Multi-axis Differential Optical Absorption Spectroscopy Instrument Research Articles

Continuous multi-component MAX-DOAS observations for the planetary boundary layer ozone variation analysis at Chiba and Tsukuba, Japan, from 2013 to 2019

Ground-based remote sensing using multi-axis differential optical absorption spectroscopy (MAX-DOAS) was used to conduct continuous simultaneous observations of ozone (O3), nitrogen dioxide (NO2), and formaldehyde (HCHO) concentrations at Chiba (35.63° N, 140.10° E, 21 m a.s.l.) and Tsukuba (36.06° N, 140.13° E, 35 m a.s.l.), Japan, for 7 years from 2013 to 2019. These are urban and suburban sites, respectively, in the greater Tokyo metropolitan area. NO2 and HCHO are considered to be proxies for nitrogen oxides (NOx) and volatile organic compounds (VOCs), respectively, both of which are major precursors of tropospheric O3. The mean concentrations below an altitude of 1 km were analyzed as planetary boundary layer (PBL) concentrations. For a more spatially representative analysis around the urban area of Chiba, four MAX-DOAS instruments directed at four different azimuth directions (north, east, west, and south) were operated simultaneously and their data were unified. During the 7-year period, the satellite observations indicated an abrupt decrease in the tropospheric NO2 concentration over East Asia, including China. This suggested that the transboundary transport of O3 originating from the Asian continent was likely suppressed or almost unchanged during the period. Over this time period, the MAX-DOAS observations revealed the presence of almost-constant annual variations in the PBL O3 concentration, whereas reductions in NO2 and HCHO concentrations occurred at rates of approximately 6–10%/year at Chiba. These changes provided clear observational evidence that a decreasing NOx concentration significantly reduced the amount of O3 quenched through NO titration under VOC-limited conditions in the urban area. Under the dominant VOC-limited conditions, the MAX-DOAS-derived concentration ratio of HCHO/NO2 was found to be below unity in all months. Thus, the multi-component observations from MAX-DOAS provided a unique data set of O3, NO2, and HCHO concentrations for analyzing PBL O3 variations.

Inter-comparison of MAX-DOAS measurements of tropospheric HONO slant column densities and vertical profiles during the CINDI-2 campaign

Abstract. We present the inter-comparison of delta slant column densities (SCDs) and vertical profiles of nitrous acid (HONO) derived from measurements of different multi-axis differential optical absorption spectroscopy (MAX-DOAS) instruments and using different inversion algorithms during the Second Cabauw Inter-comparison campaign for Nitrogen Dioxide measuring Instruments (CINDI-2) in September 2016 at Cabauw, the Netherlands (51.97∘ N, 4.93∘ E). The HONO vertical profiles, vertical column densities (VCDs), and near-surface volume mixing ratios are compared between different MAX-DOAS instruments and profile inversion algorithms for the first time. Systematic and random discrepancies of the HONO results are derived from the comparisons of all data sets against their median values. Systematic discrepancies of HONO delta SCDs are observed in the range of ±0.3×1015 molec. cm−2, which is half of the typical random discrepancy of 0.6×1015 molec. cm−2. For a typical high HONO delta SCD of 2×1015 molec. cm−2, the relative systematic and random discrepancies are about 15 % and 30 %, respectively. The inter-comparison of HONO profiles shows that both systematic and random discrepancies of HONO VCDs and near-surface volume mixing ratios (VMRs) are mostly in the range of ∼±0.5×1014 molec. cm−2 and ∼±0.1 ppb (typically ∼20 %). Further we find that the discrepancies of the retrieved HONO profiles are dominated by discrepancies of the HONO delta SCDs. The profile retrievals only contribute to the discrepancies of the HONO profiles by ∼5 %. However, some data sets with substantially larger discrepancies than the typical values indicate that inappropriate implementations of profile inversion algorithms and configurations of radiative transfer models in the profile retrievals can also be an important uncertainty source. In addition, estimations of measurement uncertainties of HONO dSCDs, which can significantly impact profile retrievals using the optimal estimation method, need to consider not only DOAS fit errors, but also atmospheric variability, especially for an instrument with a DOAS fit error lower than ∼3×1014 molec. cm−2. The MAX-DOAS results during the CINDI-2 campaign indicate that the peak HONO levels (e.g. near-surface VMRs of ∼0.4 ppb) often appeared in the early morning and below 0.2 km. The near-surface VMRs retrieved from the MAX-DOAS observations are compared with those measured using a co-located long-path DOAS instrument. The systematic differences are smaller than 0.15 and 0.07 ppb during early morning and around noon, respectively. Since true HONO values at high altitudes are not known in the absence of real measurements, in order to evaluate the abilities of profile inversion algorithms to respond to different HONO profile shapes, we performed sensitivity studies using synthetic HONO delta SCDs simulated by a radiative transfer model with assumed HONO profiles. The tests indicate that the profile inversion algorithms based on the optimal estimation method with proper configurations can reproduce the different HONO profile shapes well. Therefore we conclude that the features of HONO accumulated near the surface derived from MAX-DOAS measurements are expected to represent the ambient HONO profiles well.

