Atmospheric Measurement Techniques

Abstract. Recent advances in uncooled detector technology now offer the possibility of using relatively inexpensive thermal (7 to 14 μm) imaging devices as tools for studying and quantifying the behaviour of hazardous gases and particulates in atmospheric plumes. An experimental fast-sampling (60 Hz) ground-based uncooled thermal imager (Cyclops), operating with four spectral channels at central wavelengths of 8.6, 10, 11 and 12 μm and one broadband channel (7–14 μm) has been tested at several volcanoes and at an industrial site, where SO2 was a major constituent of the plumes. This paper presents new algorithms, which include atmospheric corrections to the data and better calibrations to show that SO2 slant column density can be reliably detected and quantified. Our results indicate that it is relatively easy to identify and discriminate SO2 in plumes, but more challenging to quantify the column densities. A full description of the retrieval algorithms, illustrative results and a detailed error analysis are provided. The noise-equivalent temperature difference (NEΔT) of the spectral channels, a fundamental measure of the quality of the measurements, lies between 0.4 and 0.8 K, resulting in slant column density errors of 20%. Frame averaging and improved NEΔT's can reduce this error to less than 10%, making a stand-off, day or night operation of an instrument of this type very practical for both monitoring industrial SO2 emissions and for SO2 column densities and emission measurements at active volcanoes. The imaging camera system may also be used to study thermal radiation from meteorological clouds and the atmosphere.

Abstract. We describe a new algorithm for the retrieval of nitrogen dioxide (NO2) vertical columns from nadir-viewing satellite instruments. This algorithm (SP2) is the basis for the Version 2.1 OMI This algorithm (SP2) is the basis for the Version 2.1 Ozone Monitoring Instrument (OMI) NO2 Standard Product and features a novel method for separating the stratospheric and tropospheric columns. NO2 Standard Product and features a novel method for separating the stratospheric and tropospheric columns. The approach estimates the stratospheric NO2 directly from satellite data without using stratospheric chemical transport models or assuming any global zonal wave pattern. Tropospheric NO2 columns are retrieved using air mass factors derived from high-resolution radiative transfer calculations and a monthly climatology of NO2 profile shapes. We also present details of how uncertainties in the retrieved columns are estimated. The sensitivity of the retrieval to assumptions made in the stratosphere–troposphere separation is discussed and shown to be small, in an absolute sense, for most regions. We compare daily and monthly mean global OMI NO2 retrievals using the SP2 algorithm with those of the original Version 1 Standard Product (SP1) and the Dutch DOMINO product. The SP2 retrievals yield significantly smaller summertime tropospheric columns than SP1, particularly in polluted regions, and are more consistent with validation studies. SP2 retrievals are also relatively free of modeling artifacts and negative tropospheric NO2 values. In a reanalysis of an INTEX-B validation study, we show that SP2 largely eliminates an ~20% discrepancy that existed between OMI and independent in situ springtime NO2 SP1 measurements.

Abstract. We describe the new version 3.0 NASA Ozone Monitoring Instrument (OMI) standard nitrogen dioxide (NO2) products (SPv3). The products and documentation are publicly available from the NASA Goddard Earth Sciences Data and Information Services Center (https://disc.gsfc.nasa.gov/datasets/OMNO2_V003/summary/). The major improvements include (1) a new spectral fitting algorithm for NO2 slant column density (SCD) retrieval and (2) higher-resolution (1° latitude and 1.25° longitude) a priori NO2 and temperature profiles from the Global Modeling Initiative (GMI) chemistry–transport model with yearly varying emissions to calculate air mass factors (AMFs) required to convert SCDs into vertical column densities (VCDs). The new SCDs are systematically lower (by ∼ 10–40 %) than previous, version 2, estimates. Most of this reduction in SCDs is propagated into stratospheric VCDs. Tropospheric NO2 VCDs are also reduced over polluted areas, especially over western Europe, the eastern US, and eastern China. Initial evaluation over unpolluted areas shows that the new SPv3 products agree better with independent satellite- and ground-based Fourier transform infrared (FTIR) measurements. However, further evaluation of tropospheric VCDs is needed over polluted areas, where the increased spatial resolution and more refined AMF estimates may lead to better characterization of pollution hot spots.

