Photolytic Converter Research Articles

An Alternative Calibration Method for Measuring N2O5 with an Iodide-Chemical Ionization Mass Spectrometer and Influencing Factors.

In this work, we developed an alternative calibration method for measuring N2O5 with an iodide adduct mass spectrometer (I-CIMS). In this calibration method, N2O5 is heated and then quantified based on the decrease in the amount of NO due to its reaction with the pyrolysis product (NO3). This alternative calibration method was compared with the commonly used method utilizing NOx analyzers equipped with a photolytic converter, which gauge NO2 reduction as a result of its reaction with O3 to quantify N2O5. It is notable that the two methodologies demonstrate favorable consistency in terms of calibrating N2O5, with a variance of less than 10 %. The alternative calibration method is a more reliable way to quantify N2O5 with CIMS, considering the instability of the NO2 conversion efficiency of photolytic converters in NOx analyzers and the loss of N2O5 in the sampling line. The effects of O3 and relative humidity (RH) on the sensitivity toward N2O5 were further examined. There was minimal perturbation of N2O5 quantification upon exposure to O3 even at high concentrations. The N2O5 sensitivity exhibited a nonlinear dependence on RH as it initially rose and then fell. Besides I(N2O5)-, the collisional interaction between I(H2O)- and N2O5 also forms I(HNO3)-, which may interfere with the accurate quantification of HNO3. As a consequence of the pronounced dependence on humidity, it is advisable to implement humidity correction procedures when conducting measurements of N2O5.

Field intercomparison of continuous ambient FRM and FEM NO2 instruments in the Athabasca Oil Sands Region, Alberta, Canada and the potential impact on ambient regulatory compliance

ABSTRACT The Canadian Federal Government promulgated new and lower NO2 Ambient Air Quality Standards (CAAQS) that went into effect in 2020 with additional decreases scheduled for 2025. The new hourly and annual NO2 CAAQS are 60 and 17 ppb, respectively, and the 2025 hourly and annual CAAQS are 42 and 12 ppb, respectively. The province of Alberta has also promulgated Ambient Air Quality Objectives (AAAQO) for NO2 currently set to 159 and 24 ppb on an hourly and annual basis, respectively. The Wood Buffalo Environmental Association (WBEA) in northeastern Alberta, Canada monitors NO2 at 21 community and industrial sites throughout the Athabasca Oil Sands Region (AOSR), for regulatory compliance using Thermo-Environmental (TEI) Model 42i Federal Reference Method (FRM) designated NO-NO2-NOx analyzers. The 42i measures NO directly via NO-O3 chemiluminescence, and NOx following the reduction of oxidized nitrogen to NO by a heated internal molybdenum converter. The difference between the NOx and NO channels is reported as NO2. This study presents the results of a three-year (2018–2021) WBEA comparison of four continuous NO2 analyzers: TEI 42i FRM; the API Model T500U cavity attenuated phase shift (CAPS) Federal Equivalent Method (FEM); a total reactive odd nitrogen analyzer (TEI Model 42i-Y); and a TEI 42i equipped with an external photolytic converter. The study showed that NO2 data from all analyzers were highly correlated and in general agreement, with r2 values (vs. the CAPS) ranging from 0.990–0.997 and slopes ranging from 0.933–0.992. Mean NO2 concentrations over the study period ranged from 7.2–7.5 ppb. Differences between the TEI 42i, TEI 42i-Y, and PhoNO, relative to the CAPS were all positive and highly significant (p < 0.0001), based upon nonparametric tests. The potential impact from the selection of different FRM/FEM measurement methods on current and future Canadian 2025 regulatory compliance in the region is evaluated. Implications: The study objective was to compare/evaluate different regulatory NO2 measurement techniques from a regional monitoring authority in a routine network operational context. Relatively small NO2 differences resulted in significant differences with respect to regulatory compliance triggers, particularly hourly standards based on daily extreme value statistics (e.g., 99th percentiles). For example, mean hourly NO2 △ differences ranged from 0.02–0.26 ppb over the study period but resulted in 2–3 ppb differences in the 3-year hourly CAAQS metrics. These differences could affect regulatory CAAQS and LARP compliance (management level) at monitoring sites observed during 2019 annual and 2020 hourly LARP trigger exceedances.

