+16
},
{
"variable": "O",
"time": 1800.0,
"expected": 128141427624250.33
},
{
"variable": "O1D",
"time": 1800.0,
"expected": 150582383.4130125
},
{
"variable": "O3",
"time": 1800.0,
"expected": 3.009464010351473e+18
},
{
"variable": "NO",
"time": 1800.0,
"expected": 785055499999053.6
},
{
"variable": "NO2",
"time": 1800.0,
"expected": 1190671189682184.5
},
{
"variable": "OH",
"time": 1800.0,
"expected": 40238958460539.49
},
{
"variable": "HO2",
"time": 1800.0,
"expected": 152175467327890.62
},
{
"variable": "Cl",
"time": 1800.0,
"expected": 141076805461.2867
},
{
"variable": "ClO",
"time": 1800.0,
"expected": 169381390755409.5
},
{
"variable": "HCl",
"time": 1800.0,
"expected": 979230999972653.2
},
{
"variable": "ClONO2",
"time": 1800.0,
"expected": 861256532466474.6
},
{
"variable": "Br",
"time": 1800.0,
"expected": 2607394237.2913184
},
{
"variable": "BrO",
"time": 1800.0,
"expected": 319155620168.79767
},
{
"variable": "HOBr",
"time": 1800.0,
"expected": 1778236985593.909
},
{
"variable": "N2O",
"time": 1800.0,
"expected": 9.298871043861064e+16
},
{
"variable": "O",
"time": 3600.0,
"expected": 128096798396110.62
},
{
"variable": "O1D",
"time": 3600.0,
"expected": 150597695.0282939
},
{
"variable": "O3",
"time": 3600.0,
"expected": 3.0097700222967506e+18
},
{
"variable": "NO",
"time": 3600.0,
"expected": 663047103541114.2
},
{
"variable": "NO2",
"time": 3600.0,
"expected": 1242043226116215.5
},
{
"variable": "OH",
"time": 3600.0,
"expected": 67989618176724.91
},
{
"variable": "HO2",
"time": 3600.0,
"expected": 277061490944765.4
},
{
"variable": "Cl",
"time": 3600.0,
"expected": 211652822841.55942
},
{
"variable": "ClO",
"time": 3600.0,
"expected": 291325977712109.1
},
{
"variable": "HCl",
"time": 3600.0,
"expected": 930785261919155.0
},
{
"variable": "ClONO2",
"time": 3600.0,
"expected": 787687107545892.2
},
{
"variable": "Br",
"time": 3600.0,
"expected": 2093687173.9980724
},
{
"variable": "BrO",
"time": 3600.0,
"expected": 176940785148.10303
},
{
"variable": "HOBr",
"time": 3600.0,
"expected": 1920965527677.8967
},
{
"variable": "N2O",
"time": 3600.0,
"expected": 9.297741760945958e+16
}
]
},
{
"id": "default_short_term_100s",
"description": "Short-window (100 s) integration capturing the fast radical transients. Atomic O, O(1D) and the halogen radicals Cl/Br relax toward their photochemical quasi-equilibria on sub-second to tens-of-seconds timescales set by the bimolecular and three-body sink reactions; this test pins those fast modes before the slow Ox / reservoir drift.",
"time_span": {
"start": 0.0,
"end": 100.0
},
"assertions": [
{
"variable": "O",
"time": 1.0,
"expected": 127760180700922.36
},
{
"variable": "O1D",
"time": 1.0,
"expected": 150103344.08720452
},
{
"variable": "O3",
"time": 1.0,
"expected": 2.999890140267367e+18
},
{
"variable": "OH",
"time": 1.0,
"expected": 1249811986320.8782
},
{
"variable": "HO2",
"time": 1.0,
"expected": 9863684280678.129
},
{
"variable": "Cl",
"time": 1.0,
"expected": 13456888905.317953
},
{
"variable": "ClO",
"time": 1.0,
"expected": 10095559422159.525
},
{
"variable": "Br",
"time": 1.0,
"expected": 26196334555.6556
},
{
"variable": "BrO",
"time": 1.0,
"expected": 1074387776724.4255
},
{
"variable": "O",
"time": 10.0,
"expected": 127765699118443.81
},
{
"variable": "O1D",
"time": 10.0,
"expected": 150106886.30410048