Abstract. We present intercomparison results for formaldehyde (HCHO) slant column measurements performed during the Cabauw Intercomparison campaign of Nitrogen Dioxide measuring Instruments (CINDI) that took place in Cabauw, the Netherlands, in summer 2009. During two months, nine atmospheric research groups simultaneously operated MAX-DOAS (MultiAXis Differential Optical Absorption Spectroscopy) instruments of various designs to record UV-visible spectra of scattered sunlight at different elevation angles that were analysed using common retrieval settings. The resulting HCHO data set was found to be highly consistent, the mean difference between instruments generally not exceeding 15% or 7.5 × 1015 molec cm−2, for all viewing elevation angles. Furthermore, a sensitivity analysis was performed to investigate the uncertainties in the HCHO slant column retrieval when varying key input parameters such as the molecular absorption cross sections, correction terms for the Ring effect or the width and position of the fitting interval. This study led to the identification of potentially important sources of errors associated with cross-correlation effects involving the Ring effect, O4, HCHO and BrO cross sections and the DOAS closure polynomial. As a result, a set of updated recommendations was formulated for HCHO slant column retrieval in the 336.5–359 nm wavelength range. To conclude, an error budget is proposed which distinguishes between systematic and random uncertainties. The total systematic error is estimated to be of the order of 20% and is dominated by uncertainties in absorption cross sections and related spectral cross-correlation effects. For a typical integration time of one minute, random uncertainties range between 5 and 30%, depending on the noise level of individual instruments.

Abstract. Tropospheric NO2 and stratospheric NO2 vertical column densities are important TROPOspheric Monitoring Instrument (TROPOMI) data products. In order to validate the TROPOMI NO2 products, KNMI Multi-AXis Differential Optical Absorption Spectroscopy (MAX-DOAS) instruments have measured NO2 on ship cruises over the Atlantic and the Pacific oceans. The MAX-DOAS instruments have participated in five cruises on board RV Sonne (in 2017 and 2019) and RV Maria S. Merian (in 2018). The MAX-DOAS measurements were acquired over 7 months and spanned about 90∘ in latitude and 300∘ in longitude. During the cruises aerosol measurements from Microtops sun photometers were also taken. The MAX-DOAS measured stratospheric NO2 columns between 1.5×1015 and 3.5×1015 molec cm−2 and tropospheric NO2 up to 0.6×1015 molec cm−2. The MAX-DOAS stratospheric NO2 vertical column densities have been compared with TROPOMI stratospheric NO2 vertical column densities and the stratospheric NO2 vertical column densities simulated by the global chemistry Transport Model, version 5, Massively Parallel model (TM5-MP). Good correlation is found between the MAX-DOAS and TROPOMI and TM5 stratospheric NO2 vertical column densities, with a correlation coefficient of 0.93 or larger. The TROPOMI and TM5 stratospheric NO2 vertical column densities are about 0.4×1015 molec cm−2 (19 %) higher than the MAX-DOAS measurements. The TROPOMI tropospheric NO2 also has good agreement with the MAX-DOAS measurements. The tropospheric NO2 vertical column density is as low as 0.5×1015 molec cm−2 over remote oceans.

Abstract. We attempt for the first time to retrieve lower-tropospheric vertical profile information for 8 quantities from ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) observations. The components retrieved are the aerosol extinction coefficients at two wavelengths, 357 and 476 nm, and NO2, HCHO, CHOCHO, H2O, SO2, and O3 volume mixing ratios. A Japanese MAX-DOAS profile retrieval algorithm, version 1 (JM1), is applied to observations performed at Cabauw, the Netherlands (51.97° N, 4.93° E), in June–July 2009 during the Cabauw Intercomparison campaign of Nitrogen Dioxide measuring Instruments (CINDI). Of the retrieved profiles, we focus here on the lowest-layer data (mean values at altitudes 0–1 km), where the sensitivity is usually highest owing to the longest light path. In support of the capability of the multi-component retrievals, we find reasonable overall agreement with independent data sets, including a regional chemical transport model (CHIMERE) and in situ observations performed near the surface (2–3 m) and at the 200-m height level of the tall tower in Cabauw. Plumes of enhanced HCHO and SO2 were likely affected by biogenic and ship emissions, respectively, and an improvement in their emission strengths is suggested for better agreement between CHIMERE simulations and MAX-DOAS observations. Analysis of air mass factors indicates that the horizontal spatial representativeness of MAX-DOAS observations is about 3–15 km (depending mainly on aerosol extinction), comparable to or better than the spatial resolution of current UV-visible satellite observations and model calculations. These demonstrate that MAX-DOAS provides multi-component data useful for the evaluation of satellite observations and model calculations and can play an important role in bridging different data sets having different spatial resolutions.