Modification of a conventional photolytic converter for improving aircraft measurements of NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; via chemiluminescence

Abstract. Nitrogen oxides (NOx≡NO+NO2) are centrally involved in the photochemical processes taking place in the Earth's atmosphere. Measurements of NO2, particularly in remote areas where concentrations are of the order of parts per trillion by volume (pptv), are still a challenge and subject to extensive research. In this study, we present NO2 measurements via photolysis–chemiluminescence during the research aircraft campaign CAFE Africa (Chemistry of the Atmosphere – Field Experiment in Africa) 2018 around Cabo Verde and the results of laboratory experiments to characterize the photolytic converter used. We find the NO2 reservoir species MPN (methyl peroxy nitrate) to produce the only relevant thermal interference in the converter under the operating conditions during CAFE Africa. We identify a memory effect within the conventional photolytic converter (type 1) associated with high NO concentrations and rapidly changing water vapor concentrations, accompanying changes in altitude during aircraft measurements, which is due to the porous structure of the converter material. As a result, NO2 artifacts, which are amplified by low conversion efficiencies, and a varying instrumental background adversely affect the NO2 measurements. We test and characterize an alternative photolytic converter (type 2) made from quartz glass, which improves the reliability of NO2 measurements in laboratory and field studies.

Long-term NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt; measurements in the remote marine tropical troposphere

Abstract. Atmospheric nitrogen oxides (NO + NO2 = NOx) have been measured at the Cape Verde Atmospheric Observatory (CVAO) in the tropical Atlantic (16∘51′ N, 24∘52′ W) since October 2006. These measurements represent a unique time series of NOx in the background remote troposphere. Nitrogen dioxide (NO2) is measured via photolytic conversion to nitric oxide (NO) by ultraviolet light-emitting diode arrays followed by chemiluminescence detection. Since the measurements began, a blue light converter (BLC) has been used for NO2 photolysis, with a maximum spectral output of 395 nm from 2006 to 2015 and of 385 nm from 2015 onwards. The original BLC used was constructed with a Teflon-like material and appeared to cause an overestimation of NO2 when illuminated. To avoid such interferences, a new additional photolytic converter (PLC) with a quartz photolysis cell (maximum spectral output also 385 nm) was implemented in March 2017. Once corrections are made for the NO2 artefact from the original BLC, the two NO2 converters are shown to give comparable NO2 mixing ratios (BLC = 0.99 × PLC + 0.7 ppt, linear least-squares regression), giving confidence in the quantitative measurement of NOx at very low levels. Data analysis methods for the NOx measurements made at CVAO have been developed and applied to the entire time series to produce an internally consistent and high-quality long-term data set. NO has a clear diurnal pattern with a maximum mixing ratio of 2–10 ppt during the day depending on the season and ∼ 0 ppt during the night. NO2 shows a fairly flat diurnal signal, although a small increase in daytime NOx is evident in some months. Monthly average mixing ratios of NO2 vary between 5 and 30 ppt depending on the season. Clear seasonal trends in NO and NO2 levels can be observed with a maximum in autumn and winter and a minimum in spring and summer.

Potential interferences in photolytic nitrogen dioxide converters for ambient air monitoring: Evaluation of a prototype