Shipborne MAX-DOAS measurements for validation of TROPOMI NO2 products

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.

Observations of Atmospheric NO2 Using a New Low-Cost MAX-DOAS System

This article describes the prototype of a new MAX-DOAS (multi-axis differential optical absorption spectroscopy) system built at “Dunarea de Jos” University of Galati (UGAL), Romania, and the first results of its use to observe NO2 content over Galati city (45.42° N, 28.04° E). The new equipment is a ground-based MAX-DOAS system capable of measuring the spatial distribution of DSCD (differential slant column densities) of several trace gases using horizontal and vertical observations. The new optic system, named UGAL-2-DOAS, is an in-house, low-cost, solution in comparison to the existing market of the MAX-DOAS systems. This paper describes the technical design and capabilities of the new MAX-DOAS instrument. The UGAL-2D-DOAS system was tested in April and June 2017 in Galati city. Measurements over three days were selected for the present manuscript. Full azimuthal (0–360°), local celestial meridian observations and other elevation angle sequence measurements (e.g., E–W) were performed. We found that the new MAX-DOAS system is able to detect diurnal variation and the local source emissions of NO2 from the urban environment. Also, we present concomitant zenith-sky car-DOAS observations measurements around the location of the new MAX-DOAS instrument. Comparing the horizontal scanning sequence of the new developed instrument with the mobile DOAS observations, we found that both systems can indicate and detect the same NO2 sources.

Studies of the horizontal inhomogeneities in NO2 concentrations above a shipping lane using ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) measurements and validation with airborne imaging DOAS measurements

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).

Investigating the temporal variation of formaldehyde using MAX-DOAS and satellite observations over Islamabad, Pakistan

Formaldehyde (HCHO) being an oxygenated Volatile Organic Compound (VOC), essentially contributes to the hazardous tropospheric ozone pollution in urban areas. Emissions from automobiles are the major contributors towards elevated formaldehyde concentrations in major urban cities of Pakistan. The current study is designed to explore the formaldehyde columns at a stationary site, Institute of Environmental Science and Engineering (IESE), National University of Science and Technology (NUST) Islamabad from September 2015 to August 2017 using Multi-Axis – Differential Optical Absorption Spectroscopy (MAX-DOAS). Observations from MAX-DOAS instrument were used to measure the diurnal, weekly and annual cycle of formaldehyde (HCHO). The diurnal concentrations of HCHO were found to be at its maximum during early morning and evening hours. Relatively insignificant weekly cycle with higher concentrations on working days and lesser during the weekend was observed at IESE-NUST monitoring site. While annual cycle showed the highest columns in summer followed by spring, autumn and winter. The suspected sources of HCHO at a fixed station were identified as natural gas consumption, biogenic emissions from vegetation, emissions from industries and vehicular emissions. Furthermore, ground-based measurements were compared with monthly Ozone Monitoring Instrument (OMI) satellite observations. A good correlation with Pearson value of 0.68 is noticed during the whole study period.