},
{
"variable": "O3",
"time": 10.0,
"expected": 2.9999609334696873e+18
},
{
"variable": "OH",
"time": 10.0,
"expected": 2734047988946.098
},
{
"variable": "HO2",
"time": 10.0,
"expected": 9396047801066.252
},
{
"variable": "Cl",
"time": 10.0,
"expected": 14299575519.460087
},
{
"variable": "ClO",
"time": 10.0,
"expected": 10989480884611.773
},
{
"variable": "Br",
"time": 10.0,
"expected": 5352733856.786856
},
{
"variable": "BrO",
"time": 10.0,
"expected": 1100440842405.1965
},
{
"variable": "O",
"time": 50.0,
"expected": 127784360496347.89
},
{
"variable": "O1D",
"time": 50.0,
"expected": 150122775.30648118
},
{
"variable": "O3",
"time": 50.0,
"expected": 3.0002784840984433e+18
},
{
"variable": "OH",
"time": 50.0,
"expected": 4494401818328.883
},
{
"variable": "HO2",
"time": 50.0,
"expected": 12112823195313.895
},
{
"variable": "Cl",
"time": 50.0,
"expected": 17977497917.23895
},
{
"variable": "ClO",
"time": 50.0,
"expected": 14975407231536.244
},
{
"variable": "Br",
"time": 50.0,
"expected": 5432901288.746634
},
{
"variable": "BrO",
"time": 50.0,
"expected": 1120953402312.4824
},
{
"variable": "O",
"time": 100.0,
"expected": 127802984366098.75
},
{
"variable": "O1D",
"time": 100.0,
"expected": 150142722.5580793
},
{
"variable": "O3",
"time": 100.0,
"expected": 3.000677141113466e+18
},
{
"variable": "OH",
"time": 100.0,
"expected": 5704377039938.06
},
{
"variable": "HO2",
"time": 100.0,
"expected": 16454857006132.604
},
{
"variable": "Cl",
"time": 100.0,
"expected": 22548335278.15812
},
{
"variable": "ClO",
"time": 100.0,
"expected": 19933969988511.91
},
{
"variable": "Br",
"time": 100.0,
"expected": 5498120783.866939
},
{
"variable": "BrO",
"time": 100.0,
"expected": 1136838526765.2346
}
]
},
{
"id": "n2o_destruction_1day",
"description": "24-hour integration tracking N2O loss. Reproduces and tightens the upstream 'N2O Destruction in Comprehensive System' test (StratosphericChemistry_test.jl:550-563) — that test asserts only N2O[end] <= N2O[1], this one pins the monotone N2O decay (photolysis j_N2O plus the two O(1D) channels, with no replenishment source) at four times spanning the day, alongside the co-evolving O3 and NOx.",
"time_span": {
"start": 0.0,
"end": 86400.0
},
"assertions": [
{
"variable": "N2O",
"time": 0.0,
"expected": 9.3e+16
},
{
"variable": "N2O",
"time": 3600.0,
"expected": 9.29774176094677e+16
},
{
"variable": "N2O",
"time": 21600.0,
"expected": 9.286563482290912e+16
},
{
"variable": "N2O",
"time": 86400.0,
"expected": 9.25115321242791e+16
},
{
"variable": "O3",
"time": 86400.0,
"expected": 6.425674328948479e+17
},
{
"variable": "NO",
"time": 86400.0,
"expected": 175939893693.65253
},
{
"variable": "NO2",
"time": 86400.0,
"expected": 1536830334668.8367
},
{
"variable": "NOx",
"time": 86400.0,
"expected": 1712770228362.4893
},
{
"variable": "Ox",
"time": 86400.0,
"expected": 6.425947143808854e+17
}
]
},
{
"id": "n2o_as_nox_source",
"description": "NOx-source test: start with NO=0 and NO2=0 but nonzero N2O and O(1D). Reproduces and tightens the upstream 'N2O as NOx Source (Section 5.3.1)' test (StratosphericChemistry_test.jl:565-588) — that test asserts only NO[end] > 0, this one pins the NO and NO2 produced from the N2O + O(1D) -> 2 NO channel over the first 100 s.",
"time_span": {
"start": 0.0,
"end": 100.0
},
"initial_conditions": {
