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Homogenization of the Observatoire de Haute Provence electrochemical concentration cell (ECC) ozonesonde data record: comparison with lidar and satellite observations

The Observatoire de Haute Provence (OHP) weekly Electrochemical Concentration Cell (ECC) ozonesonde data have been homogenized for the period 1991-2021 according to the recommendations of the Ozonesonde Data Quality Assessment (O3S-DQA) panel. The assessment of the ECC homogenization benefit has been carried out using comparisons with other ozone measuring ground based instruments at the same station (lidar, surface measurements) and with collocated satellite observations of the O3vertical profile by Microwave Limb Sounder (MLS). The major differences between uncorrected and5homogenized ECC data are related to a change of ozonesonde type in 1997, removal of the pressure dependency of the ECC background current and correction of internal pump temperature. The original 3-4 ppbv positive bias between ECC and Lidar in the troposphere is corrected with the homogenization. The ECC 30-years trends of the seasonally adjusted ozone concentrations are also significantly improved in both the troposphere and the stratosphere after the ECC homogenization, as shown by the ECC/lidar or ECC/surface ozone trend comparisons. A -0.19% per year negative trend of the normalization factor (NT)10calculated using independent measurements of the total ozone column (TOC) at OHP disappears after homogenization of the ECC data. There is however a remaining -3.7% negative bias in the TOC which is likely related to an underestimate of the ECC concentrations in the stratosphere above 50 hPa. Differences between TOC measured by homogenized ECC and satellite observations show a smaller bias of -1%. Comparisons between homogenized ECC and OHP stratospheric lidar and MLS observations below 26 km are slightly negative (-2%) or positive (+2%), respectively. Both the comparisons with lidar and15satellite observations suggest that homogenization increases the negative bias of the ECC to values lower than -6% above 28km. The reason for this bias is still unclear, but a possible explanation might be related to freezing or evaporation of the sonde solution in the stratosphere.

Ozonesondes↗

ECC Ozonesonde Reliability, Observations, and Comparisons with Satellite Ozone Instruments

Electrochemical Concentration Cell (ECC) ozone instruments depend on the quality of care exercised in their pre-flight preparation. The ozone-measuring project conducted at Goddard Space Flight Center's Wallops Flight Facility uses a number of mechanisms designed to inspect the ECC for anomalies that may interfere with the reception of valid ozone profiles. Complete electronic testing of the instrument, individually and when coupled to its radiosonde has led to exceptional monitoring of ozone for detecting long-term atmospheric changes. A number of factors are considered when preparing an ECC instrument for flight. These basically are specific calibrations of pump efficiency, volumetric flow rate, temperature of the air entering the pump, and background current. The concentration of the potassium iodide solution is also important. Wallops is the only site using a UV photometer (Dasibi) to compare ECC ozone output at various concentrations of ozone that allows adjustment to be made to offsets that may appear in the balloon-borne instrument prior to release. All of the above procedures allow identification of potential problems before release of the ECC instrument. Procedures followed at Wallops also are employed in Brazil, and Ascension Island where NASA has cooperative agreements in place to obtain ozonesondes data. All ECC instruments are prepared 3-4 weeks prior to the day of observation. We will briefly describe the instrumental tests employed. These tests have included simultaneous dual observations to compare the effect of different solution concentrations, comparison of sensors of different manufacturers, and comparisons with surface- and space-based instrumentation such as the Dobson Spectrophotometer and satellites. Vertical profiles of ozone from Arctic, mid-latitudes, and Antarctica will be discussed. Although not unusual, the data reveals ozone structure that correlate well with typical atmospheric temperatures and possibly relative humidity. Finally, vertical ozone distribution, compared with remotely measured ozone from lidar and satellite, will be discussed. Specific comparisons between ECC and HALOE measurements, integrated ECC total ozone overburden with the EP-TOMS and the Dobson, as well as comparisons with lidar are discussed. Results show agreement and some disagreement between the in situ measurements of the ECC and the remote instruments. We postulate reasons for the differences, or biases, which in spite of the excellent ECC quality control during pre-flight preparation and data analysis processes, may be due to uncertainties in both measuring systems.

