Atmos. Chem. Phys., 3, 1293–1300, 2003
www.atmos-chem-phys.org/acp/3/1293/

Atmospheric
Chemistry
and Physics

Sensitivity studies of the recent new data on O(1D) quantum yields
in O3 Hartley band photolysis in the stratosphere
N. Taniguchi1 , S. Hayashida1 , K. Takahashi2 , and Y. Matsumi2
1 Faculty of Science, Nara Women’s University, Kitauoya - Nishimachi, Nara, 630 - 8506, Japan
2 Solar - Terrestrial Environment Laboratory, Nagoya University, Honohara 3 - 13, Toyokawa, 442 - 8507, Japan

Received: 3 February 2003 – Published in Atmos. Chem. Phys. Discuss.: 12 May 2003
Revised: 8 August 2003 – Accepted: 20 August 2003 – Published: 3 September 2003
Abstract. The production yields of excited oxygen O(1 D)
atoms from the near ultraviolet O3 photolysis are essential
quantities for atmospheric chemistry calculations because of
its importance as major sources of hydroxyl (OH) radicals
and nitric oxide (NO). Recently, new O(1 D) quantum yields
from O3 photolysis between 230 and 305 nm in the Hartley band region were reported, which are almost independent of the photolysis wavelength (0.88–0.93) and smaller
than NASA/JPL-2000 recommendations (0.95 between 240
and 300 nm). In order to assess consequences of the newdata of O(1 D) quantum yields on the stratospheric chemistry,the changes in stratospheric chemical partitioning and O3
concentration are examined using a one-dimensional atmospheric model. Our steady state model simulations for 40◦ N
in March indicate that the smaller O(1 D) quantum yields result in increases of stratospheric O3 (up to ∼2% in the upper
stratosphere), which are attributed to the changes in HOx ,NOx , and ClOx abundance and their catalyzed O3 loss rates.

1 Introduction
Photodissociation by solar ultraviolet (UV) radiation drives
much of the chemistry in the stratosphere, since it contributes
to the removal of many atmospheric trace gases by decomposition and generates highly reactive radicals. One of theimportant photochemical reactions is the photolysis of O3 in
the UV region to produce O(1 D) atoms, which react withwater vapor and generate OH radicals (Brasseur et al., 1999;
Finlayson-Pitts and Pitts, 1999):
1

1

O3 + hν → O( D) + O2 ( 1g ),→ O(3 P ) + O2 (X 3

(1)

X−
g

),

Correspondence to: N. Taniguchi(ntanig@ics.nara-wu.ac.jp)
c European Geosciences Union 2003

(2)

O(1 D) + H2 O → 2OH,

(3)

where h is Planck’s constant and ν is photon frequency. The
chemical reactions of O(1 D) play important roles in determining the chemical composition of the stratosphere. Figure 1 illustrates the principal chemical reactions involving
O(1 D) in the stratosphere. Most of the O(1 D) atoms produced by the photolysis of O3 are quickly deactivated by collisions with major atmospheric species (M = N2 and O2 ) andthen form O3 molecules again:
O(1 D) + M → O(3 P ) + M,

(4)O(3 P ) + O2 + M → O3 + M.

(5)

The production rate of stratospheric OH depends on theO(1 D) production from O3 photolysis. The OH radicals
formed by reaction (3) initiate the HOx catalytic cycle ofO3 loss, which is the main process for controlling O3 loss
in both the lower and upper stratosphere (Fig. 7). OH is directly involved in a HOx catalytic cycle and also controls thepartitioning between active species such as nitrogen oxides
and chlorine oxides and their reservoirs:
OH + NO2 + M → HNO3 + M,

(6)

OH + HCl → Cl + H2 O.

(7)

The O(1 D) also produces the NO radical in the stratosphere
due to the reaction with N2 O:
O(1 D) + N2 O → 2NO.

(8)

NO is the major catalyst for O3 loss of NOx in the middle stratosphere. NOx also suppresses the halogen catalytic
destruction of O3 by sequestering them in unreactive forms
such as ClONO2 :NO2 + ClO + M → ClONO2 + M.

(9)

Figure 1. Schematic of the reaction pathways involving O(1D) formation in the O3 photolysis
in the stratosphere. Dash line means a photolysis reaction. Numbers given in parentheses
correspond to reaction numbers shown in the text.

