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NASA NTRS2020

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↗

NASA NTRS2003

Calibration of EcoBadge Test-Strips for Ozone Measurement for GLOBE

The majority of our work, therefore, centered on experiments at an extended exposure period at low ozone concentrations, creating and programming the necessary calibration curve into a Zikua reader. and verifying that the Zikua would use the curve reliably. Zikua is a device supplied by Vistanomics to 'read' the exposed EcoBadge cards and provide a read-out of measured ozone concentration in ppb. This device replaces the visual comparison to a calibrated color chart. For our initial studies, test papers were prepared by the usual method in small batches. Although testing would also eventually include Vistanomics' EcoBadge papers, we began with papers prepared in our lab so that we could be assured of the freshness of each batch. We felt this would allow us better comparison among our runs as we varied exposure time. At the outset, our target acceptable error was about +/- 10%. For example, if the actual ozone concentration was 20 ppb, then we hoped to be in the range 18-22 ppb. If the actual ozone concentration was 100 ppb. then we hoped to fall within 90-110 ppb in our measurements. Clearly a systematic error in the range of 3-4 ppb or more would significantly affect the lower exposure data.

Bush, Linda C.↗

NASA NTRS2021

Investigations on the Anthropogenic Reversal of the Natural Ozone Gradient Between Northern and Southern Midlatitudes

Our quantitative understanding of natural tropospheric ozone concentrations is limited by the paucity of reliable measurements before the 1980s. We utilize the existing measurements to compare the long-term ozone changes that occurred within the marine boundary layer at northern and southern midlatitudes. Since 1950 ozone concentrations have increased by a factor of 2.1 ± 0.2 in the Northern Hemisphere (NH) and are presently larger than in the Southern Hemisphere (SH), where only a much smaller increase has occurred. These changes are attributed to increased ozone production driven by anthropogenic emissions of photochemical ozone precursors that increased with industrial development. The greater ozone concentrations and increases in the NH are consistent with the predominant location of anthropogenic emission sources in that hemisphere. The available measurements indicate that this interhemispheric gradient was much smaller and was likely reversed in the pre-industrial troposphere with higher concentrations in the SH. Six Earth system model (ESM) simulations indicate similar total NH increases (1.9 with a standard deviation of 0.3), but they occurred more slowly over a longer time period, and the ESMs do not find higher pre-industrial ozone in the SH. Several uncertainties in the ESMs may cause these model–measurement disagreements: the assumed natural nitrogen oxide emissions may be too large, the relatively greater fraction of ozone injected by stratosphere–troposphere exchange to the NH may be overestimated, ozone surface deposition to ocean and land surfaces may not be accurately simulated, and model treatment of emissions of biogenic hydrocarbons and their photochemistry may not be adequate.

natural tropospheric ozone concentrations↗

NASA NTRS1988

Springtime surface ozone fluctuations at high Arctic latitudes and their possible relationship to atmospheric bromine

At high Arctic stations such as Barrow, Alaska, springtime near-surface ozone amounts fluctuate between the highest and lowest values seen during the course of the year. Episodes when the surface ozone concentration is essentially zero last up to several days during this time of year. In the Arctic Gas and Aerosol Sampling Program (AGASP-I and AGASP-II) in 1983 and 1986, it was found that ozone concentrations often showed a very steep gradient in altitude with very low values near the surface. The cold temperatures, and snow-covered ground make it unlikely that the surface itself would rapidly destroy significant amounts of ozone. The AGASP aircraft measurements that found low ozone concentrations in the lowest layers of the troposphere also found that filterable excess bromine (the amount of bromine in excess of the sea salt component) in samples collected wholly or partially beneath the temperature inversion had higher bromine concentrations than other tropospheric samples. Of the four lowest ozone minimum concentrations, three of them were associated with the highest bromine enrichments. Surface measurements of excess filterable bromine at Barrow show a strong seasonal dependence with values rising dramatically early in March, then declining in May. The concentration of organic bromine gases such as bromoform rise sharply during the winter and then begin to decline after March with winter and early spring values at least three times greater than the summer minimum.