Schmidlin, F. J.↗

Optimal preparation of the ECC ozonesonde

The ECC background current was identified as the removal of residual tri-iodide (iodine) as the cell approaches equilibrium. The altitude dependence of this source of the background current is expected to be only slowly changed in the troposphere with a more rapid decrease in the stratosphere. Oxygen does not play a role in the background current except in the unlikely situation where the electrodes have had all forms of iodine removed from them and the electrodes have not re-equilibrated with the sonde solutions before use. A solution mass transport parameter in the ECC was identified and its altitude dependence determined. The mass transport of tri-iodide dominates in the chemical transduction of ozone to electrical signal. The effect of the mass transport on the ECC background current is predicted. An electrochemical model of the ECC has been developed to predict the response of the ECC to various ozone vertical profiles. The model corresponds very closely to the performance of the ECC in the laboratory. Based on this model, an ECC with no background current is predicted to give total ozone values within 1% of the correct value, although the vertical profile may be in error by as much as + or - 15%.

Thornton, D. C.↗

A New Method to Correct the Electrochemical Concentration Cell (ECC) Ozonesonde Time Response and its Implications for "Background Current" and Pump Efficiency

The electrochemical concentration cell (ECC) ozonesonde has been the main instrument for in situ profiling of ozone worldwide; yet, some details of its operation, which contribute to the ozone uncertainty budget, are not well understood. Here, we investigate the time response of the chemical reactions inside the ECC and how corrections can be used to remove some systematic biases. The analysis is based on the understanding that two reaction pathways involving ozone occur inside the ECC that generate electrical currents on two very different timescales. The main fast-reaction pathway with a time constant of about 20 s is due the conversion of iodide to molecular iodine and the generation of two free electrons per ozone molecule. A secondary slow-reaction pathway involving the buffer generates an excess current of about 2 %–10 % with a time constant of about 25 min. This excess current can be interpreted as what has conventionally been considered the “background current”. This contribution can be calculated and removed from the measured current instead of the background current. Here we provide an algorithm to calculate and remove the contribution of the slow-reaction pathway and to correct for the time lag of the fast-reaction pathway. This processing algorithm has been applied to ozonesonde profiles at Costa Rica and during the Central Equatorial Pacific Experiment (CEPEX) as well as to laboratory experiments evaluating the performance of ECC ozonesondes. At Costa Rica, where a 1 % KI, 1/10th buffer solution is used, there is no change in the derived total ozone column; however, in the upper troposphere and lower stratosphere, average reported ozone concentrations increase by up to 7 % and above 30 km decrease by up to 7 %. During CEPEX, where a 1 % KI, full-buffer solution was used, ozone concentrations are increased mostly in the upper troposphere, with no change near the top of the profile. In the laboratory measurements, the processing algorithms have been applied to measurements using the majority of current sensing solutions and using only the stronger pump efficiency correction reported by Johnson et al. (2002). This improves the accuracy of the ECC sonde ozone profiles, especially for low ozone concentrations or large ozone gradients and removes systematic biases relative to the reference instruments. In the surface layer, operational procedures prior to launch, in particular the use of filters, influence how typical gradients above the surface are detected. The correction algorithm may report gradients that are steeper than originally reported, but their uncertainty is strongly influenced by the prelaunch procedures.

electrochemical concentration cell (ECC) ozonesond↗

ECC Ozonesonde Calibration and Observations: Satellite Validation

The reliability of the Electrochemical Concentration Cell (ECC) ozonesonde depends on the care exercised in preparing the instrument for use. Although the ECC can be quickly prepared and flown, generally within less then one day if necessary, it is best to prepare the instrument at least one week prior to use, and as our tests have confirmed even 2-3 weeks prior to use may actually be better. There are a number of factors that must be considered when preparing an ECC. These basically are the pump efficiency, volumetric flow rate, temperature of the air entering the pump, and the background current. Also of importance is the concentration of the potassium iodide solution. Tests conducted at Wallops Island (38 N) has enabled us to identify potential problem areas and ways to avoid them. The calibration and pre-flight preparation methods will be discussed. The method of calibrating the ECC also is used at Ascension Island (8 S) and Natal, Brazil (5 S). Comparisons between vertical profiles of the ECC instrument and satellites will be reviewed as well as comparison with ground based instruments, such as, the Dobson Spectrophotometer and hand held Microtops photometers.

Schmidlin, Francis J.↗

An evaluation of electrochemical concentration Cell (ECC) sonde measurements of atmospheric ozone

Using Dobson spectrophotometer measurements of total ozone as a comparison, an analysis of the electrochemical concentration cell (ECC) ozonesonde's measurement accuracy is presented. Days of conjunctive ECC-Dobson observations (from 1970 to 1976 at Wallops Flight Center) provide a set of 123 pairs of total ozone values. Sample set statistics are generated with means and standard deviations of total ozone values and differences being noted. An in-depth study of factors such as time assumptions used in calculating residual ozone, and other possible sources of errors are examined. A study of ECC ozone profiles is also presented with an evaluation of sonde measurement of seasonal trends, altitude or peak ozone concentration, and other important ozone parameters. Short-period changes in total ozone using Dobson data during the observational period are also described.