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N. Taniguchi et al.: Sensitivity studies of the recent new data on O(1 D) quantum yields

Fig. 1. Schematic of the reaction pathways involving O(1 D) formation in the O3 photolysis in the stratosphere. Dash line meansa photolysis reaction. Numbers given in parentheses correspond toreaction numbers shown in the text.

The net effect on stratospheric O3 depends on the relative
contributions of these mechanisms at each altitude.
The channel branching ratios between channels (1) and(2) from O3 photolysis have been examined extensively inthe wavelength range λ>306 nm at 298 K and low temperature by various laboratories over the past two decades (Matsumi et al., 2002, and references therein), which are usedin the model calculation for such a comparison of observed
and modeled OH, HOx , and O3 concentrations and photolysis rate of O3 (e.g. Wennberg et al., 1999; Pfister et al., 2000).
Although the O3 chemistry of stratosphere, especially upper
stratosphere, is quite simple and relatively well-understood(Brasseur et al., 1999; Finlayson-Pitts and Pitts, 1999), in
the upper stratosphere and mesosphere a number of models cause an under-prediction of O3 concentrations at 40–
50 km altitude compared to observations, with magnitude ofthe discrepancy increasing with altitude (Eluszkiewicz andAllen, 1993). This has been known as the “ozone deficit”
problem. In the upper stratosphere, the chemical composition is determined by chemical processes that are faster than
the relevant dynamical processes. Crutzen et al. (1995) and
Grooß et al. (1999) have investigated the O3 budget in theupper stratosphere in comparison with observations and photochemical modeling, and kinetic reaction rate coefficientsand photochemical data used in their studies were JPL-1994
and JPL-1997 recommendations for atmospheric modelingby NASA panel, respectively (DeMore et al., 1994; DeMore
et al., 1997). They have pointed out that the uncertainty
in the model parameters is a large source of the discrepancy although improvement of the observation quality andupdated the latest model parameters decreases a significant
ozone deficit. Smith et al. (2001) estimated uncertainties
in model O3 from the box model sensitivities using mechaAtmos. Chem. Phys., 3, 1293–1300, 2003

nism parameter uncertainties in JPL-2000 evaluation. They
reported O3 uncertainties still remain to be near 12% in the
middle and upper stratosphere and the uncertainties increasein the lower stratosphere. The JPL-2000 recommendations
significantly reduced several key reaction uncertainty values,that is, O3 catalytic photochemistry uncertainties, comparedwith uncertainties before JPL-2000. From the same sensitivity analysis by using JPL-1994, Dubey et al. (2000) estimated O3 uncertainties were nearly 3–5% larger than 12% of
Smith et al. (2000). Knowledge of the photochemical processes that determine stratospheric O3 concentration is stillof considerable interest. The O(1 D) quantum yields in thephotolysis of O3 at wavelengths shorter than 300 nm have notreceived much attention and JPL-2000 panel recommended
the constant value of 0.95 for the wavelength range of 240–
300 nm (Sander et al., 2000). The experimental data for theO(1 D) quantum yields from O3 photolysis over the Hartleyband (200–300 nm) are sparse, which may result in some notable uncertainties in the model calculation. Very recently,
Taniguchi et al. (2000) and Takahashi et al. (2002) have published results of the precise O(1 D) quantum yield measurements in the photolysis of O3 between 230 and 305 nm. In
this study, the atmospheric impacts of their laboratory resultsof O(1 D) quantum yields from O3 photolysis on the stratospheric chemistry have been explored, in the framework of aone-dimensional chemical model.

