Input sensitivity study of a stratospheric photochemistry model

A general technique for calculating the sensitivities, uncertainties and overall imprecision of a model to a set of input parameters is described and applied to the calculation of CFM induced stratospheric ozone depletion. The input data set used is reaction rates and the technique highlights those that most need further study in the laboratory. The convolution of individual uncertainties to obtain an overall imprecision gives good agreement with the results of Monte-Carlo calculations using the same model.A paper presented at the IAGA/IAMAP Joint Assembly at Seattle, Washington, USA. 22 August–3 September 1977.     

The effect of the HO2+NO reaction rate constant on one-dimensional model calculations of stratospheric ozone perturbations

With the aid of a one-dimensional steady-state, stratospheric model we have calculated ozone changes coused by atmosphric injections of NO_x, N₂O and chlorofluoromethanes. Adopting the fast rate constant, for the reaction HO₂+NO»OH+NO₂ measured by Howard and Evenson, we calculate much smaller perturbations of the ozone layer by NO_x and N₂O additions than previously estimated, but about two times larger ozone reductions as a result of continued emissions of chlorofluoromethanes, CF₂Cl₂ and CFCl₃.The model results are sensitive to adopted values for the rate coefficients for the reactions HO₂+O₃»OH+2O₂ and OH+HO₂»H₂O+O₂ and the eddy diffusion profile near the tropopause. More accurate assessments of ozone perturbations require the development of photochemical models that incorporate meteorological processes in more than one dimension.     

The structure of the natural stratosphere and the impact of chlorofluoromethanes on the ozone layer investigated in a 2-D time dependent model

two-dimensional time dependent model of the stratosphere incorporating the major interactions between radiative-photochemical and dynamical processes is described. The main prognostic equations considered are the thermodynamic equation and the general conservation equation for the minor chemical constituents representing the odd oxygen (O _x =O+('D)+O₃), odd hydrogen (HO _x =HO+HO₂), N₂O, odd nitrogen (NO _x =NO+NO₂+HNO₃), CF₂Cl₂, CFCl₃ and odd chlorine (Cl _x =Cl+ClO+HCl). The zonal wind and mean meridional circulations are determined diagnostically by the integration of the thermal wind equation and the stream function equation in the meridional plane espectively. The large scale eddy processes are parameterized in terms of zonal mean quantities using the generalized diffusion formulation on a sloping surface. The radiative heating and cooling and the hotochemical sources and sinks are incorporated in a form which allows for the major interactions among the minor trace constituents, temperature and mean circulation.Two integrations consisting of natural stratosphere and a stratosphere contaminated by the chlorofluoromethanes through lower boundary fluxes are carried out for 23 model years by changing the declination of the sun every day and using 6-hour time step. The model simulations of temperature, mean circulation, ozone, HO _x , N₂O and NO _x in the meridional plane for the normal stratosphere, show satisfactory agreement with the available observations. Based on the results of second integration it is found that the injection of chlorofluoromethanes in the atmosphere at the estimated current production rates can lead to significant changes in the meridional distribution of ozone, temperature and NO _x in the middle and upper stratosphere. The results also indicate that the percentage total ozone depletion increases from tropics to high latitudes and from summer to winter high latitudes. Also discussed are the results of additional experiments incorporating the reaction of HO₂ with NO and the reactions involving ClNO₃.     

Mismatch between variations of solar indices, stratospheric ozone and UV-B observed at ground

In solar cycles 22–23, all solar indices showed maxima near 1990 and 2000 and minima in 1996. The maximum to minimum variation was only 1–2% in the UV range 240–350 nm. Dobson ozone intensities did not show any clear relationship with solar cycle and ozone variations were less than 10%. The UV-B (295–325 nm) observed at ground by Brewer spectrophotometers at some locations had variations of 50–100% for 295–300 nm, and 20–50% for 305–325 nm. The maxima were in different years at different locations (even with separations of only 300 km), did not match with the solar cycle, and were far too large to be explained on the basis of ozone changes (1% decrease of ozone is expected to cause 2% increase of UV-B). Thus, if the data are not bad, the UV-B changes do not match with solar activity or ozone changes and must be mostly due to other local effects (clouds, etc.?). When data are averaged over wide geographical regions, UV-B variation ranges are smaller (10–20%, probably because localised, highly varying cloud effects get filtered out), and are roughly as expected from ozone variations.     