Vertical profiles of NO<sub>2</sub>, SO<sub>2</sub>, HONO, HCHO, CHOCHO and aerosols derived from MAX-DOAS measurements at a rural site in the central western North China Plain and their relation to emission sources and effects of regional transport

Abstract. A multi-axis differential optical absorption spectroscopy (MAX-DOAS) instrument was deployed in May and June 2016 at a monitoring station (37.18∘ N, 114.36∘ E) in the suburban area of Xingtai, which is one of the most polluted cities in the North China Plain (NCP), during the Atmosphere-Aerosol-Boundary Layer-Cloud (A2BC) experiment and Air chemistry Research In Asia (ARIAs) joint experiments to derive tropospheric vertical profiles of NO2, SO2, HONO, HCHO, CHOCHO and aerosols. Aerosol optical depths derived from MAX-DOAS were found to be consistent with collocated sun-photometer measurements. Also the derived near-surface aerosol extinction and HCHO mixing ratio agree well with the coincident visibility meter and in situ HCHO measurements, with mean HCHO near-surface mixing ratios of ∼3.5 ppb. Underestimations of MAX-DOAS results compared to in situ measurements of NO2 (∼60 %) and SO2 (∼20 %) are found expectedly due to vertical and horizontal inhomogeneity of trace gases. Vertical profiles of aerosols and NO2 and SO2 are reasonably consistent with those measured by a collocated Raman lidar and aircraft spirals over the station. The deviations can be attributed to differences in sensitivity as a function of altitude and substantial horizontal gradients of pollutants. Aerosols, HCHO and CHOCHO profiles typically extended to higher altitudes (with 75 % integrated column located below ∼1.4 km) than NO2, SO2 and HONO did (with 75 % integrated column below ∼0.5 km) under polluted conditions. Lifted layers were systematically observed for all species (except HONO), indicating accumulation, secondary formation or long-range transport of the pollutants at higher altitudes. Maximum values routinely occurred in the morning for NO2, SO2 and HONO but occurred at around noon for aerosols, HCHO and CHOCHO, mainly dominated by photochemistry, characteristic upslope–downslope circulation and planetary boundary layer (PBL) dynamics. Significant day-to-day variations are found for all species due to the effect of regional transport and changes in synoptic pattern analysed with the backward propagation approach based on HYSPLIT trajectories. Low pollution was often observed for air masses from the north-west (behind cold fronts), and high pollution was observed from the southern areas such as industrialized Wu'an. The contribution of regional transport for the pollutants measured at the site during the observation period was estimated to be about 20 % to 30 % for trace gases and about 50 % for aerosols. In addition, agricultural burning events impacted the day-to-day variations in HCHO, CHOCHO and aerosols. It needs to be noted that although several MAX-DOAS measurements of trace gases and aerosols in the NCP area have been reported in previous studies, this study is the first work to derive a comprehensive set of vertical profiles of NO2, SO2, HONO, HCHO, CHOCHO and aerosols from measurements of one MAX-DOAS instrument. Also, so far, the validation of MAX-DOAS profile results by comparison with various surface in situ measurements as well as profile measurements from lidar and aircraft is scarce. Moreover, the backward propagation approach for characterizing the contributions of regional transport of pollutants from different regions was applied to the MAX-DOAS results of trace gases and aerosols for the first time.

Ground-based MAX-DOAS observations of tropospheric aerosols, NO<sub>2</sub>, SO<sub>2</sub> and HCHO in Wuxi, China, from 2011 to 2014