Geraci, M. J.↗

ECC ozonesonde performance at high altitudes: Pump efficiency

The ECC ozonesonde sampling behavior was examined at pressures ranging from 60 to 6 hPa with the objective of evaluating uncertainties in high altitude ozone data caused by variations in pumping efficiency. The averaged pump efficiency correction curve for a 43 sample set of 3A type ECC pumps showed a 2-3% bias from the curve provided by the manufacturer. In addition, random pump to pump variations (2 sigma) + or - were 5% at 6 hPa. These values probably represent minimum errors since the pumps were from the same production batch. A seven sample set of the newer 4A type ECC pumps was examined, with similar findings as for the 3A types.

Torres, A. L.↗

Effects of solution mass transport on the ECC ozonesonde background current

A technique is developed to measure the effective mass transport parameter for the electrochemical concentration cell (ECC) ozonesonde in order to determine the mass transport rate constant for the ECC as a function of pressure. It is shown that a pressure dependent factor in the background current originates in a convective mass transport parameter. It is determined that for atmospheric pressures greater than 100 mb the mass transport parameter is a constant, while at pressures less than 100 mb it decreases logarithmically with pressure. It is suggested that the background current correction is directly correlated to the mass transport parameter pressure dependence. The presently used background current correction, which is based on the partial pressure of oxygen, is found to lead to an overestimation of the integrated ozone value in the troposphere for the ECC ozonesonde data.

Thornton, D. C.↗

Performance tests on the Kohmyr ECC ozone sonde

The reliability and accuracy of the Kohmyr ECC ozone sonde are determined. Emphasis is placed on establishing and testing for leak-free connections and stable pump flow rates as well as properly adjusting the pumping pressure. Calibration of the Kohmyr ECC ozone sondes and Dasibi monitors is described. Raw ordinate data and ozone connection data are presented in tabular form. The results of a linear regression treatment of the sonde-indicated ozone concentration vs. Dasibi readings for each switch position are included along with averages of the regression parameters over the six sequencing switch positions. It is suggested that sondes and Dasibi monitors be individually calibrated before flight.

Bandy, A. R.↗

The validation of LIMS ozone profiles using correlative rocket, ECC, and Dobson data sets

The Limb Infrared Monitor of the Stratosphere (LIMS) experiment is a limb scanning infrared sounder designed to measure vertical temperature profiles and the concentrations of key chemical compounds which are important in the stratospheric ozone-nitrogen photochemistry. Preliminary ozone profiles are being intercompared with correlative rocket and balloonsonde ozone data sets as part of the Nimbus 7 LIMS data validation activity. The LIMS ozone retrievals extend from the lower mesosphere to the tropopause (or cloud-top altitudes). In this paper, preliminary statistics of comparisons of ECC (electrochemical concentration cell) ozonesonde and rocket ozone profiles with LIMS ozone profiles are presented. ECC ozonesonde data taken at times of LIMS overpasses are also used to extend the LIMS retrieval down to ground level. Each combined profile is then integrated to obtain total column ozone. These integrated results are compared to Dobson data obtained at approximately the same time and location.

Remsberg, E. E.↗

Satellite and correlative measurements of stratospheric ozone - Comparison of measurements made by SAGE, ECC balloons, chemiluminescent, and optical rocketsondes

The validity of ozone-profile data from the satellite sensor SAGE was tested in a series of correlative experiments conducted at five fixed sites between 6 deg S and 65 deg N during 1979-1980. The intercomparisons included data taken with electrochemical ozone (ECC) balloonsondes and chemiluminescent and optical rocketsondes. The average mean difference for 17 separate comparisons between the SAGE and ECC balloonsonde observations over the altitudes 18-28 km was 9.3 percent with a standard deviation of 2.8 percent. Excluding comparisons separated by greater than 500 km reduces the average mean difference to 8.9 percent and the standard deviation to 2.1 percent. The average mean difference between SAGE and three optical rocketsonde observations over the altitudes 25-50 km was 11 percent, and between SAGE and two chemiluminescent rocketsondes over the altitudes 20-60 km it was 13.5 percent. Considering the differences in vertical resolution, experimental errors, and ozone time and space gradients, the agreement between SAGE-derived ozone profiles and these correlative measurements is considered very good. In addition, isopleths of ozone mixing ratio versus latitude and altitude are in good agreement with previously published results.