Simulation of the stratospheric ozone and temperature response to the solar irradiance variability during sun rotation cycle

Despite substantial progress in atmospheric modeling, the agreement of the simulated atmospheric response to decadal scale solar variability with the solar signal in different atmospheric quantities obtained from the statistical analysis of the observations cannot be qualified as successful. An alternative way to validate the simulated solar signal is to compare the sensitivity of the model to the solar irradiance variability on shorter time scales. To study atmospheric response to the 28-day solar rotation cycle, we used the chemistry–climate model SOCOL that represents the main physical–chemical processes in the atmosphere from the ground up to the mesopause. An ensemble simulation has been carried out, which is comprised of nine 1-year long runs, driven by the spectral solar irradiance prescribed on a daily basis using UARS SUSIM measurements for the year 1992. The correlation of zonal mean hydroxyl, ozone and temperature averaged over the tropics with solar irradiance time series have been analyzed. The hydroxyl has robust correlations with solar irradiance in the upper stratosphere and mesosphere, because the hydroxyl concentration is defined mostly by the photolysis. The simulated sensitivity of the hydroxyl to the solar irradiance changes is in good agreement with previous estimations. The ozone and temperature correlations are more complicated because their behavior depends on non-linear dynamics and transport in the atmosphere. The model simulates marginally significant ozone response to the solar irradiance variability during the Sun rotation cycle, but the simulated temperature response is not robust. The physical nature of this is not clear yet. It seems likely that the temperature (and partly the ozone) daily fields possess their own internal variability, which is not stable and can differ from year to year reflecting different dynamical states of the system.     

Transport and the seasonal variation of ozone

The transport mechanisms responsible for the seasonal behavior of total ozone are deduced from the comparison of model results to stratospheric data. The seasonal transport is dominated by a combination of the diabatic circulation and transient planetary wave activity acting on a diffusively and photochemically determined background state. The seasonal variation is not correctly modeled as a diffusive process. The buildup of total ozone at high latitudes during winter is dependent upon transient planetary wave activity of sufficient strength to cause the breakdown of the polar vortex. While midwinter warmings are responsible for enhanced ozone transport to high latitudes, the final warming marking the transition from zonal mean westerlies to zonal mean easterlies is the most important event leading to the spring maximum. The final warming is not followed by reacceleration of the mean flow; so that the ozone transport associated with this event is more pronounced than that associated with midwinter warmings.     

Annual and semiannual oscillations of stratospheric ozone

The global structures of annual oscillation (AO) and semiannual oscillation (SAO) of stratospheric ozone are examined by applying spherical harmonic analysis to the ozone data obtained from the Nimbus-7 solar backscattered UV-radiation (SBUV) measurements for the period November 1978 to October 1980. Significant features of the results are: (1) while the stratospheric ozone AO is prevalent only in the polar regions, the ozone SAO prevails both in the equatorial and polar stratospheres; (2) the vertical distribution of the equatorial ozone SAO has a broad maximum of the order of 0.5 (mixing ratio in g/g) and the maximum appears earlier at high altitude (shifting from May [and November] at 0.3 mb [60 km] to November [and May] at 40 mb); (3) above the 40 km level, the maximum of the polar ozone SAO shifts upward towards later phase with altitude with a rate of approximately 10 km/month in both hemispheres; (4) vertical distributions of the polar ozone AOs and SAOs show two peaks in amplitude with a minimum (nodal layer) in between and a rapid phase change with altitude takes place in the respective nodal layers; and (5) the heights of the ozone AO- and SAO-peaks decrease with latitude. The main part of AOs and SAOs of stratospheric ozone including hemispheric asymmetries is ascribable to: (i) temperature dependent ozone photochemistry in the upper stratosphere and mesosphere, (ii) variations of radiation field in the lower stratosphere affected by the annual cycle of solar illumination and temperature in the upper stratosphere and (iii) meridional ozone transport by dynamical processes in the lower stratosphere.     

Stochastic modelling of groundwater flow and solute transport in aquifers

This paper presents an introductory overview of recently developed stochastic theories for tackling spatial variability problems in predicting groundwater flow and solute transport. Advantages and limitations of the theories are discussed. Lastly, strategies based on the stochastic approaches to predict solute transport in aquifers are recommended.     

