Emission Monitoring Mobile Experiment (EMME): An overview and first results of the St. Petersburg megacity campaign 2019

Global climate change is one of the most important scientific, societal and economic contemporary challenges. Fundamental understanding of the major processes driving climate change is the key problem which is to be solved not only on a global but also on a regional scale. The accuracy of regional climate modelling depends on a number of factors. One of these factors is the adequate and comprehensive information on the anthropogenic impact which is highest in industrial regions and areas with dense population – modern megacities. Megacities are not only “heat islands”, but also significant sources of emissions of various substances into the atmosphere, including greenhouse and reactive gases. In 2019, the mobile experiment EMME (Emission Monitoring Mobile Experiment) was conducted within the St. Petersburg agglomeration (Russia) aiming to estimate the emission intensity of greenhouse (CO$_{2}$, CH$_{4}$) nd reactive (CO, NO$_{x}$) gases for St. Petersburg, which is the largest northern megacity. St. Petersburg State University (Russia), Karlsruhe Institute of Technology (Germany) and the University of Bremen (Germany) jointly ran this experiment. The core instruments of the campaign were two portable Bruker EM27/SUN Fourier transform infrared (FTIR) spectrometers which were used for ground-based remote sensing measurements of the total column amount of CO$_{2}$, CH$_{4}$ and CO at upwind and downwind locations on opposite sides of the city. The NO$_{2}$ tropospheric column amount was observed along a circular highway around the city by continuous mobile measurements of scattered solar visible radiation with an OceanOptics HR4000 spectrometer using the differential optical absorption spectroscopy (DOAS) technique. Simultaneously, air samples were collected in air bags for subsequent laboratory analysis. The air samples were taken at the locations of FTIR observations at the ground level and also at altitudes of about 100 m when air bags were lifted by a kite (in case of suitable landscape and favourable wind conditions). The entire campaign consisted of 11 mostly cloudless days of measurements in March–April 2019. Planning of measurements for each day included the determination of optimal location for FTIR spectrometers based on weather forecasts, combined with the numerical modelling of the pollution transport in the megacity area. The real-time corrections of the FTIR operation sites were performed depending on the actual evolution of the megacity NO$_{x}$ plume as detected by the mobile DOAS observations. The estimates of the St. Petersburg emission intensities for the considered greenhouse and reactive gases were obtained by coupling a box model and the results of the EMME observational campaign using the mass balance approach. The CO$_{2}$ emission flux for St. Petersburg as an area source was estimated to be 89 ± 28 ktkm$^{-2}$ yr $^{-2}$ , which is 2 times higher than the corresponding value in the EDGAR database. The experiment revealed the CH$_{4}$ emission flux of 135 ± 68 tkm $^{-2}$ yr $^{-1}$, which is about 1 order of magnitude greater than the value reported by the official inventories of St. Petersburg emissions (∼ 25 tkm$^{-2}$ yr $^{-1}$ or 2017). At the same time, for the urban territory of St. Petersburg, both the EMME experiment and the official inventories for 2017 give similar results for the CO anthropogenic flux (251 ± 104 tkm $^{-2}$ yr $^{-1}$ s. 410 tkm $^{-2}$ yr $^{-1}$) nd for the NO$_{x}$ anthropogenic flux (66 ± 28 tkm$^{-2}$ yr $^{-1}$ vs. 69 tkm $^{-2}$ yr $^{-1}$)

The CU mobile Solar Occultation Flux instrument: structure functions and emission rates of NH₃, NO₂ and C₂H₆