ABSTRACT Mixing ratios of the criteria air contaminant nitrogen dioxide (NO2) are commonly quantified by reduction to nitric oxide (NO) using a photolytic converter followed by NO-O3 chemiluminescence (CL). In this work, the performance of a photolytic NO2 converter prototype originally designed for continuous emission monitoring and emitting light at 395 nm was evaluated. Mixing ratios of NO2 and NOx (= NO + NO2) entering and exiting the converter were monitored by blue diode laser cavity ring-down spectroscopy (CRDS). The NO2 photolysis frequency was determined by measuring the rate of conversion to NO as a function of converter residence time and found to be 4.2 s−1. A maximum 96% conversion of NO2 to NO over a large dynamic range was achieved at a residence time of (1.5 ± 0.3) s, independent of relative humidity. Interferences from odd nitrogen (NOy) species such as peroxyacyl nitrates (PAN; RC(O)O2NO2), alkyl nitrates (AN; RONO2), nitrous acid (HONO), and nitric acid (HNO3) were evaluated by operating the prototype converter outside its optimum operating range (i.e., at higher pressure and longer residence time) for easier quantification of interferences. Four mechanisms that generate artifacts and interferences were identified as follows: direct photolysis, foremost of HONO at a rate constant of 6% that of NO2; thermal decomposition, primarily of PAN; surface promoted photochemistry; and secondary chemistry in the connecting tubing. These interferences are likely present to a certain degree in all photolytic converters currently in use but are rarely evaluated or reported. Recommendations for improved performance of photolytic converters include operating at lower cell pressure and higher flow rates, thermal management that ideally results in a match of photolysis cell temperature with ambient conditions, and minimization of connecting tubing length. When properly implemented, these interferences can be made negligibly small when measuring NO2 in ambient air. Implications: A new near-UV photolytic converter for measurement of the criteria pollutant nitrogen dioxide (NO2) in ambient air by CL was characterized. Four mechanisms that generate interferences were identified and investigated experimentally: direct photolysis of HONO which occurred at a rate constant 6% that of NO2, thermal decomposition of PAN and N2O5, surface promoted chemistry involving HNO3, and secondary chemistry involving NO in the tubing connecting the converter and CL analyzer. These interferences are predicted to occur in all NO2 P-CL systems but can be avoided by appropriate thermal management and operating at high flow rates.

The IAGOS NO&amp;lt;sub&amp;gt;&amp;lt;i&amp;gt;x&amp;lt;/i&amp;gt;&amp;lt;/sub&amp;gt; instrument – design, operation and first results from deployment aboard passenger aircraft

Abstract. We describe the nitrogen oxide instrument designed for the autonomous operation on board passenger aircraft in the framework of the European Research Infrastructure IAGOS (In-service Aircraft for a Global Observing System). We demonstrate the performance of the instrument using data from two deployment periods aboard an A340-300 aircraft of Deutsche Lufthansa. The well-established chemiluminescence detection method is used to measure nitrogen monoxide (NO) and nitrogen oxides (NOx). NOx is measured using a photolytic converter, and nitrogen dioxide (NO2) is determined from the difference between NOx and NO. This technique allows measuring at high time resolution (4 s) and high precision in the low ppt range (NO: 2σ = 24 pptv; NOx: 2σ = 35 pptv) over different ambient temperature and ambient pressure altitude ranges (from surface pressure down to 190 hPa). The IAGOS NOx instrument is characterized for (1) calibration stability and total uncertainty, (2) humidity and chemical interferences (e.g., ozone; nitrous acid, HONO; peroxyacetyl nitrate, PAN) and (3) inter-instrumental precision. We demonstrate that the IAGOS NOx instrument is a robust, fully automated, and long-term stable instrument suitable for unattended operation on airborne platforms, which provides useful measurements for future air quality studies and emission estimates.

Seasonal variations in the NO2 artifact from chemiluminescence measurements with a molybdenum converter at a suburban site in Korea (downwind of the Asian continental outflow) during 2015–2016

This paper investigates the NO2 artifact associated with the chemiluminescence measurement technique that uses a molybdenum converter by applying the same technique but with a photolytic converter at a site downwind of the Asian continental outflow (Daejeon, Korea). The NO2 to NO conversion efficiencies of the molybdenum and photolytic converters were found to be 100% and 95%, respectively, at an ambient level of NO2 (<100 ppbv). Two NO2 monitors equipped with molybdenum and photolytic converters were deployed for ambient NO2 measurements in Daejeon, Korea between the fall of 2015 and the summer of 2016. It was found that the monitor equipped with the molybdenum converter overestimated NO2 levels by 20.4 ± 14.7% when compared with the actual NO2 level in the Daejeon atmosphere over the entire measurement period. This NO2 artifact (ΔNO2), defined as the difference between molybdenum NO2 and photolytic NO2 values, correlated well with the PM2.5 mass concentration during the fall and winter seasons. Based on these findings, this study develops a simple correction model for ΔNO2 using the PM2.5 mass concentration during the fall and winter seasons. The model-corrected NO2 concentration correlated well with the actual NO2 values with a slope of approximately 1.0 and R2 value of 0.98 during the fall and winter seasons.

