Abstract Methane (CH4) is a potent greenhouse gas with high radiative forcing and a relatively short atmospheric lifetime of around a decade. We used a decade‐long data set (2011–2022) from the Fourier transform spectrometer at the California Laboratory for Atmospheric Remote Sensing (CLARS‐FTS) to quantify a dramatic increase in methane observed in 2020. We report a significant acceleration of the short‐term growth rate of 1.37 ± 0.20 ppb/month starting in 2020 until the end of 2021, a substantial increase relative to the near‐zero and negative rates of the preceding 4 years (2016–2019). The observed increase in methane concentrations in 2020 is of significant concern due to its potential contribution to global warming. The Total Carbon Column Observing Network (TCCON) is then used to examine the global geospatial variability of the increase in methane. The results suggest an approximately uniform rise in methane globally. Finally, results from a two‐box model used to simulate atmospheric chemical processes of methane production and loss indicate that changes in OH alone are insufficient to explain the rise in atmospheric methane. Recent data from 2022 suggest a deceleration in the methane growth rate, indicating a potential slowdown in the methane increase observed in 2020.

Abstract. The SWIR module of the TROPOMI instrument on board ESA's Sentinel-5p mission has been very stable during its five years in orbit. Calibration was performed on-ground, complemented by measurements during inflight instrument commissioning. The radiometric response and general performance of the SWIR module are monitored by onboard calibration sources. We show that after five years in orbit, TROPOMI-SWIR has continued to show excellent performance with degradation of at most 0.1 % in transmission and having lost less than 0.3 % of the detector pixels. Independent validation of the instrument calibration, via vicarious calibration, can be done through comparisons with ground-based reflectance data. In this work, measurements at the Railroad Valley Playa are used to perform vicarious calibration of the TROPOMI-SWIR measurements, using both dedicated measurement campaigns, as well as automated reflectance measurements through RADCALNET. As such, TROPOMI-SWIR is an excellent test case to explore the methodology of vicarious calibration applied to infrared spectroscopy. Using methodology developed for the vicarious calibration of the OCO-2 and GOSAT missions, the absolute radiometry of TROPOMI-SWIR performance is independently verified to be stable down to ~ 6–10 % using the Railroad Valley, both on the absolute and, thus, relative radiometric calibration. Differences with the onboard calibration originate from the BRDF effects of the desert surface, the large variety in viewing angles, and the different sizes of footprints of the TROPOMI pixels. However, vicarious calibration is shown to be an additional valuable tool in validating radiance-level performances of infra-red instruments such as TROPOMI-SWIR in the field of atmospheric composition.

Methane, a powerful greenhouse gas, has a short atmospheric lifetime ( ~ 12 years), so that emissions reductions will have a rapid impact on climate forcing. In megacities such as Los Angeles (LA), natural gas (NG) leakage is the primary atmospheric methane source. The magnitudes and trends of fugitive NG emissions are largely unknown and need to be quantified to verify compliance with emission reduction targets. Here we use atmospheric remote sensing data to show that, in contrast to the observed global increase in methane emissions, LA area emissions decreased during 2011-2020 at a mean rate of (–1.57 ± 0.41) %/yr. However, the NG utility calculations indicate a much larger negative emissions trend of −5.8 %/yr. The large difference between top-down and bottom-up trends reflects the uncertainties in estimating the achieved emissions reductions. Actions taken in LA can be a blueprint for COP28 and future efforts to reduce methane emissions.

Precise knowledge of sources and sinks in the carbon cycle is desired to understand its sensitivity to climate change and to account and verify man-made emissions. In this context, extended sources like urban areas play an important role. While in-situ measurements of carbon dioxide (CO2) and methane (CH4) are highly accurate but localized, satellites measure column-integrated concentrations over an extended footprint. The CLARS-FTS [1, 2] stationed at the Mt. Wilson observatory looking downward into the Los Angeles basin has pioneered an innovative measurement technique that fills the sensitivity gap between in-situ and satellite measurements. The technique enables mapping the urban greenhouse gas concentration fields by collecting spectra of ground scattered sunlight and scanning through the region. We develop a similar but portable instrument using a CLARS-FTS-like measurement geometry. It is based on the EM27/SUN FTS with a modified pointing system, increased throughput and a more sensitive detector than the standard type. The compact setup enables campaign-based observations in various source regions of interest, utilizing the increased sensitivity to boundary layer concentration by the horizontal light path component. Here, we present the portable instrument setup and its performance. Throughout April 2022, we observed the Los Angeles basin with both the portable setup and the CLARS-FTS simultaneously. The retrieval algorithm is based on the RemoTeC software, previously employed for solar backscatter satellite measurements. From this, we evaluate the XCO2 and XCH4 precision of our setup under field conditions, and compare our instrument to the concurrent CLARS-FTS measurements. References:[1] Fu, D. et al., 2014: Near-infrared remote sensing of Los Angeles trace gas distributions from a mountaintop site, Atmos. Meas. Tech., 7, 713–729, https://doi.org/10.5194/amt-7-713-2014[2] Wong, K. W. et al., 2015: Mapping CH4 : CO2 ratios in Los Angeles with CLARS-FTS from Mount Wilson, California, Atmos. Chem. Phys., 15, 241–252, https://doi.org/10.5194/acp-15-241-2015