We describe the University of Colorado mobile Solar Occultation Flux instrument (CU mobile SOF). The instrument consists of a digital mobile solar tracker that is coupled to a Fourier transform spectrometer (FTS) of 0.5 cm−1 resolution and a UV–visible spectrometer (UV–vis) of 0.55 nm resolution. The instrument is used to simultaneously measure the absorption of ammonia (NH3), ethane (C2H6) and nitrogen dioxide (NO2) along the direct solar beam from a moving laboratory. These direct-sun observations provide high photon flux and enable measurements of vertical column densities (VCDs) with geometric air mass factors, high temporal resolution of 2 s and spatial resolution of 5–19 m. It is shown that the instrument line shape (ILS) of the FTS is independent of the azimuth and elevation angle pointing of the solar tracker. Further, collocated measurements next to a high-resolution FTS at the National Center for Atmospheric Research (HR-NCAR-FTS) show that the CU mobile SOF measurements of NH3 and C2H6 are precise and accurate; the VCD error at high signal to noise ratio is 2–7 %. During the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) from 21 July to 3 September 2014 in Colorado, the CU mobile SOF instrument measured median (minimum, maximum) VCDs of 4.3 (0.5, 45)  ×  1016 molecules cm−2 NH3, 0.30 (0.06, 2.23)  ×  1016 molecules cm−2 NO2 and 3.5 (1.5, 7.7)  ×  1016 molecules cm−2 C2H6. All gases were detected in larger 95 % of the spectra recorded in urban, semi-polluted rural and remote rural areas of the Colorado Front Range. We calculate structure functions based on VCDs, which describe the variability of a gas column over distance, and find the largest variability for NH3. The structure functions suggest that currently available satellites resolve about 10 % of the observed NH3 and NO2 VCD variability in the study area. We further quantify the trace gas emission fluxes of NH3 and C2H6 and production rates of NO2 from concentrated animal feeding operations (CAFO) using the mass balance method, i.e., the closed-loop vector integral of the VCD times wind speed along the drive track. Excellent reproducibility is found for NH3 fluxes and also, to a lesser extent, NO2 production rates on 2 consecutive days; for C2H6 the fluxes are affected by variable upwind conditions. Average emission factors were 12.0 and 11.4 gNH3 h−1 head−1 at 30 °C for feedlots with a combined capacity for  ∼  54 000 cattle and a dairy farm of  ∼  7400 cattle; the pooled rate of 11.8 ± 2.0 gNH3 h−1 head−1 is compatible with the upper range of literature values. At this emission rate the NH3 source from cattle in Weld County, CO (535 766 cattle), could be underestimated by a factor of 2–10. CAFO soils are found to be a significant source of NOx. The NOx source accounts for  ∼  1.2 % of the N flux in NH3 and has the potential to add  ∼  10 % to the overall NOx emissions in Weld County and double the NOx source in remote areas. This potential of CAFO to influence ambient NOx concentrations on the regional scale is relevant because O3 formation is NOx sensitive in the Colorado Front Range. Emissions of NH3 and NOx are relevant for the photochemical O3 and secondary aerosol formation

Evaluation and Application of Max-DOAS Methods for Monitoring Aerosols, NO2, and SO2 in Urban and Industrial Environments

The ideal measurement technique to effectively address an air quality problem depends on the chemical and physical properties of the species and its environment. Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) techniques allow a diversity of applications for studying atmospheric species, including the determination of emissions, vertical profiles, and the tropospheric column loading of trace gases. Deployment of the MAX-DOAS instrument during the comprehensive air quality campaign in the Athabasca Oil Sands Region in 2013 provided a rare opportunity to evaluate the performance of multiple aspects of the MAX-DOAS retrievals. Retrievals of aerosol extinction, NO2, and SO2 were compared to data from lidar, sun photometer, Active-DOAS, and airborne in-situ measurements of trace gases. The MAX-DOAS retrievals performed well except under conditions of rapidly changing vertical profiles of pollution. Important elements required to achieve useful inter-comparisons of MAX-DOAS with other instruments (e.g., the lidar S-ratio) and advantages of the MAX-DOAS technique were identified. MAX-DOAS measurements of SO2 gas calibration cells were conducted to determine the optimal settings for fitting SO2 differential slant column densitities (dSCDs), currently absent in the literature. Fitting dSCDs of SO2 from solar measurements is challenging due to the effects of stray light, potential interference by O3 absorption, and low solar intensity in wavelength regions where SO2 absorption features are strong. Based on the experiments, the use of a short-pass filter and a fitting window of 307.5 < <319 nm are recommended. MAX-DOAS measurements in Toronto, Ontario, during 2015 quantified the impact of lake-breeze circulations on the tropospheric loading of NO2 and aerosol extinction. These first measurements of the total tropospheric loading of pollutants behind a lake breeze front on multiple days using MAX-DOAS confirms previously theorized 3-D structures of lake breezes. Finally, the mobile-MAX-DOAS technique of estimating NOx and SO2 emissions was improved by conducting simultaneous Mobile-MAX-DOAS and in-situ NO-NO2-NOx measurements and deploying a modular meteorological station while observing urban plumes in the industrial city of Sarnia, Ontario. These studies demonstrated the utility of MAX-DOAS techniques for monitoring tropospheric air quality in industrial and urban settings when in-situ and other remote sensing techniques are limited

Estimation of NOx Emissions from Delhi Using Car MAX-DOAS Observations and Comparison with OMI Satellite Data