Physically based modelling of sediment generation and transport under a large rainfall simulator

A series of large rainfall simulator experiments was conducted in 2002 and 2003 on a small plot located in an experimental catchment in the North Island of New Zealand. These experiments measured both runoff and sediment transport under carefully controlled conditions. A physically based hydrological modelling system (SHETRAN) was then applied to reproduce the observed hydrographs and sedigraphs. SHETRAN uses physically based equations to represent flow and sediment transport, and two erodibility coefficients to model detachment of soil particles by raindrop erosion and overland flow erosion. The rate of raindrop erosion also depended on the amount of bare ground under the simulator; this was estimated before each experiment. These erodibility coefficients were calibrated systematically for summer and winter experiments separately, and lower values were obtained for the summer experiments. Earlier studies using small rainfall simulators in the vicinity of the plot also found the soil to be less erodible in summer and autumn. Limited validation of model parameters was carried out using results from a series of autumn experiments. The modelled suspended sediment load was also sensitive to parameters controlling the generation of runoff from the rainfall simulator plot; therefore, we found that accurate runoff predictions were important for the sediment predictions, especially from the experiments where the pasture cover was good and overland flow erosion was the dominant mechanism. The rainfall simulator experiments showed that the mass of suspended sediment increased post‐grazing, and according to the model this was due to raindrop detachment. The results indicated that grazing cattle or sheep on steeply sloping hill‐country paddocks should be carefully managed, especially in winter, to limit the transport of suspended sediment into watercourses. Copyright © 2006 John Wiley & Sons, Ltd.     

Possible effects of volcanic eruptions on stratospheric minor constituent chemistry

Although stratosphere penetrating volcanic eruptions have been infrequent during the last half century, periods have existed in the last several hundred years when such eruptions were significantly more frequent. Several mechanisms exist for these injections to affect stratospheric minor constitutent chemistry, both on the long-term average and for short-term perturbations. These mechanisms are reviewed and, because of the sensitivity of current models of stratospheric ozone to chlorine perturbations, quantitative estimates are made of chlorine injection rates. It is found that, if chlorine makes up as much as 0.5 to 1% of the gases released and if the total gases released are about the same magnitude as the fine ash, then a major stratosphere penetrating eruption could deplete the ozone column by several percent. The estimate for the Agung eruption of 1963 is just under 1% an amount not excluded by the ozone record but complicated by the peak in atmospheric nuclear explosions at about the same time. The long-term contribution to stratospheric CIX by volcanic eruptions is estimated as 0.1 ppbv for the period 1900–60 and 1 ppbv for the much more volcanically active period 1780–1840. All of the estimates are subject to large uncertainties, perhaps a factor of 2 or 3 on the high side and a factor of 10 or more on the low side.Paper presented at the IAGA/IAMAP Joint Assembly, Seattle, WA, U.S.A., August 1977.     

Selenium transport and transformation modelling in soil columns and ground water contamination prediction

Selenium transport and transformation were simulated in a soil column. A one‐dimensional dynamic mathematical and computer model is formulated to simulate, selenate, selenite, selenomethionine, organic selenium, and gaseous selenium. This computer model is based on the mass balance equation, including convective transport, dispersive transport, surface adsorption, oxidation and reduction, volatilization, chemical and biological transformation. The mathematical solution is obtained by the finite difference implicit method. The model was verified by comparison of model results with experimental measurements and also using mass balance calculations in each time step of calculation. For example after 4 days of simulation, the simulated value of adsorbed selenate for depth of 20 cm is 0·2 µmol kg^?1 and the measured value is 0·25 µmol kg^?1. Therefore simulated results are in good agreement with measured values. With this study and its results the distribution of various forms of selenium in soil column to ground water table can be predicted. Copyright © 2008 John Wiley & Sons, Ltd.     

Uncertainty in modelling of faecal coliform overland transport associated with manure application in Maryland

Concerns for microbial safety of surface water facilitate development of predictive models that estimate concentrations and total numbers of pathogen and indicator organisms leaving manure‐fertilized fields in overland flow during runoff events. Spatial variability of bacterial concentrations in applied manure introduces high uncertainty in the model predictions. The objective of this work was to evaluate the uncertainty in model predictions of the manure‐borne bacteria overland transport caused by limited information on the spatial distribution of bacteria in surface‐applied manure. Experiments were carried out at the ARS Beltsville experimental watershed site (OPE3) in Maryland. Dairy bovine manure was applied at a 59·3 t/ha rate on the 3·55 hectare experimental field. Faecal coliform (FC) concentrations in manure measured in 2004, 2005, 2007, and 2009 varied by 4 orders of magnitude each year. Both runoff volume and FC concentrations in runoff water were monitored using a runoff flume equipped with a refrigerated pump sampler. Two runoff events occurred before the manure was incorporated into the soil. A bacteria transport add‐on module simulator of transport with infiltration and runoff (STWIR) was linked with the event‐based kinematic runoff and erosion model (KINEROS2) to simulate convective‐dispersive overland transport, bacteria release from manure, reversible attachment–detachment to soil, and surface straining of infiltrating bacteria. The model was successfully calibrated with the field experiment data. Monte Carlo simulations were carried out to account for the spatial variation in FC in applied manure and uncertainty in the FC distribution in manure caused by the small number of samples. A tenfold and twofold variation in FC concentrations in the runoff were obtained within the 90% probability interval when initial FC spatial distributions in the manure were represented by 5 and 29 samples, respectively. Copyright © 2011 John Wiley & Sons, Ltd.     