A portable device for fast analysis of explosives in the environment

A novel portable device for fast and sensitive analysis of explosives in environmental samples is presented. The developed system consists of miniaturized microcolumn liquid chromatograph, photolytic converter and chemiluminescence detector. The device is able to determine selectively nitramine- and nitroester- and most of nitroaromates-based explosives as well as inorganic nitrates at trace concentrations in water or soil extracts in less than 8min. The device allows to analyze various environmental samples such as soils or water materials without previous preconcentration. Because of internal power supply, the device ensures 12h of continuous operation. Limits of detection of compounds of interest are in the range of concentrations from 5.0×10−9M to 8.0×10−5M for a signal-to-noise ratio of 3. Limits of quantification are in the range of concentrations from 1.7×10−8M to 2.7×10−4M for a signal-to-noise ratio of 10. The repeatability of the method (RSD=2.9–5.6%) was determined by repeated injections (n=10) of the standard samples during 4h.

Evaluation of OMI operational standard NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; column retrievals using in situ and surface-based NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; observations

Abstract. We assess the standard operational nitrogen dioxide (NO2) data product (OMNO2, version 2.1) retrieved from the Ozone Monitoring Instrument (OMI) onboard NASA's Aura satellite using a combination of aircraft and surface in~situ measurements as well as ground-based column measurements at several locations and a bottom-up NOx emission inventory over the continental US. Despite considerable sampling differences, NO2 vertical column densities from OMI are modestly correlated (r = 0.3–0.8) with in situ measurements of tropospheric NO2 from aircraft, ground-based observations of NO2 columns from MAX-DOAS and Pandora instruments, in situ surface NO2 measurements from photolytic converter instruments, and a bottom-up NOx emission inventory. Overall, OMI retrievals tend to be lower in urban regions and higher in remote areas, but generally agree with other measurements to within ± 20%. No consistent seasonal bias is evident. Contrasting results between different data sets reveal complexities behind NO2 validation. Since validation data sets are scarce and are limited in space and time, validation of the global product is still limited in scope by spatial and temporal coverage and retrieval conditions. Monthly mean vertical NO2 profile shapes from the Global Modeling Initiative (GMI) chemistry-transport model (CTM) used in the OMI retrievals are highly consistent with in situ aircraft measurements, but these measured profiles exhibit considerable day-to-day variation, affecting the retrieved daily NO2 columns by up to 40%. This assessment of OMI tropospheric NO2 columns, together with the comparison of OMI-retrieved and model-simulated NO2 columns, could offer diagnostic evaluation of the model.

The Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI): design, execution, and early results

Abstract. From June to July 2009 more than thirty different in-situ and remote sensing instruments from all over the world participated in the Cabauw Intercomparison campaign for Nitrogen Dioxide measuring Instruments (CINDI). The campaign took place at KNMI's Cabauw Experimental Site for Atmospheric Research (CESAR) in the Netherlands. Its main objectives were to determine the accuracy of state-of-the-art ground-based measurement techniques for the detection of atmospheric nitrogen dioxide (both in-situ and remote sensing), and to investigate their usability in satellite data validation. The expected outcomes are recommendations regarding the operation and calibration of such instruments, retrieval settings, and observation strategies for the use in ground-based networks for air quality monitoring and satellite data validation. Twenty-four optical spectrometers participated in the campaign, of which twenty-one had the capability to scan different elevation angles consecutively, the so-called Multi-axis DOAS systems, thereby collecting vertical profile information, in particular for nitrogen dioxide and aerosol. Various in-situ samplers and lidar instruments simultaneously characterized the variability of atmospheric trace gases and the physical properties of aerosol particles. A large data set of continuous measurements of these atmospheric constituents has been collected under various meteorological conditions and air pollution levels. Together with the permanent measurement capability at the CESAR site characterizing the meteorological state of the atmosphere, the CINDI campaign provided a comprehensive observational data set of atmospheric constituents in a highly polluted region of the world during summertime. First detailed comparisons performed with the CINDI data show that slant column measurements of NO2, O4 and HCHO with MAX-DOAS agree within 5 to 15%, vertical profiles of NO2 derived from several independent instruments agree within 25% of one another, and MAX-DOAS aerosol optical thickness agrees within 20–30% with AERONET data. For the in-situ NO2 instrument using a molybdenum converter, a bias was found as large as 5 ppbv during day time, when compared to the other in-situ instruments using photolytic converters.