Oltmans, Samuel J.↗

NASA NTRS1994

Results of ozone measurements in Northern Germany: A case study

At most of the German ozone recording stations which have records over a sufficiently long period, the results of the summer months of 1989 showed the highest values since the beginning of the measurements. One of the reasons for this phenomenon was the high duration of sunshine in that summer; for example, in Potsdam near Berlin in May 1989 the sunshine duration was the highest in May since the beginning of the records in 1893. For that reason we selected this summer for a case study. The basis for the study was mainly the ozone measuring stations of the network of Lower Saxony and the Federal Office of Environment (Umweltbundesamt). The results of these summer measurements point to intense sources of ozone, probably in form of gaseous precursors, in the Middle German industrial areas near Leipzig and Halle and in Northwestern Czechoslovakia, with coal-mining, chemical and petrochemical industries, coking plants and others. The maps of average ozone concentrations, number or days with high ozone maxima, ozone-windroses of the stations, etc., suggest that these areas could be a main source of precursors and of photochemical ozone production in summer smog episodes in Central Europe. Stations on the North Sea coast, at which early ozone measurements were made by our institute in 1973/74 are compared with similarly located stations of the Lower Saxon network in 1989 and the results show a reversal of the ozone-windroses. In 1973/74, the highest ozone concentrations were correlated with wind directions from the sea while in 1989 these concentrations were correlated with directions from the continent. In the recent years, photochemical ozone production on the continent is probably predominant, while in former years the higher ozone content of the maritime subpolar air masses has been explained by stratospheric-tropospheric exchange.

Schmidt, Manfred↗

NASA NTRS1998

Fiber-Optic Coupled Lidar Receiver System to Measure Stratospheric Ozone

The measurement of ozone in the atmosphere has become increasingly important over the past two decades. Significant increases of ozone concentrations in the lower atmosphere, or troposphere, and decreases in the upper atmosphere, or stratosphere, have been attributed to man-made causes. High ozone concentrations in the troposphere pose a health hazard to plants and animals and can add to global warming. On the other hand, ozone in the stratosphere serves as a protective barrier against strong ultraviolet (UV) radiation from the sun. Man-made CFC's (chlorofluorocarbons) act as a catalyst with a free oxygen atom and an ozone molecule to produce two oxygen molecules therefore depleting the protective layer of ozone in the stratosphere. The beneficial and harmful effects of ozone require the study of ozone creation and destruction processes in the atmosphere. Therefore, to provide an accurate model of these processes, an ozone lidar system must be able to be used frequently with as large a measurement range as possible. Various methods can be used to measure atmospheric ozone concentrations. These include different airborne and balloon measurements, solar occulation satellite techniques, and the use of lasers in lidar (high detection and ranging,) systems to probe the atmosphere. Typical devices such as weather balloons can only measure within the direct vicinity of the instrument and are therefore used infrequently. Satellites use solar occulation techniques that yield low horizontal and vertical resolution column densities of ozone.

Harper, David Brent↗

NASA NTRS1979

Ozone contamination in aircraft cabins: Objectives and approach

Three panels were developed to solve the problem of ozone contamination in aircraft cabins. The problem is defined from direct in-flight measurements of ozone concentrations inside and outside airliners in their normal operations. Solutions to the cabin ozone problem are discussed under two areas: (1) flight planning to avoid high ozone concentrations, and (2) ozone destruction techniques installed in the cabin air systems.