2

O(1 D) quantum yield data in the photolysis of O3

The absolute quantum yields of O(1 D) formation from O3
photolysis between 306 and 328 nm have been evaluated by
Matsumi et al. (2002) with the detailed examination of recent
experimental measurements as a joint activity of SPARC and
IGAC. Very recently, Takahashi et al. (2002) have measured
the O(1 D) quantum yields from O3 photolysis between 230
and 308 nm using a new experimental technique. Using thesame technique, Taniguchi et al. (2000) have indicated that
the O(1 D) quantum yield in the wavelength range of 297–
306 nm is almost independent of the wavelength (∼0.89). In
Fig. 2, the yield values presented by Taniguchi et al. (2000)
and Takahashi et al. (2002) are compared with both values
previously reported by other different groups (Trolier andWiesenfeld, 1988; Cooper et al., 1993; Talukdar et al., 1997,1998) and JPL-2000 recommendations (Sander et al., 2000).
Talukdar et al. (1998) reported that the O(1 D) quantum yield
between 289 and 305 nm was 0.89±0.02, which is in good
agreement with results presented by Taniguchi et al. (2000)
and Takahashi et al. (2002). The yield values reported by
Trolier and Wiesenfeld (1988) and JPL-2000 recommendations in this wavelength region are larger than values reported
by Talukdar et al. (1998) , Taniguchi et al. (2000), and Takahashi et al. (2002). At shorter wavelengths, JPL-2000 panel
has recommended a constant value of 0.95 for the O(1 D)
quantum yield in the Hartley band photolysis of O3 between
www.atmos-chem-phys.org/acp/3/1293/

obtained by Taniguchi et al. (2000) and Takahashi et al. (2002). For comparison, the yieldvalues reported by other groups are also shown (Trolier and Wiesenfeld, 1988; Cooper et al.,
1993; Talukdar et al., 1997, 1998). Solid line indicates the yield values recommended by
JPL-2000 evaluations for atmospheric modeling by NASA panel (Sander et al., 2000), which
are constant (0.95) between 240 and 300 nm.

Figure 3. Ultraviolet absorption spectrum of O3 in the Hartley band at 263 K (Malicet et al.,1995) and actinic fluxes as a function of altitudes of 15, 25, and 40 km when the solar zenith
angle is 40 degree (Finlayson-Pitts et al., 1999).

2
–18

cm )

1
0.9
0.8

1

220

240

260

280

300

Wavelength (nm)Fig. 2. The quantum yields for O(1 D) formation in the Hartley band
photolysis of O3 obtained by Taniguchi et al. (2000) and Takahashi
et al. (2002). For comparison, the yield values reported by othergroups are also shown (Trolier and Wiesenfeld, 1988; Cooper et al.,
1993; Talukdar et al., 1997, 1998). Solid line indicates the yield values recommended by JPL-2000 evaluations for atmospheric modeling by NASA panel (Sander et al., 2000), which are constant (0.95)
between 240 and 300 nm.

240 and 300 nm. The O(1 D) quantum yields presented by
Takahashi et al. (2002) are almost independent of the photolysis wavelengths (∼0.91) between 230 and 300 nm, which
are 4∼5% smaller than the JPL-2000 recommendation values and in good agreement with values determined by Cooper
et al. (1993), except for 228.5 and 231 nm. Talukdar et al.
(1997) reported the room temperature O(1 D) quantum yieldof 0.91±0.06 at 248 nm, which is in good agreement with thevalue of 0.914±0.019 presented by Takahashi et al. (2002).
Talukdar et al. (1998) showed that the O(1 D) quantum yields
between 289 and 305 nm were independent of the temperature (203–320 K). Talukdar et al. (1997) and Takahashi
et al. (1998) reported a negligible temperature dependenceof O(1 D) quantum yields at 248 nm and 305 nm, respectively. We have focused on the difference in the wavelength
range of 230–305 nm between the new quantum yield values(Taniguchi et al., 2000; Takahashi et al., 2002) and JPL-2000
recommendations, and examined the consequences of thedifference in the chemical compositions in the mid-latitudestratosphere using a one-dimensional chemical model. The
effect of the difference of the O(1 D) quantum yield values in
the wavelength region of 230–305 nm should be significant
in the stratosphere and very little in the troposphere, since
the solar radiation at the wavelengths shorter than 305 nm
mainly affects the stratospheric chemistry.
www.atmos-chem-phys.org/acp/3/1293/

15 km

5

10

14

10

13

O3 Abs.

–1

0.5

25 km

s )

0.6

Trolier and Wiesenfeld [1988]
Cooper et al. [1993]
Talukdar et al. [1997]
Talukdar et al. [1998]
JPL–2000, Sander et al. [2000]
Taniguchi et al. [2000]
Takahashi et al. [2002]

40 km

10

–2

Absorption Cross Section, σ (10

1.1

0.7

1295

Solar Flux, F (Photons cm

O( D) Quantum Yield, Φ1 D

N. Taniguchi et al.: Sensitivity studies of the recent new data on O(1 D) quantum yields

0

240

260
280
Wavelength (nm)300

Fig. 3. Ultraviolet absorption spectrum of O3 in the Hartley bandat 263 K (Malicet et al., 1995) and actinic fluxes as a function ofaltitudes of 15, 25, and 40 km when the solar zenith angle is 40
degree (Finlayson-Pitts et al., 1999).