Interferences of commercial NO&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt; instruments in the urban atmosphere and in a smog chamber

Abstract. Reliable measurements of atmospheric trace gases are necessary for both, a better understanding of the chemical processes occurring in the atmosphere, and for the validation of model predictions. Nitrogen dioxide (NO2) is a toxic gas and is thus a regulated air pollutant. Besides, it is of major importance for the oxidation capacity of the atmosphere and plays a pivotal role in the formation of ozone and acid precipitation. Detection of NO2 is a difficult task since many of the different commercial techniques used are affected by interferences. The chemiluminescence instruments that are used for indirect NO2 detection in monitoring networks and smog chambers use either molybdenum or photolytic converters and are affected by either positive (NOy) or negative interferences (radical formation in the photolytic converter). Erroneous conclusions on NO2 can be drawn if these interferences are not taken into consideration. In the present study, NO2 measurements in the urban atmosphere, in a road traffic tunnel and in a smog-chamber using different commercial techniques, i.e. chemiluminescence instruments with molybdenum or photolytic converters, a Luminol based instrument and a new NO2-LOPAP, were compared with spectroscopic techniques, i.e. DOAS and FTIR. Interferences of the different instruments observed during atmospheric measurements were partly characterised in more detail in the smog chamber experiments. Whereas all the commercial instruments showed strong interferences, excellent agreement was obtained between a new NO2-LOPAP instrument and the FTIR technique for the measurements performed in the smog chamber.

Development of a Selective Light-Emitting Diode Photolytic NO2 Converter for Continuously Measuring NO2 in the Atmosphere

A photolytic converter of nitrogen dioxide (NO(2)) to nitric oxide (NO) using light-emitting diodes (LEDs) has been designed to measure NO(2) in the troposphere. The typical electrical power consumption of the photolytic converter (PLC) is only 44 W. The maximum conversion efficiency of NO(2) to NO of the photolytic converter is around 90%, which is higher than that of metal halides or high-pressure Xe arc lamps (up to ∼70%). The conversion efficiency of the PLC was almost constant for at least 2.5 months. The conversion efficiency of peroxyacetyl nitrate by the LED-PLC was measured to be 2.6 ± 0.1% (1σ). The interference of HONO using the PLC was experimentally estimated to be less than 3%, which is within the uncertainty of the instrument. An intercomparison of NO(2) measurements between the PLC-CLD and the laser-induced fluorescence (LIF) technique was conducted, and the NO(2) concentrations measured by the PLC-CLD method were in agreement with those obtained by the LIF technique, within the uncertainties of the instruments. Continuous observations were made on Fukue Island, a remote area. These results demonstrate the performance of the PLC for continuous ambient measurements.

Nitrogen oxide measurements at rural sites in Switzerland: Bias of conventional measurement techniques

Nitrogen oxides (NOx = NO + NO2) in the atmosphere are often measured using instruments equipped with molybdenum converters. NO2 is catalytically converted to NO on a heated molybdenum surface and subsequently measured by chemiluminescence after reaction with ozone. The drawback of this technique is that other oxidized nitrogen compounds such as peroxyacetyl nitrate and nitric acid are also partly converted to NO. Thus such NO2 measurements are really surrogate NO2 measurements because the resultant values systematically overestimate the true value because of interferences of these compounds, especially when sampling photochemically aged air masses. However, molybdenum converters are widely used, and a dense network of surrogate NO2 measurements exists. As an alternative with far less interference, photolytic converters using ultraviolet light are nowadays applicable also for long‐term measurements. This work presents long‐term collocated NO2 measurements using molybdenum and photolytic converters at two rural sites in Switzerland. On a relative scale, the molybdenum converter instruments overestimate the NO2 concentrations most during spring/summer because of prevalent photochemistry. On a monthly basis, only 70–83% of the “surrogate” NO2 can be attributed to “real” NO2 at the non‐elevated site and even less (43–76%) at the elevated one. The observed interferences have to be taken into account for monitoring and regulatory issues and to be considered when using these data for ground‐truthing of satellite data or for validation of chemical transport models. Alternatively, an increased availability of artifact‐free data would also be beneficial for these issues.