Perkins, P. J.↗

NASA NTRS1995

Surface ozone levels at Table Mountain during STOIC 1989

As a part of the routine operations of the Jet Propulsion Laboratory atmospheric measurements program at the Table Mountain Facility, the surface ozone concentration is continuously monitored using a Dasibi photometer. The influence of the Los Angeles basin to the southwest of the facility and the height of the inversion layer cause large fluctuations in the ozone concentration. Peaks as high as 200 parts per billion by volume (ppbv) were observed during the Stratospheric Ozone Intercomparison Campaign (STOIC) compared to a normal background level near 50 ppbv. These measurements, made during STOIC, were important in assessing the impact of the surface ozone concentration on the various instruments participating in the campaign.

McDermid, I. Stuart↗

NASA NTRS2000

Stratospheric Ozone Climatology from Lidar Measurements at Table Mountain (34.0 deg N, 117.7 deg W) and Mauna Loa (19.5 deg N, 155.6 deg W)

Using more than 1600 nighttime profiles obtained by the JPL differential absorption lidars (DIAL) located at Table Mountain Facility (TMF, 34.4 N) and Mauna Loa Observatory (MLO, 19.5 N) is presented in this paper. These two systems have been providing high-resolution vertical profiles of ozone number density between 15-50 km, several nights a week since 1989 (TMF) and 1993 (MLO). The climatology presented here is typical of early night ozone values with only a small influence of the Pinatubo aerosols and the 11-year solar cycle. The observed seasonal and vertical structure of the ozone concentration at TMF is consistent with that typical of mid- to subtropical latitudes. A clear annual cycle in opposite phase below and above the ozone concentration peak is observed. The observed winter maximum below the ozone peak is associated with a maximum day-to-day variability, typical of a dynamically driven lower stratosphere. The maximum concentration observed in summer above the ozone peak emphasizes the more dominant role of photochemistry. Unlike TMF, the ozone concentration observed at MLO tends to be higher during the summer months and lower during the winter months throughout the entire stratospheric ozone layer. Only a weak signature of the extra-tropical latitudes is observed near 19-20 km, with a secondary maximum in late winter. The only large variability observed at MLO is associated with the natural variability of the tropical tropopause.

Leblanc, T.↗

NASA NTRS1978

The 1977 surface ozone study of eastern Virginia

Data were collected by primarily twelve ground stations positioned throughout the eastern shore - tidewater area of Virginia and North Carolina. From an analysis of the ozone and wind data, certain trends were found such as the existence of a bias in ozone concentrations between stations and a linear correlation between average ozone concentration and latitude. In addition, higher ozone levels were found with surface winds from certain preferred directions at the various sites. The results, however, do not substantiate ozone or ozone precursor transport.

Williams, M. E.↗

NASA NTRS1979

The effect of the sea breeze circulation on surface ozone levels at Wallops Island, Virginia

Surface measurements of windspeed, direction, and ozone concentration collected at Wallops Island, Virginia, during the summers of 1977 and 1978 are analyzed to study the effects of the dominant mesoscale sea breeze circulation on the local photochemical oxidant levels. A bimodality in the atmospheric dynamics is linked to systematic variations in ozone concentration. It is concluded that during certain phases of the two circulation modes, increased wind speed reduces the resistance of the earth's surface to the deposition of ozone, and decreased ozone concentration levels result. For other phases, light winds occur, signifying high resistance to deposition and high ozone levels. This modulation by the local dynamics is a major impediment for pollutant studies in coastal environments, especially those centering on transport, because it tends to mask other processes that may be occurring.

Parsons, C. L.↗

NASA NTRS1988

Ozone measurements in the troposphere of an Amazonian rain forest environment

Ozone concentration profiles from the ground to above the stratospheric peak were obtained in an equatorial rain forest environment near Manaus in the Amazon Basin between July and August of 1985. The peak ozone concentration (4.4 x 10 to the 22 molecules/cu cm) was found at 20 mbar (26.6 km). A major pollution (biomass-burning) event which occurred near the end of the experiment was responsible for large changes in ozone concentration.