We present the first Multi-Axis-(MAX-) DOAS observations in India performed during April 2010 and January 2011 in Delhi and nearby regions. The MAX-DOAS instrument was mounted on a car roof, which allowed us to perform measurements along individual driving routes. From car MAX-DOAS observations along closed circles around Delhi, together with information on wind speed and direction, the NOx emissions from the greater Delhi area were determined: our estimate of 4.4 x 10(25) molecules s(-1) is found to be slightly lower than the corresponding emission estimates using the EDGAR emission inventory and substantially smaller compared to a recent study by Gurjar et al. (2004). We also determined NOx emissions from Delhi using OMI satellite observations on the same days. These emissions are slightly smaller than those from the car MAX-DOAS measurements. Finally the car MAX-DOAS observations were also used for the validation of simultaneous OMI satellite measurements of the tropospheric NO2 VCD and found a good agreement of the spatial patterns. Concerning the absolute values, OMI data are, on average, higher than the car MAX-DOAS observations close to strong emission sources, and vice versa over less polluted regions. Our results indicate that OMI NO2 VCDs are biased low over strongly polluted regions, probably caused by inadequate a-priori profiles used in the OMI satellite retrieval

High-resolution airborne imaging DOAS measurements of NO2 above Bucharest during AROMAT

In this study we report on airborne imaging DOAS measurements of NO2 from two flights performed in Bucharest during the AROMAT campaign (Airborne ROmanian Measurements of Aerosols and Trace gases) in September 2014. These measurements were performed with the Airborne imaging Differential Optical Absorption Spectroscopy (DOAS) instrument for Measurements of Atmospheric Pollution (AirMAP) and provide nearly gapless maps of column densities of NO2 below the aircraft with a high spatial resolution of better than 100 m. The air mass factors, which are needed to convert the measured differential slant column densities (dSCDs) to vertical column densities (VCDs), have a strong dependence on the surface reflectance, which has to be accounted for in the retrieval. This is especially important for measurements above urban areas, where the surface properties vary strongly. As the instrument is not radiometrically calibrated, we have developed a method to derive the surface reflectance from intensities measured by AirMAP. This method is based on radiative transfer calculation with SCIATRAN and a reference area for which the surface reflectance is known. While surface properties are clearly apparent in the NO2 dSCD results, this effect is successfully corrected for in the VCD results. Furthermore, we investigate the influence of aerosols on the retrieval for a variety of aerosol profiles that were measured in the context of the AROMAT campaigns. The results of two research flights are presented, which reveal distinct horizontal distribution patterns and strong spatial gradients of NO2 across the city. Pollution levels range from background values in the outskirts located upwind of the city to about 4  ×  1016 molec cm−2 in the polluted city center. Validation against two co-located mobile car-DOAS measurements yields good agreement between the datasets, with correlation coefficients of R =  0.94 and R =  0.85, respectively. Estimations on the NOx emission rate of Bucharest for the two flights yield emission rates of 15.1 ± 9.4 and 13.6 ± 8.4 mol s−1, respectively

Optical remote sensing of industrial gas emission fluxes

Mobile optical remote sensing techniques offer promising possibilities to quantify and geographically attribute local industrial gaseous emissions to the atmosphere. Studies have repeatedly shown that such emissions are often poorly understood, underestimated, and thereby not properly accounted for in emission inventories and regional atmospheric chemistry models, especially for emissions of VOCs. A better understanding and quantification of industrial VOC emissions is crucial for combating ground-level ozone, a serious problem facing most of the world's larger urban areas. This thesis presents results from a number of measurement campaigns primarily conducted in the area around Houston, Texas, USA, which has one of the world's largest concentrations of oil, gas and petrochemical industries. In the campaigns, the two flux measurement methods Solar Occultation Flux (SOF) and Mobile DOAS were used to quantify emissions of VOCs (alkanes and alkenes), SO2, NO2, and formaldehyde (HCHO) from the largest industrial conglomerates in the area. Measured emissions are compared to industry estimates reported to emission inventories, showing discrepancies of up to an order of magnitude for VOCs but not for SO2 and NO2. Emission factor models are used to estimate effects on VOC emissions of unrepresentative meteorological conditions during the measurement campaigns. These effects are determined to be too small to explain the discrepancies between measurements and reported emissions seen for VOCs. A plume chemistry model is applied to a number of cases where formaldehyde were detected together with significant amounts of alkenes in order to assess whether the formaldehyde could be explained as a secondary pollutant from the oxidation of alkenes. The results of the modeling shows that secondary emissions can only explain a small fraction of the measured formaldehyde flux in most cases, suggesting that most of the formaldehyde emissions measured from local sources were primary emissions. Secondary emissions are, however, still believed to be the largest source of formaldehyde further downwind from sources

An overview of the MILAGRO 2006 Campaign: Mexico City emissions and their transport and transformation