Mccormick, M. P.↗

Effects of solution mass transport on the ECC ozonesonde background current

Measurement of the mass transport rate constant for the electrochemical concentration cell in an ozonesonde as a function of the pressure is reported. The investigation was performed to accurately model the residual current present in the ECC cell in the absence of ozone. The convective mass transport for two sondes were determined while maintaining a sufficiently negative cathodic potential to eliminate electron transfer at the cathode surface. A sonde was placed in a bell jar and subjected to varying pressure levels. When the background current was kept below 0.1 microamp and pressure was from 100-1000 mb, the necessary correction term for the pressure was independent of pressure. However, below 100 mb, a logarithmic decrease in the background current with pressure is expected. Present practices, involving a sensitivity to oxygen, are calculated to result in overestimation of the total ozone between 1000-10 mb by 0.0096 atm-cm with a background current of 0.1 microamp at 1000 mb.

Thornton, D. C.↗

The latitudinal distribution of ozone to 35 km altitude from ECC ozonesonde observations, 1982-1990

Electrochemical concentration cell (ECC) ozone-sonde observations, made in recent years at ten stations whose locations range from the Arctic to Antarctica, have yielded a self-consistent ozone data base from which mean seasonal and annual latitudinal ozone vertical distributions to 35 km have been derived. Ozone measurement uncertainties are estimated, and results are presented in the Bass-Paur (1985) ozone absorption coefficient scale adopted for use with Dobson ozone spectrophotometers January 1, 1992. The data should be useful for comparison with model calculations of the global distribution of atmospheric ozone, for serving as apriori statistical information in deriving ozone vertical distributions from satellite and Umkehr observations, and for improving the satellite and Umkehr ozone inversion algorithms. Attention is drawn to similar results based on a less comprehensive data set published in Ozone in the Atmosphere, Proceedings of the 1988 Quadrennial Ozone Symposium where errors in data tabulations occurred for three of the stations due to inadvertent transposition of ozone partial pressure and air temperature values.

Komhyr, W. D.↗

Sources of background current in the ECC ozonesonde - Implications for total ozone measurements

The source of the background current in the usual operation of the electrochemical concentration cell ozonesonde is the reduction of tri-iodide normally present in the cathode solution. The time variations in the background current can be explained by the slow rates of solution mass transport and of heterogeneous electron transfer for tri-iodide. Oxygen does not contribute to the background current through reaction with iodide to produce tri-iodide. Direct reduction of oxygen at the cathode is negligible once the electrodes have been exposed to iodide for 24 hours. The present background current correction is altitude-dependent, since it is based on an assumed sensitivity of the electrochemical concentration cell to oxygen. If the background current is independent of altitude and of oxygen, a constant, uncorrected, background current of 0.1 microamp would produce an error of +5.5% for the total ozone value of the electrochemical concentration cell for a typical midlatitude total ozone value of 0.345 atm-cm.

Thornton, D. C.↗

Ensemble Cannonical Correlation Prediction of Seasonal Precipitation Over the US

This paper presents preliminary results of an ensemble cannonical correlation (ECC) prediction scheme developed at the Climate and Radiation Branch, NASA/Goddard Space Flight Center for determining the potential predictability of regional precipitation, and for climate downscaling studies. The scheme is tested on seasonal hindcasts of anomalous precipitation over the continental United States using global sea surface temperature (SST) for 1951-2000. To maximize the forecast skill derived from SST, the world ocean is divided into nonoverlapping sectors. The cannonical SST modes for each sector are used as the predictor for the ensemble hindcasts. Results show that the ECC yields a substantial (10-25%) increase in prediction skills for all regions of the US and for all seasonal compared to traditional CCA prediction schemes. For the boreal winter, the tropical Pacific contributes the largest potential predictability to precipitation in the southwestern and southeastern regions, while the North Pacific and the North Atlantic are responsible for enhanced forecast skills in the Pacific Northwest, the northern Great Plains and Ohio Valley. Most importantly, the ECC increases skill for summertime precipitation prediction and substantially reduced the spring predictability barrier over all regions of the US continent. Besides SST, the ECC is designed with the flexibility to include any number of predictor fields, such as soil moisture, snow cover and regional regional data. Moreover, the ECC forecasts can be applied to other climate subsystems and, in conjunction with further diagnostic or model studies will enables a better understanding of the dynamic links between climate variations and precipitation, not only for the US, but also for other regions of the world.

Lau, William K. M.↗