Exact transverse macro dispersion coefficients for transport in heterogeneous porous media

We study transport through heterogeneous media. We derive the exact large scale transport equation. The macro dispersion coefficients are determined by additional partial differential equations. In the case of infinite Peclet numbers, we present explicit results for the transverse macro dispersion coefficients. In two spatial dimensions, we demonstrate that the transverse macro dispersion coefficient is zero. The result is not limited on lowest order perturbation theory approximations but is an exact result. However, the situation in three spatial dimensions is very different: The transverse macro dispersion coefficients are finite – a result which is confirmed by numerical simulations we performed.     

Relationship of atmospheric ozone profiles to solar magnetic activity

The observed relationship between atmospheric vorticity variations and solar magnetic sector boundary passages is examined for a possible connection via ionization changes affecting ozone distributions. A superposed epoch analysis was performed on Umkehr distributions for 18 years from Arosa, Switzerland, with use of more than 500 solar sector boundary passages as keyday zero. No significant responses are observed in any Umkehr level or in total observed ozone amounts. Further analyses on shorter records for Belsk, Poland, and Hohenpeissenberg, West Germany, corroborate these results. Another analysis for Arosa with about 100 type IV solar flares as keyday zero also shows no definitive trend. It is concluded that ozone distribution changes cannot be the primary causative mechanism for vorticity variations.Journal Paper No. J-8838 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa. Project No. 1852.     

Representativeness of total ozone trends as derived from satellite BUV and ground-based measurements

The information content of the 7-year BUV data set has been reexamined by a comparison with a fairly large set of ground Dobson and M-83 instruments. The satellite-ground intercomparison of total ozone was done under different types of ground observation techniques (observation code) and different instrument exposure (exposure code) and for various distances of the subsatellite point from the station. Because of the existing latitudinal gradient in total ozone, at a given station the bias ground-BUV tends to be smaller when the subsatellite point is at a latitude higher than the station's latitude. Knowing the total ozone gradient at a given station, the BUV total ozone has been corrected to account for the ozone gradient and the correlation was calculated with the corresponding ground observations. These correlations seem to offer no improvement when compared with the correlations between the ground ozone and the actual BUV ozone at distances of the subsatellite point from the station within 200 km from the station used in previous studies. The seasonal variation of the BUV-ground correlation reveals information on the noise level of the measurements and the geographical distribution of the percentage mean bias: (Ground-BUV)×100/(Ground) is discussed. Both on short and on longer time scales it appears that the BUV derived recommended total ozone data set is reasonably good and possible instrumental drifts are not large. The analysis includes an extension through April 1977 of the BUV and contour-derived total ozone trends byLondon andLing (1980). Over the northern hemisphere both data sets (contour and BUV) show comparable trends over middle and high latitudes which range from –3 D.U./year to –5 D.U./year during the 7-year period April 1970–April 1977. In the southern hemisphere, however, long-term variation in total ozone cannot be determined from ground observations alone. It is concluded that for unknown reasons during the 7-year period of study, total ozone has been decreasing over most of the globe. The negative growth rates at high latitudes of the northern hemisphere are highly significant.     

Variability in the determination of total atmospheric ozone using remote sensing spectroscopic techniques

A spectroscopic method for optical remote sensing of total ozone (O₃) is described. It involves detailed spectral matching of near ultraviolet solar observations with synthetic profiles containing various amounts of ozone absorption. Application of this technique is made to airborne solar measurements in the 3100 to 3600 Å wavelength region. In the 3100 to 3200 Å region, measurements made above the tropopause (around geographic latitude 36.7°N, longitude 121.7°W at 0045 UT on 1/23/74) generally fit synthetic profiles constructed with 0.3 atm cm of O₃ absorption andBroadfoot's (1972) extra-terrestrial solar irradiance values. However, there are several sections of the solar spectra where the observed intensity is either significantly higher or lower than the calculated value. In addition, several maxima and minima in the observed spectra do not coincide in wavelength with corresponding features in the synthetic profile. Such problems also appear when comparison is made with synthetic profiles based onArvesen et al.'s (1969) extra-terrestrial solar irradiance measurements. These discrepancies may arise from a combination of sources, including errors in laboratory measured O₃ absorption coefficients, the extra-terrestrial solar irradiance values and the presence of other UV absorbing species in the stratosphere.     