"NO": 0.0,
"NO2": 0.0,
"N2O": 9.3e+16,
"O1D": 50000000.0
},
"assertions": [
{
"variable": "NO",
"time": 10.0,
"expected": 17625779901.016895
},
{
"variable": "NO2",
"time": 10.0,
"expected": 1080410131.5393243
},
{
"variable": "NOx",
"time": 10.0,
"expected": 18706190032.55622
},
{
"variable": "NO",
"time": 50.0,
"expected": 73093961878.30247
},
{
"variable": "NO2",
"time": 50.0,
"expected": 20443427981.822216
},
{
"variable": "NOx",
"time": 50.0,
"expected": 93537389860.1247
},
{
"variable": "NO",
"time": 100.0,
"expected": 125893660649.20647
},
{
"variable": "NO2",
"time": 100.0,
"expected": 61194364081.84326
},
{
"variable": "NOx",
"time": 100.0,
"expected": 187088024731.04974
}
]
},
{
"id": "chemical_families_evolution",
"description": "Tracks the five algebraic chemical families (Ox, NOx, HOx, ClOx, BrOx) under default conditions over one hour. The families are diagnostic sums that name the partitioning of odd oxygen and the catalytic radical pools; pinning them is a regression target on the algebraic-equation machinery distinct from the 15 ODE states.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"assertions": [
{
"variable": "Ox",
"time": 0.0,
"expected": 3.00001e+18
},
{
"variable": "NOx",
"time": 0.0,
"expected": 2000000000000000.0
},
{
"variable": "HOx",
"time": 0.0,
"expected": 11000000000000.0
},
{
"variable": "ClOx",
"time": 0.0,
"expected": 10010000000000.0
},
{
"variable": "BrOx",
"time": 0.0,
"expected": 1100000000000.0
},
{
"variable": "Ox",
"time": 600.0,
"expected": 3.0043610061363174e+18
},
{
"variable": "NOx",
"time": 600.0,
"expected": 1997476875039353.0
},
{
"variable": "HOx",
"time": 600.0,
"expected": 75540776162853.55
},
{
"variable": "ClOx",
"time": 600.0,
"expected": 67815745438862.94
},
{
"variable": "BrOx",
"time": 600.0,
"expected": 887555990180.9417
},
{
"variable": "Ox",
"time": 3600.0,
"expected": 3.0098981190951465e+18
},
{
"variable": "NOx",
"time": 3600.0,
"expected": 1905090329657329.8
},
{
"variable": "HOx",
"time": 3600.0,
"expected": 345051109121490.3
},
{
"variable": "ClOx",
"time": 3600.0,
"expected": 291537630534950.7
},
{
"variable": "BrOx",
"time": 3600.0,
"expected": 179034472322.1011
}
]
},
{
"id": "cold_temperature_perturbation",
"description": "Cold-stratosphere case: T lowered from 227 K to 200 K (polar-vortex regime). Every Arrhenius rate coefficient k = A*exp(C/T) and the two power-law coefficients k2 and k_ClO_NO2_M shift; the joint response of the coupled O / NOx / HOx / ClOx / BrOx pools is pinned at t=3600 s.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"parameter_overrides": {
"T": 200.0
},
"assertions": [
{
"variable": "O",
"time": 3600.0,
"expected": 94956100243302.08
},
{
"variable": "O3",
"time": 3600.0,
"expected": 3.02309440641961e+18
},
{
"variable": "NO",
"time": 3600.0,
"expected": 800626244953650.1
},
{
"variable": "NO2",
"time": 3600.0,
"expected": 1078043926479622.4
},
{
"variable": "OH",
"time": 3600.0,
"expected": 94351205599270.73
},
{
"variable": "HO2",
"time": 3600.0,
"expected": 216395572546115.3
},
{
"variable": "Cl",
"time": 3600.0,
"expected": 289537975122.5762
},
{
"variable": "ClO",
"time": 3600.0,
"expected": 281509217887617.0
},
{
"variable": "Br",
"time": 3600.0,
"expected": 3246201737.850831
},
{
"variable": "BrO",
"time": 3600.0,
"expected": 222382092549.44464
