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Samuel J. Oltmans

Publications and source records attributed to Samuel J. Oltmans.

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↗

Estimating Wildfire-Generated Ozone Over North America Using Ozonesonde Profiles and a Differential Back Trajectory Technique

An objective method, employing HYSPLIT back-trajectories and Moderate Resolution Imaging Spectroradiometer (MODIS) fire observations, is developed to estimate ozone enhancement in air transported from regions of active forest fires at 18 ozone sounding sites located across North America. The Differential Back Trajectory (DBT) method compares mean differences between ozone concentrations associated with fire-affected and fire-unaffected parcels. It is applied to more than 1100 ozonesonde profiles collected from these sites during the summer months June to August, 2006, 2008, 2010 and 2011. Layers of high ozone associated with low humidity were first removed from the ozonesonde profiles to minimize the potential effects of stratospheric intrusions on the calculations. No significant influence on average ozone levels by North American fires was found for stations located at Arctic latitudes. The ozone enhancement for stations nearer large fires, such as Trinidad Head and Bratt’s Lake, was up to 324.8% of the TTOC (Total Tropospheric Ozone Column). Fire ozone accounted for up to 8.3% of TTOC at downwind sites such as Yarmouth, Sable Island, Narragansett, and Walsingham. The results are consistent with other studies that have reported an increase in ozone production with the age of the smoke plume.

Moderate Resolution Imaging Spectroradiometer (MOD↗

Tropospheric Ozone Assessment Report: Tropospheric Ozone From 1877 to 2016, Observed Levels, Trends and Uncertainties

From the earliest observations of ozone in the lower atmosphere in the 19th century, both measurement methods and the portion of the globe observed have evolved and changed. These methods have different uncertainties and biases, and the data records differ with respect to coverage (space and time), information content, and representativeness. In this study, various ozone measurement methods and ozone datasets are reviewed and selected for inclusion in the historical record of background ozone levels, based on relationship of the measurement technique to the modern UV absorption standard, absence of interfering pollutants, representativeness of the well-mixed boundary layer and expert judgement of their credibility. There are significant uncertainties with the 19th and early 20th-century measurements related to interference of other gases. Spectroscopic methods applied before 1960 have likely underestimated ozone by as much as 11% at the surface and by about 24% in the free troposphere, due to the use of differing ozone absorption coefficients. There is no unambiguous evidence in the measurement record back to 1896 that typical mid-latitude background surface ozone values were below about 20 nmol mol–1, but there is robust evidence for increases in the temperate and polar regions of the northern hemisphere of 30–70%, with large uncertainty, between the period of historic observations, 1896–1975, and the modern period (1990–2014). Independent historical observations from balloons and aircraft indicate similar changes in the free troposphere. Changes in the southern hemisphere are much less. Regional representativeness of the available observations remains a potential source of large errors, which are difficult to quantify. The great majority of validation and intercomparison studies of free tropospheric ozone measurement methods use ECC ozonesondes as reference. Compared to UV-absorption measurements they show a modest (~1–5% ±5%) high bias in the troposphere, but no evidence of a change with time. Umkehr, lidar, and FTIR methods all show modest low biases relative to ECCs, and so, using ECC sondes as a transfer standard, all appear to agree to within one standard deviation with the modern UV-absorption standard. Other sonde types show an increase of 5–20% in sensitivity to tropospheric ozone from 1970–1995. Biases and standard deviations of satellite retrieval comparisons are often 2–3 times larger than those of other free tropospheric measurements. The lack of information on temporal changes of bias for satellite measurements of tropospheric ozone is an area of concern for long-term trend studies.

UV absorption standard↗

Evaluating Long-Term Changes in Atmospheric Ozone

Ozonesondes have made inexpensive, accurate measurements of ozone from the ground to 30km for more than 50 years. The data are used extensively for trend analyses and for evaluation of satellite and model data products, and are also part of climatologies that are used as a priori data for satellite retrievals. They are essential as a transfer standard when merging shorter satellite-derived time series, and are the most important source of trend-quality long-term records below about 18 km. The importance of long-term ozonesonde records as a stable reference has led to increased attention to quantifying uncertainties and changes in ozonesonde data. Based on past intercomparison data, ECC sondes show a modest (~1-5%) high bias with respect to UV-absorption measurements (including MOZAIC-IAGOS) in the troposphere, with an uncertainty of 5%, but no evidence of a change with time. Other sonde types show an increase of 5-20% in sensitivity to tropospheric ozone from 1970-1995. Agreement in the stratosphere is much better. In the past 20 years ozonesonde precision has improved by a factor of 2, primarily through the adoption of strict standard operating procedures. In addition, many of the most important ozonesonde records have been re-evaluated and corrected, and detailed estimates made of their biases and uncertainties. Corrections to historical data for known issues may reduce biases but simultaneously introduce additional uncertainties. The uncertainty budget for the ozone partial pressure reading has contributions from stoichiometry, cell background current, pump efficiency and temperature, sensing solution type and volume. The much-discussed “background current” has recently been shown to be primarily related to reaction stoichiometry. Several quality assurance issues remain, but are tractable problems that can be addressed with further research. This will be required if the present goal of better than 5% overall uncertainty throughout the global ozonesonde network is to be achieved. Finally, the importance of regular sonde intercomparisons, employing UV photometers traceable to the modern UV-absorption standard, and of regular comparison of operational station records with multiple satellite sensors, is emphasized.

Ozonesondes↗