Evaluation of short-term Ogawa passive, photolytic, and federal reference method sampling devices for nitrogen oxides in El Paso and Houston, Texas

Passive Sampling Devices (PSDs) have been successfully used by government and academic agencies to monitor common ambient air pollutants such as ozone and nitrogen dioxide (NO(2)). Most PSD studies have involved long-term (e.g. bi-weekly or monthly) sampling. But the Passive Ozone Network of Dallas (POND) studies of 1998 and 1999 showed that high quality 24-hour and 12-hour data using the Ogawa PSD could be collected for ambient ozone concentrations. This paper presents an evaluation of short-term passive sampling results for nitrogen oxides (NO(x)) in El Paso and Houston, Texas, using the Ogawa PSD. The Ogawa NO(x) PSDs were compared to both Federal Reference Method (FRM) monitors and a photolytic converter, with the photolytic converter designed to report closer concentrations to "true" NO(x) by more effectively limiting the interferences of other nitrogen species. Overall, good agreement was noted for all three monitor types in both cities, supporting the potential use of lower cost Ogawa PSDs for large multi-site episodic NO(x)/NO(2)/NO saturation screening studies. This evaluation was conducted during two separate six week periods of the cooler winter months so additional testing of the Ogawa PSDs during different seasons is recommended.

Direct measurement of NO 2 in the marine atmosphere by laser-induced fluorescence technique

A simple and compact instrument for NO 2 measurement by laser-induced fluorescence (LIF) technique with a pulsed solid state laser and a multi-pass excitation system was developed and optimized for several conditions. As a result of laboratory experiment, the limit of detection (LOD) reached 94 pptv for 60 s integration. It was thought that an LIF instrument with this LOD value would be capable of quantifying sub-ppbv NO 2 in unpolluted marine atmosphere. As the second step, a field test of the instrument was conducted in the marine atmosphere at Cape Hedo, Okinawa Island, Japan, in summer 1999. Intercomparison between the LIF instrument and a chemiluminescence detector with a photolytic converter (PLC-CL) was also made in this test. Consequently, the LIF instrument was shown to be of practical use for measuring NO 2 in clean maritime air.

An efficient photolysis system for fast‐response NO2 measurements

A new photolytic converter for NO2 measurement is described and its performance assessed using laboratory, ground‐, and aircraft‐based field data. Focusing the output of a 200‐W short‐arc Hg lamp into a photolytic cell attains conversion fractions of NO2 to NO greater than 0.70 in cell residence times of less than a second. Limiting lamp output to wavelengths greater than 350 nm by means of optical filters increases specificity for NO2, affording a peroxyacetyl nitrate conversion fraction of less than 0.006 and negligible conversion of HNO3. Unwanted (artifact) signal in clean synthetic air is also greatly minimized through the use of optical filters. Fast instrument response is achieved by minimizing NO2 inlet line and photolysis cell residence times. NO and NO2 sample residence times are matched in a multichannel instrument so that signal from ambient NO may be easily subtracted from the total signal and ambient NO2 calculated by difference at high time resolution. Induced change in the ambient ratio of NO to NO2, due to reaction of ozone and other oxidants with NO during sampling, is minimized in the new design. This configuration permits simple and accurate retrieval of NO2 concentrations in aircraft transects of power plant plumes, where ambient NO concentrations can change over several orders of magnitude in seconds. At lower concentrations found in the planetary boundary layer, agreement between calculated and observed NO2 is within ±(40 pptv+7%) for a 10‐s average. The new converter consumes less power, is more efficient, and is less expensive to operate than previous photolysis designs.

An intercomparison of results from ferrous sulphate and photolytic converter techniques for measurements of NOx made during the NASA GTE/CITE 1 aircraft program

Two techniques designed for measurements of NOx (NO + NO2) were intercompared during aircraft flights made in the spring of 1984 in the middle free troposphere over the eastern Pacific Ocean and southwestern United States. One NO chemiluminescence instrument was equipped with a ferrous sulphate converter, another with a photolytic converter. The ferrous sulphate‐equipped instrument was apparently much less specific for NO2. It registered levels about 3 times larger than the photolytic converter and gave NO2/NO ratios that were much larger than photochemical calculations would indicate as reasonable. Additionally, the results imply that active NOx was only 10–20% of total odd nitrogen in the middle free troposphere.