Abstract. We characterize the temporal variation and vertical distribution of nitrogen dioxide (NO2), sulfur dioxide (SO2), formaldehyde (HCHO) and aerosol extinction based on long-term multi-axis differential optical absorption spectroscopy (MAX-DOAS) observations from May 2011 to November 2014 in Wuxi, China. A new inversion algorithm (PriAM) is implemented to retrieve profiles of the trace gases (TGs) and aerosol extinction (AE) from the UV spectra of scattered sunlight recorded by the MAX-DOAS instrument. We investigated two important aspects of the retrieval process. We found that the systematic seasonal variation of temperature and pressure (which is regularly observed in Wuxi) can lead to a systematic bias of the retrieved aerosol profiles (e.g. up to 20 % for the AOD) if it is not explicitly considered. In this study we take this effect into account for the first time. We also investigated in detail the reason for the differences of tropospheric vertical column densities derived from either the geometric approximation or by the integration of the retrieved profiles, which were reported by earlier studies. We found that these differences are almost entirely caused by the limitations of the geometric approximation (especially for high aerosol loads). The results retrieved from the MAX-DOAS observations are compared with independent techniques not only under cloud-free sky conditions, but also under various cloud scenarios. Under most cloudy conditions (except fog and optically thick clouds), the trace gas results still show good agreements. In contrast, for the aerosol results, only near-surface AE could be still well retrieved under cloudy situations. After applying a quality control procedure, the MAX-DOAS data are used to characterize the seasonal, diurnal and weekly variations of NO2, SO2, HCHO and aerosols. A regular seasonality of the three trace gases is found, but not for aerosols. Similar annual variations of the profiles of the trace gases appear in different years. Only NO2 shows a significant seasonality of the diurnal variations. Considerable amplitudes of weekly cycles occur for NO2 and SO2, but not for HCHO and aerosols. The TGs and aerosols show good correlations, especially for HCHO in winter. More pronounced wind direction dependencies, especially for the near-surface concentrations, are found for the trace gases than for the aerosols, which implies that the local emissions from nearby industrial areas (including traffic emissions) dominate the local pollution, while long-distance transport might also considerably contribute to the local aerosol levels.

Estimates of free-tropospheric NO<sub>2</sub> and HCHO mixing ratios derived from high-altitude mountain MAX-DOAS observations at midlatitudes and in the tropics

Abstract. In this study, mixing ratios of NO2 (XNO2) and HCHO (XHCHO) in the free troposphere are derived from two multi-axis differential optical absorption spectroscopy (MAX-DOAS) data sets collected at Zugspitze (2650 m a.s.l., Germany) and Pico Espejo (4765 m a.s.l., Venezuela). The estimation of NO2 and HCHO mixing ratios is based on the modified geometrical approach, which assumes a single-scattering geometry and a scattering point altitude close to the instrument altitude. Firstly, the horizontal optical path length (hOPL) is obtained from O4 differential slant column densities (DSCDs) in the horizontal (0°) and vertical (90°) viewing directions. Secondly, XNO2 and XHCHO are estimated from the NO2 and HCHO DSCDs at the 0° and 90° viewing directions and averaged along the obtained hOPLs. As the MAX-DOAS instrument was performing measurements in the ultraviolet region, wavelength ranges of 346–372 and 338–357 nm are selected for the DOAS analysis to retrieve NO2 and HCHO DSCDs, respectively. In order to compare the measured O4 DSCDs and moreover to perform some sensitivity tests, the radiative transfer model SCIATRAN with adapted altitude settings for mountainous terrain is operated to simulate synthetic spectra, on which the DOAS analysis is also applied. The overall agreement between measured and synthetic O4 DSCDs is better for the higher Pico Espejo station than for Zugspitze. Further sensitivity analysis shows that a change in surface albedo (from 0.05 to 0.7) can influence the O4 DSCDs, with a larger absolute difference observed for the horizontal viewing direction. Consequently, the hOPL can vary by about 5 % throughout the season, for example when winter snow cover fully disappears in summer. Typical values of hOPLs during clear-sky conditions are 19 km (14 km) at Zugspitze and 34 km (26.5 km) at Pico Espejo when using the 346–372 (338–357 nm) fitting window. The estimated monthly values of XNO2 (XHCHO), averaged over these hOPLs during clear-sky conditions, are in the range of 60–100 ppt (500–950 ppt) at Zugspitze and 8.5–15.5 ppt (255–385 ppt) at Pico Espejo. Interestingly, multi-year-averaged monthly means of XNO2 and XHCHO increase towards the end of the dry season at the Pico Espejo site, suggesting that both trace gases are frequently lifted above the boundary layer as a result of South American biomass burning.