},
{
"variable": "N2O",
"time": 3600.0,
"expected": 9.297773992203994e+16
}
]
},
{
"id": "warm_temperature_perturbation",
"description": "Warm-stratosphere case: T raised from 227 K to 270 K. Together with cold_temperature_perturbation this brackets the dynamic range of the temperature-dependent rate coefficients across the stratospheric temperature range; species pinned at t=3600 s.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"parameter_overrides": {
"T": 270.0
},
"assertions": [
{
"variable": "O",
"time": 3600.0,
"expected": 191841595728349.4
},
{
"variable": "O3",
"time": 3600.0,
"expected": 2.974917375090135e+18
},
{
"variable": "NO",
"time": 3600.0,
"expected": 424047559793705.2
},
{
"variable": "NO2",
"time": 3600.0,
"expected": 1510960851664036.8
},
{
"variable": "OH",
"time": 3600.0,
"expected": 45548119085312.375
},
{
"variable": "HO2",
"time": 3600.0,
"expected": 338977645433418.9
},
{
"variable": "Cl",
"time": 3600.0,
"expected": 145436033482.69016
},
{
"variable": "ClO",
"time": 3600.0,
"expected": 301366395931698.2
},
{
"variable": "Br",
"time": 3600.0,
"expected": 1318573778.4632356
},
{
"variable": "BrO",
"time": 3600.0,
"expected": 146444965204.73782
},
{
"variable": "N2O",
"time": 3600.0,
"expected": 9.297703299971918e+16
}
]
},
{
"id": "dense_air_perturbation",
"description": "Lower-altitude (denser air) case: M raised from 3.1e23 to 1.0e24 m^-3. The three-body channels (O+O2+M, ClO+NO2+M) scale super-linearly with M while the bimolecular catalytic sinks scale linearly, shifting the ozone balance; species pinned at t=3600 s.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"parameter_overrides": {
"M": 1e+24
},
"assertions": [
{
"variable": "O",
"time": 3600.0,
"expected": 12987361839561.111
},
{
"variable": "O1D",
"time": 3600.0,
"expected": 48739974.99013316
},
{
"variable": "O3",
"time": 3600.0,
"expected": 3.142232590195239e+18
},
{
"variable": "NO",
"time": 3600.0,
"expected": 603237053940819.8
},
{
"variable": "NO2",
"time": 3600.0,
"expected": 1182259921294448.2
},
{
"variable": "ClO",
"time": 3600.0,
"expected": 164213638576476.38
},
{
"variable": "ClONO2",
"time": 3600.0,
"expected": 886855327335839.4
},
{
"variable": "Ox",
"time": 3600.0,
"expected": 3.1422455775570785e+18
}
]
},
{
"id": "nighttime_photolysis_off",
"description": "Polar-night / dark-chemistry case: all seven photolysis rates (j_O2, j_O3, j_O3_O1D, j_NO2, j_ClONO2, j_HOBr, j_N2O) set to 0. With no photochemical sources the odd-oxygen production shuts off and the system relaxes purely through its catalytic and reservoir-forming sinks; species pinned at t=3600 s. The abs floor accommodates radicals decaying below the atol=1e-12 integrator floor.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"tolerance": {
"rel": 1e-06,
"abs": 1e-06
},
"parameter_overrides": {
"j_O2": 0.0,
"j_O3": 0.0,
"j_O3_O1D": 0.0,
"j_NO2": 0.0,
"j_ClONO2": 0.0,
"j_HOBr": 0.0,
"j_N2O": 0.0
},
"assertions": [
{
"variable": "O",
"time": 3600.0,
"expected": 0.0
},
{
"variable": "O1D",
"time": 3600.0,
"expected": 0.0
},
{
"variable": "O3",
"time": 3600.0,
"expected": 2.998770432902956e+18
},
{
"variable": "NO",
"time": 3600.0,
"expected": 4.1705393178305094e-05
},
{
"variable": "NO2",
"time": 3600.0,
"expected": 1993241748110059.2
},
{
"variable": "OH",
"time": 3600.0,