Kirchhoff, V. W. J. H.↗

NASA NTRS1990

The significance of biomass burning as a source of carbon monoxide and ozone in the Southern Hemisphere tropics - A satellite analysis

Carbon monoxide mixing ratios obtained by the October 1984 Measurement of Air Pollution from Satellites (MAPS) experiment are compared with the distribution of October 1984 Total Ozone Mapping Spectrometer (TOMS) ozone concentrations. The TOMS and MAPS data show coincident high values of ozone and carbon monoxide over central South America and southeastern Africa. The 1984 MAPS data are also compared with tropospheric ozone concentrations derived from 6 years of TOMS and Stratospheric Aerosol and Gas Experiment (SAGE) I and II measurements. Examination of the October climatological distribution of tropospheric ozone also reveals high concentrations over central South America and southeastern Africa. These coincident high values of CO and ozone in the rural southern tropics are most likely due to biomass burning and the subsequent transport of CO and ozone by large-scale weather patterns. It appears that both CO and ozone are being transported thousands of kilometers from their source regions by the prevailing winds.

Watson, Catherine E.↗

NASA NTRS2017

The Effect of Entrainment Through Atmospheric Boundary Layer Growth on Observed and Modeled Surface Ozone in the Colorado Front Range

Ozone concentrations at the Earth's surface are controlled by meteorological and chemical processes and are a function of advection, entrainment, deposition, and net chemical production/loss. The relative contributions of these processes vary in time and space. Understanding the relative importance of these processes controlling surface ozone concentrations is an essential component for designing effective regulatory strategies. Here we focus on the diurnal cycle of entrainment through atmospheric boundary layer (ABL) growth in the Colorado Front Range. Aircraft soundings and surface observations collected in July/August 2014 during the DISCOVER-AQ/FRAPPÉ (Deriving Information on Surface conditions from Column and Vertically Resolved Observations Relevant to Air Quality/Front Range Air Pollution and Photochemistry Éxperiment) campaigns and equivalent data simulated by a regional chemical transport model are analyzed. Entrainment through ABL growth is most important in the early morning, fumigating the surface at a rate of ~5 ppbv/h. The fumigation effect weakens near noon and changes sign to become a small dilution effect in the afternoon on the order of -1 ppbv/h. The chemical transport model WRF-Chem (Weather Research and Forecasting Model with chemistry) underestimates ozone at all altitudes during this study on the order of 10-15 ppbv. The entrainment through ABL growth is overestimated by the model in the order of 0.6-0.8 ppbv/h. This results from differences in boundary layer growth in the morning and ozone concentration jump across the ABL top in the afternoon. This implicates stronger modeled fumigation in the morning and weaker modeled dilution after 11:00 LT.

Entrainment through ABL Growth↗

NASA NTRS1973

The Development of a Stochastic Model of the Atmosphere Between 30 and 90 Km to Be Used in Determining the Effect of Atmospheric Variability on Space Shuttle Entry Parameters

A stochasitc model of the atmosphere between 30 and 90 km was developed for use in Monte Carlo space shuttle entry studies. The model is actually a family of models, one for each latitude-season category as defined in the 1966 U.S. Standard Atmosphere Supplements. Each latitude-season model generates a pseudo-random temperature profile whose mean is the appropriate temperature profile from the Standard Atmosphere Supplements. The standard deviation of temperature at each altitude for a given latitude-season model was estimated from sounding-rocket data. Departures from the mean temperature at each altitude were produced by assuming a linear regression of temperature on the solar heating rate of ozone. A profile of random ozone concentrations was first generated using an auxiliary stochastic ozone model, also developed as part of this study, and then solar heating rates were computed for the random ozone concentrations.