Coupled inverse modelling of groundwater flow and mass transport and the worth of concentration data

This paper presents the extension of the self-calibrating method to the coupled inverse modelling of groundwater flow and mass transport. The method generates equally likely solutions to the inverse problem that display the variability as observed in the field and are not affected by a linearisation of the state equations. Conditioning to the state variables is measured by an objective function including, among others, the mismatch between the simulated and measured concentrations. Conditioning is achieved by minimising the objective function by gradient-based methods. The gradient contains the partial derivatives of the objective function with respect to: log conductivities, log storativities, prescribed heads at boundaries, retardation coefficients and mass sources. The derivatives of the objective function with respect to log conductivity are the most cumbersome and need the most CPU-time to be evaluated. For this reason, to compute this derivative only advective transport is considered. The gradient is calculated by the adjoint-state method. The method is demonstrated in a controlled, synthetic study, in which the worth of concentration data is analysed. It is shown that concentration data are essential to improve transport predictions and also help to improve aquifer characterisation and flow predictions, especially in the upstream part of the aquifer, even in the case that a considerable amount of other experimental data like conductivities and heads are available. Besides, conditioning to concentration data reduces the ensemble variances of estimated transmissivity, hydraulic head and concentration.     

Significance of particle interaction to the modelling of cohesive sediment transport in rivers

Aggregation processes of fine sediments have rarely been integrated in numerical simulations of cohesive sediment transport in riverine systems. These processes, however, can significantly alter the hydrodynamic characteristics of suspended particulate matter (SPM), modifying the particle settling velocity, which is one of the most important parameters in modelling suspended sediment dynamics. The present paper presents data from field measurements and an approach to integrate particle aggregation in a hydrodynamic sediment transport model. The aggregation term used represents the interaction of multiple sediment classes (fractions) with corresponding multiple deposition behaviour. The k–ε–turbulence model was used to calculate the coefficient of vertical turbulent mixing needed for the two‐dimensional vertical‐plane simulations. The model has been applied to transport and deposition of tracer particles and natural SPM in a lake‐outlet lowland river (Spree River, Germany). The results of simulations were evaluated by comparison with field data obtained for two levels of river discharge. Experimental data for both discharge levels showed that under the prevailing uniform hydraulic conditions along the river reach, the settling velocity distribution did not change significantly downstream, whereas the amount of SPM declined. It was also shown that higher flow velocities (higher fluid shear) resulted in higher proportions of fast settling SPM fractions. We conclude that in accordance with the respective prevailing turbulence structures, typical aggregation mechanisms occur that continuously generate similar distribution patterns, including particles that settle toward the river bed and thus mainly contribute to the observed decline in the total SPM concentration. In order to determine time‐scales of aggregation and related mass fluxes between the settling velocity fractions, results of model simulations were fitted to experimental data for total SPM concentration and of settling velocity frequency distributions. The comparison with simulations for the case of non‐interacting fractions clearly demonstrated the practical significance of particle interaction for a more realistic modelling of cohesive sediment and contaminant transport. Copyright © 2004 John Wiley & Sons, Ltd.     

Impact of coupled perturbations of atmospheric trace gases on Earth's climate and ozone

We have studied the effects on the ozone concentration and surface temperature, of perturbations in the atmospheric content of nitrous oxide, methane, carbon dioxide and chlorofluorocarbons (CFC). The sensitivity study has been carried out with a radiative-convective-photochemical model. The doubling of carbon dioxide concentration has the effect of warming the troposphere and cooling the stratosphere. As a result of this cooling, the change of ozone columnar density produced by 10 ppb of chlorine amount to 9.3% as compared to –10.9% obtained without temperature feedback. Perturbation in nitrous oxide correspond to an increase in NO _x of the stratosphere with consequent ozone reduction while doubling the methane concentration correspond to a slight increase in columnar density. The effect of the increased methane concentration in the stratosphere contributes to reduce the effect of CFC due to the enhanced formation of HCl. The perturbation of these two minor constituents appreciably increase the greenhouse effect to 2.30 from 1.67°, obtained when carbon dioxide alone is considered.