3

O(1 D) production rates in the stratosphere

The total production rates of O(1 D) atom from O3 photolysis
at several altitudes, Ptotal (O1 D), were calculated byZ
Ptotal (O1 D) = P (λ)dλZ= F (λ)σ (λ, T )81D (λ, T )dλ,(10)where λ is the wavelength, and T is the temperature and F
the actinic flux at the altitude. σ defines the absorption crosssection of the O3 molecule and 81D the O(1 D) quantum
yield from O3 photolysis which is the probability for a process (1) to occur upon absorption of a photon. We calculated
the Ptotal (O1 D) values for the altitudes of 15, 25, and 40 km.
The numerical data of F at solar zenith angle of 40 degree
were taken from Finlayson-Pitts and Pitts (1999) and σ at
228 and 263 K were taken from Malicet et al. (1995) (Fig. 3).
The photoabsorption cross section measurements reported by
Malicet et al. (1995) are in good agreement with the recommended values by NASA/JPL 1997 and 2000 (DeMore etal., 1997; Sander et al., 2000). It should be noted that the relative O(1 D) production rate function, P(λ), predominantly
depends on the wavelength region ∼230–320 nm, which islimited by the sunlight spectrum penetrating into the stratosphere and by the absorption properties of O3 molecules.
Therefore, the O(1 D) quantum yield from O3 photolysis in
this wavelength region and its temperature dependence is a
key input parameter for modeling calculations in the stratospheric chemistry since the predominat source of the O(1 D)
atoms in the stratosphere is the photolysis of O3 . Due to the
Atmos. Chem. Phys., 3, 1293–1300, 2003

N. Taniguchi et al.: Sensitivity studies of the recent new data on O(1 D) quantum yields

1296

Table 1. List of chemical species used in the one-dimensional
chemical model calculations.
Initially set by Brasseur et al. (1999)
O3
NO
CH4
HCl

H
NO2
N2 O
CCl4

OH
N2 O5
Cl
CFCl3

HO2
HNO4
ClO
CF2 Cl2

H2 O2
HNO3
HOCl
CH3 ClN
H2 O
ClONO2CO

Calculated to be in steady stateO(3 P )HBr
H2O(1 D)
Br
ClOO

NO3
BrO
CHClF2Cl2HOBr
CH3 BrCl2 O2BrONO2OClO
CO2temperature dependence of σ and 81D , the ambient temperature influences the O(1 D) production rate functions at each
altitude. At λ>310 nm, the O(1 D) formation via photodissociation of the vibrationally and rotationally excited O3 andspin-forbidden process takes place (Matsumi et al., 2002).
Since the population of the internally excited O3 molecules
is dependent on the temperature, the O(1 D) quantum yields
at λ>310 nm (up to ∼325 nm) change as a function of thetemperature (Talukdar et al., 1998; Takahashi et al., 1998;
Smith et al., 2000). In the calculations for the wavelengths
longer than 308 nm, the expression for the O(1 D) quantum
yields recommended by JPL-2000 (Sander et al., 2000) wasused, which is a function of photolysis wavelength and temperature.
We found that the total O(1 D) production rates
Ptotal (O 1 D) estimated with the new O(1 D) quantum yields
are smaller than those with the JPL-2000 recommendations
by 2.5, 3.8 and 5.1%, at 15, 25 and 40 km, respectively.
Atmospheric O3 is photolyzed mainly by the UV radiation
wavelength ∼295–315 nm at 25 km and ∼250–310 nm at
40 km, respectively. Therefore, the decreases in O(1 D) production rates caused by the new O(1 D) quantum yields in the
wavelength range of 230–305 nm change the Ptotal (O 1 D)
more effectively at 40 km than that at 25 km. Comparisonsof results obtained using the smaller values of O(1 D) quantum yields with those using the recommendations of JPL2000 clearly suggest the significance of new O(1 D) yielddata. Therefore, we examined the effects of the new O(1 D)yields on the stratospheric chemistry by model calculations,as described in the following section.
4 One-dimensional atmospheric model calculations
We have examined the effect of the smaller values of O(1 D)
quantum yields (Taniguchi et al., 2000; Takahashi et al.,2002) using a one-dimensional chemical model, in which all
the chemical reactions related to O3 chemistry are reasonably
represented and it is suitable for assessing the impact of the
new O(1 D) quantum yield data on stratospheric chemistry.
Atmos. Chem. Phys., 3, 1293–1300, 2003