Abstract. We present an innovative instrument telescope and describe a retrieval method to probe three-dimensional (3-D) distributions of atmospheric trace gases that are relevant to air pollution and tropospheric chemistry. The University of Colorado (CU) two-dimensional (2-D) multi-axis differential optical absorption spectroscopy (CU 2-D-MAX-DOAS) instrument measures nitrogen dioxide (NO2), formaldehyde (HCHO), glyoxal (CHOCHO), oxygen dimer (O2–O2, or O4), and water vapor (H2O); nitrous acid (HONO), bromine monoxide (BrO), and iodine monoxide (IO) are among other gases that can in principle be measured. Information about aerosols is derived through coupling with a radiative transfer model (RTM). The 2-D telescope has three modes of operation: mode 1 measures solar scattered photons from any pair of elevation angle (−20° < EA < +90° or zenith; zero is to the horizon) and azimuth angle (−180° < AA < +180°; zero being north); mode 2 measures any set of azimuth angles (AAs) at constant elevation angle (EA) (almucantar scans); and mode 3 tracks the direct solar beam via a separate view port. Vertical profiles of trace gases are measured and used to estimate mixing layer height (MLH). Horizontal distributions are then derived using MLH and parameterization of RTM (Sinreich et al., 2013). NO2 is evaluated at different wavelengths (350, 450, and 560 nm), exploiting the fact that the effective path length varies systematically with wavelength. The area probed is constrained by O4 observations at nearby wavelengths and has a diurnal mean effective radius of 7.0 to 25 km around the instrument location; i.e., up to 1960 km2 can be sampled with high time resolution. The instrument was deployed as part of the Multi-Axis DOAS Comparison campaign for Aerosols and Trace gases (MAD-CAT) in Mainz, Germany, from 7 June to 6 July 2013. We present first measurements (modes 1 and 2 only) and describe a four-step retrieval to derive (a) boundary layer vertical profiles and MLH of NO2; (b) near-surface horizontal distributions of NO2; (c) range-resolved NO2 horizontal distribution measurements using an "onion-peeling" approach; and (d) the ratios HCHO to NO2 (RFN), CHOCHO to NO2 (RGN), and CHOCHO to HCHO (RGF) at 14 pre-set azimuth angles distributed over a 360° view. Three-dimensional distribution measurements with 2-D-MAX-DOAS provide an innovative, regional perspective of trace gases as well as their spatial and temporal concentration gradients, and they maximize information to compare near-surface observations with atmospheric models and satellites.

Abstract. This study describes a novel application of an “onion-peeling” approach to multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements of shipping emissions aiming at investigating the strong horizontal inhomogeneities in NO2 over a shipping lane. To monitor ship emissions on the main shipping route towards the port of Hamburg, a two-channel (UV and visible) MAX-DOAS instrument was deployed on the island Neuwerk in the German Bight, 6–7 km south of the main shipping lane. Utilizing the fact that the effective light path length in the atmosphere depends systematically on wavelength, simultaneous measurements and DOAS retrievals in the UV and visible spectral ranges are used to probe air masses at different horizontal distances to the instrument to estimate two-dimensional pollutant distributions. Two case studies have been selected to demonstrate the ability to derive the approximate plume positions in the observed area. A situation with northerly wind shows high NO2 concentrations close to the measurement site and low values in the north of the shipping lane. The opposite situation with southerly wind, unfavorable for the on-site in situ instrumentation, demonstrates the ability to detect enhanced NO2 concentrations several kilometers away from the instrument. Using a Gaussian plume model, in-plume NO2 volume mixing ratios can be derived from the MAX-DOAS measurements. For validation, a comparison to airborne imaging DOAS measurements during the NOSE campaign in July 2013 is performed, showing good agreement between the approximate plume position derived from the onion-peeling MAX-DOAS and the airborne measurements as well as between the derived in-plume NO2 volume mixing ratios (VMRs).

Abstract. We present car Multi-Axis (MAX-) DOAS observations of tropospheric NO2 carried out on circles around the cities of Mannheim and Ludwigshafen (Germany) on 24 August 2006. Together with information on wind speed and direction, the total emissions of the encircled source(s) are quantified from these measurements. In contrast to recent similar studies based on zenith scattered sun light (elevation angle of 90°), we use a MAX-DOAS instrument mounted on a car, which observes scattered sun light under different elevation angles (here 45°, and 90°). Compared to simple zenith sky observations, MAX-DOAS observations have higher sensitivity and reduced uncertainty, and avoid systematic offsets in the determination of the vertically integrated trace gas concentration. The determination of the absolute value of the integrated tropospheric trace gas concentrations is especially important for the calculation of absolute trace gas fluxes through arbitrary transects. However, even if emission sources are completely surrounded, systematic offsets in the measured vertically integrated trace gas concentration can lead to errors in the determined total emissions, especially for observations around extended areas. In this study we discuss and quantify different error sources. In most cases, the largest error source is the variability and imperfect knowledge of the wind field. In addition – depending on the trace species observed - also chemical transformations between the emission sources and the measurement location have to be considered. For that purpose we use local observations within the encircled area to quantify and/or correct these errors. From our observations we derive a total NOx emission from the Mannheim/Ludwigshafen area of (7.4±1.8)×1024 molec/sec, which if assumed to be constant throughout the year would correspond to a total emission of 17 830±4340 t/yr (calculated with the mass of NO2 t/yr, consistent with existing emission estimates. From our observations it is also possible to separately determine the average influx into the Mannheim/Ludwigshafen area (5.4±0.9×1024 molec/sec or 13 010±2170 t/yr) and the average outflux (12.8±1.8×1024 molec/sec or 13 010±4340 t/yr).