Intercomparison of slant column measurements of NO2 by ground-based MAX-DOAS

In September 2011, we used 3 ground-based multi-axis differential optical absorption spectroscopy (MAX-DOAS) instruments of different designs and operation protocols to measure tropospheric NO2 for about 20 days, at the Station of Atmospheric Comprehensive Observatory, Institute of Atmospheric Physics, Chinese Academy of Sciences (Xianghe 117.0N, 39.77E). All instruments are oriented to an azimuth angle of 270 (north), in a common wavelength range and with a set of cross sections for the inversion of NO2 slant column in visible and UV wavelength range respectively. Intercomparison of NO2 slant columns among three MAX-DOAS is introduced. The results obtained from the different instruments are in good accordance with each other, and the correlation coefficients are all higher than 0.95, but systematical errors exist. Daily average errors of three MAX-DOAS instruments are almost below 6%, showing that the instruments work steadily and the data are cogent. The UV results are smaller than those in the visible range, especially on the overcast days, related to the wavelength dependence of Rayleigh and Mie scattering. After the correction of systematical errors, there is better consistency among different results, which indicates that the three MAX-DOAS instruments have a capability to validate the atmospheric component products of satellite.

Retrieval of surface NO2 mixing ratio from multi-axis differential optical absorption spectroscopy

The multi-axis differential optical absorption spectroscopy (MAX-DOAS) technique, in which solar scattered light beams of different elevation angles are used and the spatial distribution of various trace gases is derived, has been widely used for monitoring the NO2 slant column density. Due to the lack of information in a detectable horizontal range of the MAX-DOAS instrument, the concentration of trace gases including NO2 is unable to yield directly. In this work, the relationship between extinction coefficient and light path length of MAX-DOAS observation is analyzed, and a retrieval algorithm to convert the horizontal NO2 differential slant column density into the volume mixing ratio with the information of visibility is described. This algorithm has been used in the MAX-DOAS observation at Hefei, and volume NO2 mixing ratio is derived from MAX-DOAS measurement combining the data of visibility. The NO2 concentration measured with MAX-DOAS shows that it is in good agreement with the result obtained with long path differential optical absorption spectroscopy, proving the feasibility of the retrieval method. This research presents a simple and effective monitoring method of volume NO2 mixing ratio with MAX-DOAS, there by expanding the application scope of MAX-DOAS technique.

Atmospheric measurements at Reunion Island

It is now well-known that the climate is changing, but the effects of climate change vary at different atmospheric levels. For example, climatemodels predict up to a 7K cooling of the stratosphere, but a warming of the troposphere of about 2K. Thus, it is of primary importance to detect and quantify such changes, and to identify and measure exchanges between atmospheric levels. Achieving this goal requires long-term data records documenting the atmosphere’s vertical temperature profile and chemical composition. Ideally, this data should reflect varying types of instruments and approaches (i.e., ground based observations, satellite data, andmodels). At an atmospheric station on Reunion Island, scientists are contributing to this data set (see Figure 1) using the systems at their disposal. There have been five main instruments available at the island in recent years. First, the systeme d’analyse par observation zenitale (SAOZ) is a UV-visible spectrometer providing total ozone (O3) and NO2 columns twice a day, at sunrise and sunset. This instrument has worked to this schedule since 1993. SAOZ data is being extensively used for the validation of satellite data. The multi-axis differential optical absorption spectroscopy instrument (MAXDOAS) is another UV-visible spectrometer designed to measure stratospheric and/or tropospheric columns of atmospheric trace gases NO2, BrO, HCHO, O3 , SO2, IO, and O4. This was installed in July 2004 andoperated continuously for a period of one year. In 2007, it is expected to resume operations. Third is a high-spectral-resolution Fourier-transform infrared spectrometer (FTIR) that provides quasi-simultaneous total column and/or vertical profiles of about 20 atmospheric species, including O3 , CO, N2O, OCS, HF, HCl, and HNO3. So far, this instrument has been operated as needed, rather than on a routine basis, with longer-term operation expected to begin in 2007. Next, a light detection and ranging (lidar) system based on the active emission of laser pulses into the atmosphere is Figure 1. Atmospheric parameters are measured at a variety of altitudes by an instrumental set developed at Reunion Island. Hatched rectangles and lines represent total column measurements and profiles, respectively. Radiometers are in blue, sondes in red, and lidar in green.