All chemical schemes in this one-dimensional model usedhere are the same as those used in the Garcia-Solomon twodimensional (GS-2D) model (e.g., Solomon et al., 1996),
which includes 90 kinetic reactions, 30 photolysis reactions,and 40 chemical species. Table 1 summarizes all 40 species
included in this model. This one-dimensional model calculated diurnal averaged values of photolysis rates and therefore diurnal averaged mixing ratios of chemical species (byusing the family method) for a specific altitude and season in
mid-latitude in the northern hemisphere, by using the same
formulations as those of G-S 2-D model. However, thereis large difference in parameterizations of the effect of dynamics between the one-dimensional model which includes
the effect of vertical diffusion and the G-S 2-D model which
considers the effect of meridional transport. For the vertical eddy diffusion coefficients in the one-dimensional model,
values have been chosen to match the estimates of Chang(1974). The incident solar actinic fluxes specified at the topof atmosphere are taken from World Meteorological Organization workshop report (1985) and their atmospheric attenuation is calculated in the model. The reaction rate coefficients and the absorption cross sections are taken from
NASA/JPL-1997 and -2000 recommendations (DeMore etal., 1997; Sander et al., 2000). The initial mixing ratiosof 24 chemical species including O3 are taken from reference values in March at 30◦ N from Brasseur et al. (1999)(Table 1). The model results of vertical distributions of thechemical species and photolysis rates calculated in the onedimensional model used in our study are approximately ingood agreement with model results of vertical distributions
presented in JPL-1997 and Brasseur et al. (1999) in the same
conditions of latitude, altitude, and season in the northernhemisphere. This means that all the chemical reactions related to ozone chemistry are reasonably represented in our
one-dimensional model and thus the model is suitable forassessing the impact of new O(1 D) quantum yield data on
stratospheric chemistry. Since model responses of chemical
species due to the change in O(1 D) quantum yields represent the time-dependent propagation of infinitesimal perturbations, individual responses grow and converge on the timescale associated with that process. Therefore, calculations
for all chemical species with the new values or JPL-2000 recommendations for the O(1 D) quantum yields were run longenough to ensure convergence (±0.2% in concentration of all
chemical species). The vertical profiles of O3 , HNO3 , andchemical families, HOx , ClOx , and NOx , for 40◦ N in Marchpredicted by the model are illustrated in Fig. 4, when the
new quantum yield values are used. Here, the families aredefined as HOx = H + OH + HO2 , ClOx = Cl + ClO, andNOx = NO + NO2 . The solar spectral intensity is calculated
for equinox in March (the solar declination angle is zero degree).
We have estimated how model concentration results forO3 and other chemical species are affected when a new set ofmodel parameters, that is, the new O(1 D) quantum yields arewww.atmos-chem-phys.org/acp/3/1293/

Figure 4. Results of the one-dimensional chemical model calculations. Diurnally averaged
vertical profiles of NOx, HOx, ClOx, HNO3 and O3 (dot-dash, dot, solid, thick dash, and thicksolid lines, respectively) predicted for 40° N in March using the O(1D) quantum yield values
measured by Taniguchi et al. (2000) and Takahashi et al. (2002).

and 60° N (dot, solid, and dot-dash lines, respectively) in March as a function of altitude
using the O(1D) quantum yield values measured by Taniguchi et al. (2000) and Takahashi etal. (2002), relative to those predicted using JPL-2000 recommendations for atmosphericmodeling by NASA evaluation panel (Sander et al., 2000), that is, δO(1D) and δO3 defined byeq. (11)
1 in the text.