Campbell, J. W.↗

NASA NTRS2017

Influence of Mid-Latitude Cyclones on European Background Surface Ozone Investigated in Observations, MACC and MERRA-2 Reanalyses

The relationship between springtime mid-latitude cyclones and background ozone at two rural monitoring sites on the west coast of Europe -- Mace Head, Ireland and Monte Velho, Portugal -- is explored using a combination of observations and three reanalyses: 1) the European Centre for Medium-Range Weather Forecasts' (ECMWF) ERA-Interim reanalysis, 2) the Monitoring Atmospheric Composition and Climate (MACC) reanalysis and 3) NASA's Modern-Era Retrospective Analysis for Research and Applications Version-2 (MERRA-2) reanalysis. The ERA-Interim cyclone tracks are used here to establish the long-term relationship between cyclones and ozone observations (since 1988). The MACC reanalysis data set, which covers the period 2003-2012, is produced with the ECMWF integrated forecast system (IFS) model two-way coupled to a chemistry transport model (CTM). Since the MACC reanalysis uses a similar atmospheric model to ERA-Interim, MACC is used to explore the mechanisms within the case study cyclones that can influence surface ozone concentrations at Mace Head and Monte Velho. The MERRA-2 reanalysis also provides 3D distributions of ozone, although less ideal for analysis of surface ozone concentrations since MERRA-2 ozone under represents ozone variability outside the stratosphere as it does not have a detailed chemistry scheme or emission sources for the troposphere. The MERRA-2 reanalysis, which has the potential to identify more features within the cyclones as the resolution is higher than the MACC reanalysis, is used in conjunction with the MACC reanalysis to provide a measure of uncertainty to the case study analysis. We found the main source of high ozone to these two sites is from the stratosphere, which is well represented in both the MERRA-2 and the MACC reanalyses, either from direct injection into the cyclone or associated with aged airstreams from decaying downstream cyclones that can become entrained and descend toward the surface within new cyclones over the NA region.

MERRA-2↗

NASA NTRS1992

Measured trends in stratospheric ozone

Recent findings, based on both ground-based and satellite measurements, have established that there has been an apparent downward trend in the total column amount of ozone over mid-latitude areas of the Northern Hemisphere in all seasons. Measurements of the altitude profile of the change in the ozone concentration have established that decreases are taking place in the lower stratosphere in the region of highest ozone concentration. Analysis of updated ozone records, through March of 1991, including 29 stations in the former Soviet Union, and analysis of independently calibrated satellite data records from the Total Ozone Mapping Spectrometer and Stratospheric Aerosol and Gas Experiment instruments confirm many of the findings originally derived from the Dobson record concerning northern midlatitude changes in ozone. The data from many instruments now provide a fairly consistent picture of the change that has occurred in stratospheric ozone levels.

Stolarski, Richard↗

NASA NTRS2001

Urban and Rural Ozone Pollution Over Lusaka (Zambia, 15.5S, 25E) During SAFARI-2000 (September 2000)

In early September, throughout south central Africa, seasonal clearing of dry vegetation and the production of charcoal for cooking leads to intense smoke haze and ozone formation. Ozone soundings made over Lusaka during a six-day period in early September 2000 recorded layers of high ozone (greater than 125 ppbv at 5 km) during two stagnant periods, interspersed by a frontal passage that reduced boundary layer ozone by 30 percent. Smoke aerosol column variations aloft and total ozone were monitored by a sun photometer. During the 6-day measurement period, surface ozone concentrations ranged from 50-95 ppbv and integrated tropospheric ozone from the soundings was 39- 54 Dobson Units (note 1.3 km elevation at the launch site). High ozone concentrations above the mixed and inversion layers were advected from rural burning regions in western Zambia where SAFARI aircraft and ground-based instruments observed intense biomass fires and elevated aerosol and trace gas amounts. TOMS tropospheric ozone and smoke aerosols products show the distribution of biomass burning and associated pollution throughout southern Africa in September 2000. Animations of satellite images and trajectories confirm pollutant recirculation over south central African fires, exit of ozone from Mozambique and Tanzania to the Indian Ocean and the characteristic buildup of tropospheric ozone over the Atlantic from western African outflow.

Thompson, Anne M.↗