Effects of Chlorine and Chlorine Monoxide on Stratospheric Ozone Depletion

This paper presents a system approach of mass balance calculations of ozone and other species under diffusion-convection-reaction processes to study the impacts of major ozone-depleting chemicals, chlorine (Cl) and chlorine monoxide (ClO), and the effect of photolysis on ozone concentrations, ozone depletion, total ozone abundance, and ozone layer along the altitude in the stratosphere. The calculated ozone concentrations and profile of the layer followed a similar trend and were generally in good agreement with the measurements above the tropical area. The calculated peak of the layer was at the same mid-stratosphere at Z = 30 km with a peak concentration and total ozone abundance about 20% higher than the measured peak concentration of 8.0 ppm and total abundance of 399 DU. In the presence of Cl and ClO, the calculated ozone concentrations and total abundance were substantially reduced. Cl generally depleted more uniformly of ozone across the altitude, while ClO reduced substantially the ozone in the upper stratosphere and thus shifted the peak of the layer to a much lower elevation at Z = 14 km. Although both ClO and Cl are active ozone-depleting chemicals, ClO was found to have a more pronounced impact on ozone depletion and distribution than Cl. The possible explanations of these interesting phenomena were discussed and elaborated. The approach and calculations in this paper were shown to be useful in providing an initial insight into the structure and behavior of the complex ozone layer.

2-D Modeling and Calculations of Stratospheric Ozone and Influences of Convection, Diffusion, and Time

An engineering system approach of 2-D cylindrical model of transient mass balance calculations of ozone and other concerned chemicals along with fourteen photolysis, ozone-generating and ozone-depleting chemical reaction equations was developed, validated, and used for studying the ozone concentrations, distribution and peak of the layer, ozone depletion and total ozone abundance in the stratosphere. The calculated ozone concentrations and profile at both the Equator and a 60˚N location were found to follow closely with the measured data. The calculated average ozone concentration was within 1% of the measured average, and the deviation of ozone profiles was within 14%. The monthly evolution of stratospheric ozone concentrations and distribution above the Equator was studied with results discussed in details. The influences of slow air movement in both altitudinal and radial directions on ozone concentrations and profile in the stratosphere were explored and discussed. Parametric studies of the influences of gas diffusivities of ozone DO3 and active atomic oxygen DO on ozone concentrations and distributions were also studied and delineated. Having both influences through physical diffusion and chemical reactions, the diffusivity (and diffusion) of atomic oxygen DO was found to be more sensitive and important than that of ozone DO3 on ozone concentrations and distribution. The 2-D ozone model present in this paper for stratospheric ozone and its layer and depletion is shown to be robust, convenient, efficient, and executable for analyzing the complex ozone phenomena in the stratosphere. .

Calculations and Sensitivity Analysis of Chlorine-,NO_(x)-,and Bromine-Depleting Cycles of Stratospheric Ozone

This paper presents an engineering system approach using a 2D model of conservation of mass to study the dynamics of ozone and concerned chemical species in the stratosphere.By considering all fourteen photolysis,ozone-generating,and-depleting chemical reactions,the model calculated the transient,spatial changes of ozone under different physical-chemical-radiative conditions.Validation against the measured data demonstrated good accuracy,close match of our model with the observed ozone concentrations at both 20°S and 90°N locations.The deviation in the average concentration was less than 1% and in ozone profiles less than 17%.The impacts of various chlorine-(Cl),nitrogen oxides-(NO_(x)),and bromine-(Br)depleting cycles on ozone concentrations and distribution were investigated.The chlorine catalytic depleting cycle was found to exhibit the most significant impact on ozone dynamics,confirming the key role of chlorine in the problem of ozone depletion.Sensitivity analysis was conducted with levels of 25%,50%,100%,200%,and 400% of the baseline value.The combined cycles(Cl+NO_(x)+Br)showed the most significant influence on ozone behavior.The total ozone abundance above the South Pole could decrease by a small 3%,from 281 DU(Dubson Units)to 273 DU for the 25% level,or by a huge thinning of 60%to 114 DU for the 400% concentration level.When the level of chlorine gases increased beyond 200%,it would cause ozone depletion to a level of ozone hole(below 220 DU).The 2D Ozone Model presented in this paper demonstrates robustness,convenience,efficiency,and executability for analyzing complex ozone phenomena in the stratosphere.

Calculations of Stratospheric Ozone and Effects of Diffusivity

This paper presents a system approach of mass balance of ozone and other species under diffusion-convection-reaction processes to study the ozone layer along the altitude in the stratosphere. The ozone abundance and general distribution above the tropical area were calculated and compared to the published measured data. The peak ozone layer was found to be 21 mPa at 22 km or 9.7 ppm at 30 km, and the involved competing processes depicting the ozone layer were explained in details. In the entire stratosphere from 10 km to 50 km, the calculated ozone distribution displayed a similar profile and trend to the observational data, with the calculation in ppm slightly above the measurement by 12%. The standard deviation of the differences between calculated and measured data was close to 0.25. A sensitivity study of gas diffusivities of molecular ozone D3 and atomic oxygen D1 on changing the ozone abundance and profile in the stratosphere showed that in the upper two-third of the stratosphere, D1 evidently exhibited a pronounced impact on ozone, as much as 24-fold larger than D3. The mechanism leading to this finding was also elaborated. The approach and calculations in this paper are shown to be useful for providing an initial insight into the structure and behavior of the complex ozone layer.

Modelling,Validation,and Calculations of Stratospheric Ozone Dynamics and Latitudinal Changes

This paper presents an engineering system approach of 2-D cylindrical model of mass balance calculations with convection,diffusion,and all potential photolysis,ozone generating and depleting chemical reactions considered.This model was developed,validated,and tested under different conditions for the stratospheric ozone.The calculated ozone concentrations and profile in the stratosphere at both the Equator and mid-latitudinal location of 40°S were found to exhibit a similar and close profile and peak value of the published measured data.The discrepancy between the calculations and measurements for the average ozone concentration was shown to be less than 1%and the variation of distributions to be less than 19%.The latitudinal changes of ozone concentrations,distribution,and peak of the layer were found to shift from 9.41 ppm at mid-altitude of z=30 km at the Equator,to 7.81 ppm at z=34.5 km at 40°S,to 5.78 ppm at higher altitude z=39 km at the South Pole.The total ozone abundances at strategic latitudes at 0°S,20°S,40°S,60°S,and 90°S,were found to remain stable and not much changed,from 305 DU to 335 DU,except a smaller value of 288 DU at the South Pole.The possible explanations of ozone profile change and peak shifting as affected by solar/UV radiation,latitudinal locations,and ozone-depleting reactions were discussed and elaborated.The 2-D ozone Model presented in this paper is a robust,efficient,executable,and validated model for studying the complex ozone phenomena in the stratosphere.