N. Taniguchi et al.: Sensitivity studies of the recent new data on O( D) quantum yields

50

1297

50

O3
NOX

40

Altitude (km)Altitude (km)

HNO3

HOX
30

40
1

O( D )
30

O3
ClOX
20

20
6

8

10

12

–6

10
10
10
10
–3
Concentration (molecules cm )adopted. The change in O3 concentration, δO3 , is the relativechange in a predicted model concentration:[O3 ]N ew − [O3 ]J P L[O3 ]J P L(11)

where [O3 ]N ew is concentration of O3 calculated with the
new values of O(1 D) quantum yields from O3 photolysis between 230 and 308 nm (Taniguchi et al., 2000; Takahashi etal., 2002), while [O3 ]J P L is that using JPL-2000 recommendations as a standard model (Sander et al., 2000). Figure 5
shows the results of the diurnally averaged chemical model
calculations, which indicates the change of the O(1 D) andO3 concentrations, δO(1 D) and δO3 , versus altitude for 20,
40, and 60◦ N in March between the model runs with the
new O(1 D) values and the JPL-2000 recommendations. The
partitioning changes in the chemical families, NOx , HOx ,and ClOx , predicted as a result of the parameter changes ofO(1 D) quantum yields from JPL-2000 recommendations to
the new values are shown in Fig. 6.
Here, the mixing ratios of chemical species are initialized
by using reference values reported by Brasseur et al. (1999)
as the typical values for 30◦ N in March, in which mixing ratios of Cly are corresponded to be 0.7, 2.5, 3.2, and 3.3 ppb
at 20, 30, 40, and 50 km respectively, and are in good agreement with those of WMO report (1999). Moreover, we performed sensitivity study to evaluate the impact of initial mixing ratio of Cly on our model results. In Fig. 5, we showed
www.atmos-chem-phys.org/acp/3/1293/

–2

0

2

Change in Concentration (%)

Fig. 4. Results of the one-dimensional chemical model calculations.
Diurnally averaged vertical profiles of NOx , HOx , ClOx , HNO3
and O3 (dot-dash, dot, solid, thick dash, and thick solid lines, respectively) predicted for 40◦ N in March using the O(1 D) quantum
yield values measured by Taniguchi et al. (2000) and Takahashi etal. (2002).

δO3 ≡

–4

Fig. 5. Results of the one-dimensional chemical model calculations.
The percentage changes in diurnally averaged O(1 D) and O3 concentrations predicted for latitude of 20, 40, and 60◦ N (dot, solid,
and dot-dash lines, respectively) in March as a function of altitude
using the O(1 D) quantum yield values measured by Taniguchi et al.
(2000) and Takahashi et al. (2002), relative to those predicted using
JPL-2000 recommendations for atmospheric modeling by NASAevaluation panel (Sander et al., 2000), that is, δO(1 D) and δO3 defined by Eq. (11) in the text.

the relative changes in the chemical concentrations calculated on the bases of the “new experimental data” and theJPL-2000 recommendations of O(1 D) quantum yields by using Cly initial mixing ratios from Brasseur et al. (1999). Ina similar method, we calculated the relative changes in thechemical concentrations calculated on the bases of the “newexperimental data” and the JPL-2000 recommendations byusing the initial mixing ratios ten times as large as those of
Brasseur et al. (1999). We found that there is no serious
difference (±0.1%) between the relative changes calculatedwith Cly initial mixing rations of Brasseur et al. (1999) andthe relative changes with the initial mixing ratios ten times
larger than Brasseur et al. (1999). These relative changes in
the chemical concentrations of all 40 species included in ourmodel (Table 1) are respectively calculated on the bases of
the “new experimental data” and the JPL-2000 recommendations. In this way, we also found that that such changes in
the initial mixing ratios of Cly as demonstrated in this sensitivity study are not likely to affect substantial influence on theevaluations of relative changes in chemical concentrations of
O3 , NOx , HOx and ClOx as shown in Fig. 6.
Changes in the reactive families influence O3 loss rates
via the catalytic cycles involving those families. Figure 7
Atmos. Chem. Phys., 3, 1293–1300, 2003

and thick lines, respectively) predicted for latitude of 40° N in March as a function of altitude
using the O(1D) quantum yield values measured by Taniguchi et al. (2000) and Takahashi etal. (2002), relative to those predicted using JPL-2000 recommendations for atmosphericmodeling by NASA evaluation panel (Sander et al., 2000).