"expected": 378680023761.4681
},
{
"variable": "HO2",
"time": 3600.0,
"expected": 8924312035631.322
},
{
"variable": "Cl",
"time": 3600.0,
"expected": 7442552.435161241
},
{
"variable": "ClO",
"time": 3600.0,
"expected": 4117871570316.1436
},
{
"variable": "Br",
"time": 3600.0,
"expected": 1519250.2617148836
},
{
"variable": "BrO",
"time": 3600.0,
"expected": 277072887067.7773
},
{
"variable": "N2O",
"time": 3600.0,
"expected": 9.3e+16
}
]
}
],
"analyses": [
{
"id": "default_run_1hour",
"description": "One-hour integration under the S&P Chapter 5 mid-stratosphere defaults (T=227 K, M=3.1e23 m^-3, ~30 km). Shows the coupled evolution of the ozone reservoir and the NOx / HOx / ClOx / BrOx catalytic radical pools that destroy it.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"plots": [
{
"id": "o3_vs_time",
"type": "line",
"description": "Ozone O3 over one hour.",
"x": {
"variable": "t",
"label": "time (s)"
},
"y": {
"variable": "O3",
"label": "O3 (m^-3)"
}
},
{
"id": "clo_vs_time",
"type": "line",
"description": "Chlorine monoxide ClO over one hour.",
"x": {
"variable": "t",
"label": "time (s)"
},
"y": {
"variable": "ClO",
"label": "ClO (m^-3)"
}
},
{
"id": "no2_vs_time",
"type": "line",
"description": "Nitrogen dioxide NO2 over one hour.",
"x": {
"variable": "t",
"label": "time (s)"
},
"y": {
"variable": "NO2",
"label": "NO2 (m^-3)"
}
},
{
"id": "oh_vs_time",
"type": "line",
"description": "Hydroxyl radical OH over one hour.",
"x": {
"variable": "t",
"label": "time (s)"
},
"y": {
"variable": "OH",
"label": "OH (m^-3)"
}
}
]
},
{
"id": "temperature_sensitivity_sweep",
"description": "Stratospheric temperature sweep over 200-280 K (cold polar vortex to warm sub-tropical mid-stratosphere). Each temperature drives an independent one-hour integration; the plots show the t=3600 s ozone and ClO against T, surfacing the net effect of the temperature-dependent rate coefficients on the catalytic balance.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"parameter_sweep": {
"type": "cartesian",
"dimensions": [
{
"parameter": "T",
"values": [
200.0,
210.0,
220.0,
230.0,
240.0,
250.0,
260.0,
270.0,
280.0
]
}
]
},
"plots": [
{
"id": "o3_vs_T",
"type": "line",
"description": "Ozone at t=3600 s vs temperature.",
"x": {
"variable": "T",
"label": "Temperature (K)"
},
"y": {
"variable": "O3",
"label": "O3 (m^-3)"
}
},
{
"id": "clo_vs_T",
"type": "line",
"description": "Chlorine monoxide at t=3600 s vs temperature.",
"x": {
"variable": "T",
"label": "Temperature (K)"
},
"y": {
"variable": "ClO",
"label": "ClO (m^-3)"
}
}
]
},
{
"id": "altitude_density_sweep",
"description": "Air-density sweep across the stratospheric range, mimicking altitude: M from 1e22 m^-3 (~60 km) to 3e24 m^-3 (~20 km). Each density drives an independent one-hour integration; the plot shows the t=3600 s ozone against M, illustrating how the M-dependent three-body production competes with the bimolecular catalytic sinks.",
"time_span": {
"start": 0.0,
"end": 3600.0
},
"parameter_sweep": {
"type": "cartesian",
"dimensions": [
{
"parameter": "M",
"values": [
1e+22,
3e+22,
1e+23,
3e+23,
1e+24,
3e+24
]
}
]
},
"plots": [
{
"id": "o3_vs_M",
"type": "line",
"description": "Ozone at t=3600 s vs air number density.",
"x": {
"variable": "M",
"label": "M (m^-3)"
},
"y": {
"variable": "O3",
"label": "O3 (m^-3)"
}
}
]
}
]
}