MILAGRO (Megacity Initiative: Local And Global Research Observations) is an international collaborative project to examine the behavior and the export of atmospheric emissions from a megacity. The Mexico City Metropolitan Area (MCMA) – one of the world's largest megacities and North America's most populous city – was selected as the case study to characterize the sources, concentrations, transport, and transformation processes of the gases and fine particles emitted to the MCMA atmosphere and to evaluate the regional and global impacts of these emissions. The findings of this study are relevant to the evolution and impacts of pollution from many other megacities. The measurement phase consisted of a month-long series of carefully coordinated observations of the chemistry and physics of the atmosphere in and near Mexico City during March 2006, using a wide range of instruments at ground sites, on aircraft and satellites, and enlisting over 450 scientists from 150 institutions in 30 countries. Three ground supersites were set up to examine the evolution of the primary emitted gases and fine particles. Additional platforms in or near Mexico City included mobile vans containing scientific laboratories and mobile and stationary upward-looking lidars. Seven instrumented research aircraft provided information about the atmosphere over a large region and at various altitudes. Satellite-based instruments peered down into the atmosphere, providing even larger geographical coverage. The overall campaign was complemented by meteorological forecasting and numerical simulations, satellite observations and surface networks. Together, these research observations have provided the most comprehensive characterization of the MCMA's urban and regional atmospheric composition and chemistry that will take years to analyze and evaluate fully. In this paper we review over 120 papers resulting from the MILAGRO/INTEX-B Campaign that have been published or submitted, as well as relevant papers from the earlier MCMA-2003 Campaign, with the aim of providing a road map for the scientific community interested in understanding the emissions from a megacity such as the MCMA and their impacts on air quality and climate. This paper describes the measurements performed during MILAGRO and the results obtained on MCMA's atmospheric meteorology and dynamics, emissions of gases and fine particles, sources and concentrations of volatile organic compounds, urban and regional photochemistry, ambient particulate matter, aerosol radiative properties, urban plume characterization, and health studies. A summary of key findings from the field study is presented.Mexico. Comisión Ambiental MetropolitanaMexico. Ministry of the EnvironmentConsejo Nacional de Ciencia y Tecnología (Mexico)Petróleos MexicanosNational Science Foundation (U.S.). Atmospheric Chemistry ProgramAtmospheric Sciences Program (U.S.)United States. National Aeronautics and Space Administration. Radiation Science Progra

The glyoxal budget and its contribution to organic aerosol for Los Angeles, California, during CalNex 2010

Recent laboratory and field studies have indicated that glyoxal is a potentially large contributor to secondary organic aerosol mass. We present in situ glyoxal measurements acquired with a recently developed, high sensitivity spectroscopic instrument during the CalNex 2010 field campaign in Pasadena, California. We use three methods to quantify the production and loss of glyoxal in Los Angeles and its contribution to organic aerosol. First, we calculate the difference between steady state sources and sinks of glyoxal at the Pasadena site, assuming that the remainder is available for aerosol uptake. Second, we use the Master Chemical Mechanism to construct a two-dimensional model for gas-phase glyoxal chemistry in Los Angeles, assuming that the difference between the modeled and measured glyoxal concentration is available for aerosol uptake. Third, we examine the nighttime loss of glyoxal in the absence of its photochemical sources and sinks. Using these methods we constrain the glyoxal loss to aerosol to be 0-5 × 10-5 s-1 during clear days and (1 ± 0.3) × 10-5 s-1 at night. Between 07:00-15:00 local time, the diurnally averaged secondary organic aerosol mass increases from 3.2 μg m-3 to a maximum of 8.8 μg m -3. The constraints on the glyoxal budget from this analysis indicate that it contributes 0-0.2 μg m-3 or 0-4% of the secondary organic aerosol mass. Copyright 2011 by the American Geophysical Union

Measurements of industrial emissions of alkenes in Texas using the solar occultation flux method

Solar occultation flux (SOF) measurements of alkenes have been conducted to identify and quantify the largest emission sources in the vicinity of Houston and in SE Texas during September 2006 as part of the TexAQS 2006 campaign. The measurements have been compared to emission inventories and have been conducted in parallel with airborne plume studies. The SOF measurements show that the hourly gas emissions from the large petrochemical and refining complexes in the Houston Ship Channel area and Mount Belvieu during September 2006 corresponded to 1250 +/- 180 kg/h of ethene and 2140 +/- 520 kg/h of propene, with an estimated uncertainty of about 35%. This can be compared to the 2006 emission inventory value for ethene and propene of 145 +/- 4 and 181 +/- 42 kg/h, respectively. On average, for all measurements during the campaign, the discrepancy factor is 10.2(+ 8,-5) for ethene and 11.7(+ 7,-4) for propene. The largest emission source was Mount Belvieu, NE of the Houston Ship Channel, with ethene and propene emissions corresponding to 440 +/- 130 kg/h and 490 +/- 190 kg/h, respectively. Large variability of propene was observed from several petrochemical industries, for which the largest reported emission sources are flares. The SOF alkene emissions agree within 50% with emissions derived from airborne measurements at three different sites. The airborne measurements also provide support to the SOF error budget