Figure 7. Results of the one-dimensional chemical model calculations. Diurnally averaged
O3 loss rates due to NOx, HOx, and ClOx chemistry (dot-dash, dot, and solid lines,
respectively) predicted for latitude of 40° N in March using the O(1D) quantum yield values
measured by Taniguchi et al. (2000) and Takahashi et al. (2002). Thick line shows the total
1 D) quantum yields
N. Taniguchi et al.: Sensitivity
studiesrecentnewdataO(O3 loss rate
which isof
the thesum ofthe O3 loss
rates
in NOonClOx catalytic cycles.
x, HOx, and

1298

50

50

40

Altitude (km)Altitude (km)

O3

ClOX
30

HOX

40

30

ClOX

NOX

Total

HOX
20

NOX

–4

20

–2

0

2

Change in Concentration (%)
Fig. 6. Results of the one-dimensional chemical model calculations. The percentage changes in durnally averaged NOx , HOx ,ClOx , and O3 concentrations (dot-dash, dot, solid, and thick lines,
respectively) predicted for latitude of 40◦ N in March as a function of altitude using the O(1 D) quantum yield values measured
by Taniguchi et al. (2000) and Takahashi et al. (2002), relative tothose predicted using JPL-2000 recommendations for atmosphericmodeling by NASA evaluation panel (Sander et al., 2000).

shows the O3 loss rates by the three principal reactive families, NOx , HOx , and ClOx , versus altitude for latitude of40◦ N in March, which were calculated based on the newO(1 D) quantum yield values.

5

Discussions

The steady-state O(1 D) concentration for 40◦ N becomes
smaller by ∼2–6% with a negative peak at 35 km due tothe smaller O(1 D) quantum yields from O3 photolysis between 230 and 308 nm (Fig. 2), depending on altitude in
the stratosphere as shown in Fig. 5. This result is consistent with our evaluation of the altitudinal changes in the totalO(1 D) production rate Ptotal (O1 D). This indicates the consistency between the simple calculation with Eq. (10) and theone-dimensional chemical calculation, and that the concentration of O(1 D) is influenced only by the production processof O(1 D). The loss process of O(1 D) is determined by thequenching process (4) which is not affected by the changes of
the concentrations of minor species in the atmosphere. The
O3 concentration calculated with the new O(1 D) quantum
yields is higher than that with the JPL-2000 recommendations throughout the stratosphere. It should be noted that thechange in the O(1 D) concentration influences O3 abundance
Atmos. Chem. Phys., 3, 1293–1300, 2003

10

5

6

7

10

O3 Loss Rate (molecule cm

10
–3

–1

s )

Fig. 7. Results of the one-dimensional chemical model calculations. Diurnally averaged O3 loss rates due to NOx , HOx , and ClOx
chemistry (dot-dash, dot, and solid lines, respectively) predicted for
latitude of 40◦ N in March using the O(1 D) quantum yield values
measured by Taniguchi et al. (2000) and Takahashi et al. (2002).
Thick line shows the total O3 loss rate which is the sum of the O3
loss rates in NOx , HOx , and ClOx catalytic cycles.

even though atmospheric concentration of O(1 D) atoms ismuch lower than O3 concentration, since the O(1 D) reactions (3) and (8) are the direct source for stratospheric HOx
and NOx molecules which control the stratospheric radical
partitioning and O3 abundance through catalytic reactions(Fig. 1). The calculated response of O3 concentration fromthese changes in the concentration of HOx and NOx is different between the upper, middle, and lower stratospheres because of the interdependence of the O3 loss catalytic cycles.
As shown in Figs. 5 and 6, the absolute change in thestratospheric O3 concentration is the largest at ∼40–45 km(increase up to ∼2%). This results from effect of the suppression of O3 loss by the decrease of the NOx , HOx , andClOx concentrations in their catalytic O3 loss cycles (Fig. 6).
Figure 7 shows that total O3 loss rate, that is, the sum of
the O3 loss rates in NOx , HOx , and ClOx catalytic cycles
has a peak around 40 km. Changes in O3 loss rates in NOx ,HOx , and ClOx catalytic cycles, which were calculated frommodel runs with the new O(1 D) quantum yields and with
the JPL-2000 recommendations, were similar to changes in
NOx , HOx , and ClOx concentrations which are shown in
Fig. 6. Above this region, the contribution of the HOx cycle
becomes predominant drastically as the altitude increases.
The HOx concentration in the upper stratosphere is decreasedby the decrease of the OH formation trough reaction (3) due
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N. Taniguchi et al.: Sensitivity studies of the recent new data on O(1 D) quantum yields
to the smaller O(1 D) quantum yield (Fig. 6). In the upper
stratosphere, atomic O(3 P ) constitutes efficiently the following catalytic cycle in which the rate-limiting step in the cycle
is reaction (12):OH + O3 → HO2 + O2 ,(12)

HO2 + O → OH + O2 .
(Net : O + O3 → 2O2 )(13)

Therefore, the decrease in HOx concentration in the upper
stratosphere caused by the smaller O(1 D) quantum yields results in the O3 concentration increase most effectively in thisregion. On the other hand, HOx concentration increases in
the middle and lower stratosphere (Fig. 6). The NOx concentration is reduced by the decrease of the O(1 D) formation via reaction (8). This reduction of the NOx concentration takes place throughout the stratosphere. The increaseof HOx concentration in the middle and lower stratospheremay be attributed to the decrease of the rate of reaction (6)due to the smaller concentration of NOx . Since the contribution of three-body reaction (6) becomes more significant
at lower stratospheric altitudes, HOx increases in the lower
stratosphere as shown in Fig. 6.
ClOx concentration also decreases in the upper-middle
stratosphere with the smaller O(1 D) quantum yields, and alittle increases in the lower stratosphere. The behavior of
ClOx concentration change is similar to that of HOx concentration. The chlorine reservoir compound HCl is activatedto ClOx by reaction (7), that is, the reaction between OH
and HCl (Fig. 1). The decreased OH production rate due tothe smaller O(1 D) quantum yield results in the smaller ClOx
concentration. In the lower stratosphere, the decrease of thethird body reaction (9) with smaller NOx concentration may
lead to the increase of ClOx . ClOx cycle is important especially around 45 km and accounts for about ∼35% of thetotal O3 loss rate in this region (Fig. 7).
As shown in Fig. 6, NOx concentration is decreased
throughout the stratosphere by the smaller O(1 D) quantum
yields, while the enhancement of O3 takes place around 20–
25 km (up to ∼1%), but slightly less around 30 km. In the
middle stratosphere, the NOx catalytic cycle has the largest
effect on the O3 reduction (Fig. 7). The enhancements of O3
concentration around 20–25 km with the new O(1 D) quantum yields should be attributed to the decrease of NOx catalytic O3 loss.

6

Additional note

After submitting this paper, a new edition of the NASA/JPL
evaluations has been released (Sander et al., Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies,
Evaluation Number 14, JPL Publication 02-25, 2003). The
www.atmos-chem-phys.org/acp/3/1293/

1299

O(1 D) quantum yield values in the NASA/JPL-2003 recommendation have been updated from those in the NASA/JPL2000 recommendation. The O(1 D) quantum yields fromO3 photolysis for λ<306 nm are recommended to be 0.95
in JPL-2000 but to be 0.90 in the latest JPL-2003. The
new laboratory O(1 D) data used in this work are in closely
agreement with the NASA/JPL-2003 recommendations. Actually, we performed one-dementional model calculations
to compare changes in the O3 concentration between the
NASA/JPL-2003 recommendations and the new laboratory
O(1 D) data, and the result showed very small differences in
the O3 concentration throughout the stratosphere (<0.14%).
7

Conclusions

Consequences of the new data of O(1 D) quantum yields fromO3 photolysis between 230 and 305 nm in the Hartley band
region on the stratospheric chemistry are examined using a
one-dimensional atmospheric model. Our sensitivity studies for mid-latitude in March indicate that the smaller O(1 D)
quantum yields increase the O3 concentration throughout
stratosphere via a decrease in the importance of NOx concentration in the middle stratosphere and the HOx in the upper
stratosphere. The enhancement of O3 concentration in our
chemical model calculations around 40–50 km altitude by using new O(1 D) quantum yields contributes to precise assessment of the photochemical O3 budget including the “ozone
deficit” problem.
Acknowledgements. N. T. thanks the Japan Society for Promotion of Science for a fellowship for young scientists. The onedimensional model used in this study was originally offered by Dr.
Susan Solomon, NOAA Aeronomy Laboratory. N. T. gives special
thank to Prof. Masahiro Kawasaki, Kyoto University, for his helpful discussions and encouragements. N. T. would like to thank Dr.
Akiko Kagawa for her valuable comments on the manuscript. This
work was partly supported by a Grant-in-Aid from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.

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