Mapping the greenhouse gases (GHGs) carbon dioxide (CO2) and methane (CH4) above source regions such as urban areas can deliver insights into the distribution and dynamics of local emission patterns. Here, we present the prototype development and an initial performance evaluation of a portable spectrometer that allows for measuring CO2 and CH4 concentrations integrated along a long (>10 km) horizontal path component through the atmospheric boundary layer above a target region. To this end, the spectrometer is positioned at an elevated site from which it points downward at reflection targets in the region, collecting the reflected sunlight at shallow viewing angles. The path-integrated CO2 and CH4 concentrations are inferred from the absorption fingerprint in the shortwave–infrared (SWIR) spectral range. While mimicking the concept of the stationary California Laboratory for Atmospheric Remote Sensing – Fourier Transform Spectrometer (CLARS-FTS) in Los Angeles, our portable setup requires minimal infrastructure and is straightforward to duplicate and to operate in various locations. For performance evaluation, we deployed the instrument, termed EM27/SCA, side by side with the CLARS-FTS at the Mt. Wilson Observatory (1670 m a.s.l.) above Los Angeles for a 1-month period in April/May 2022. We determined the relative precision of the retrieved slant column densities (SCDs) for urban reflection targets to be 0.36 %–0.55 % for O2, CO2 and CH4, where O2 is relevant for light path estimation. For the partial vertical column (VCD) below instrument level, which is the quantity carrying emission information, the propagated precision errors amount to 0.75 %–2 % for the three gases depending on the distance to the reflection target and solar zenith angle. The comparison to simultaneous CLARS-FTS measurements shows good consistency, but the observed diurnal patterns highlight the need to take light scattering into account to enable detection of emission patterns.

Atmospheric isotopologues of water vapor (e.g., HDO) are important tracers for understanding Earth's hydrological cycles. Most remote sensing and in-situ measurements of these isotopologues, however, are either column averaged values or sparse in space and time. Measurements targeting the planetary boundary layer (PBL), the part of the atmosphere that has high sensitivity to surface sources of water vapor isotopologues, are much rarer. In this study, we retrieved HDO and H2O columns from observations by the California Laboratory for Atmospheric Remote Sensing Fourier Transform Spectrometer (CLARS-FTS), a mountaintop observatory on Mt. Wilson (1.67 km a.s.l.) overlooking the Los Angeles (LA) basin in southern California. CLARS-FTS observations are highly sensitive to the lower atmosphere due to the long light path along the PBL. Retrievals were conducted using spectral windows between 6000 and 7000 cm(-1) from CLARS-FTS observations (2011-2019). The isotopological abundance delta(D), which represents the relative difference of the HDO/H2O ratio to a standard abundance ratio, is also calculated. The averaged delta(D) retrievals are (-156.1 +/- 60.0)parts per thousand with an uncertainty of (6.1 +/- 10.2)parts per thousand for LA Basin Survey mode and (-344.7 +/- 95.0)parts per thousand with an uncertainty of (42.4 +/- 31.6)parts per thousand for Spectralon Viewing Observation mode. In LA, the delta(D) shows a seasonal cycle that is primarily driven by the change of atmospheric humidity. A comparison analysis shows that the delta(D) measurements by CLARS-FTS, a collocated Total Carbon Column Observing Network (TCCON), and the TROPOspheric Monitoring Instrument (TROPOMI) are in good agreement. The difference between CLARS and TCCON delta(D) retrievals can primarily be attributed to the difference in their observation geometries. We envision that the HDO and delta(D) measurements from CLARS-FTS provide high spatial and temporal resolution datasets for further study of hydrological processes, such as the partitioning of the water flux into soil evaporation and transpiration, standing water evaporation, or transport and mixing from the oceans, in the LA megacity. (C) 2022 Elsevier Ltd. All rights reserved.

Remote sensing of greenhouse gases (GHGs) in cities, where high GHG emissions are typically associated with heavy aerosol loading, is challenging due to retrieval uncertainties caused by the imperfect characterization of scattering by aerosols. We investigate this problem by developing GFIT3, a full physics algorithm to retrieve GHGs (CO2 and CH4) by accounting for aerosol scattering effects in polluted urban atmospheres. In particular, the algorithm includes coarse- (including sea salt and dust) and fine- (including organic carbon, black carbon, and sulfate) mode aerosols in the radiative transfer model. The performance of GFIT3 is assessed using high-spectral-resolution observations over the Los Angeles (LA) megacity made by the California Laboratory for Atmospheric Remote Sensing Fourier transform spectrometer (CLARS-FTS). CLARS-FTS is located on Mt. Wilson, California, at 1.67 km a.s.l. overlooking the LA Basin, and it makes observations of reflected sunlight in the near-infrared spectral range. The first set of evaluations are performed by conducting retrieval experiments using synthetic spectra. We find that errors in the retrievals of column-averaged dry air mole fractions of CO2 (XCO2) and CH4 (XCH4) due to uncertainties in the aerosol optical properties and atmospheric a priori profiles are less than 1 % on average. This indicates that atmospheric scattering does not induce a large bias in the retrievals when the aerosols are properly characterized. The methodology is then further evaluated by comparing GHG retrievals using GFIT3 with those obtained from the CLARS-GFIT algorithm (used for currently operational CLARS retrievals) that does not account for aerosol scattering. We find a significant correlation between retrieval bias and aerosol optical depth (AOD). A comparison of GFIT3 AOD retrievals with collocated ground-based observations from AErosol RObotic NETwork (AERONET) shows that the developed algorithm produces very accurate results, with biases in AOD estimates of about 0.02. Finally, we assess the uncertainty in the widely used tracer–tracer ratio method to obtain CH4 emissions based on CO2 emissions and find that using the CH4/CO2 ratio effectively cancels out biases due to aerosol scattering. Overall, this study of applying GFIT3 to CLARS-FTS observations improves our understanding of the impact of aerosol scattering on the remote sensing of GHGs in polluted urban atmospheric environments. GHG retrievals from CLARS-FTS are potentially complementary to existing ground-based and spaceborne observations to monitor anthropogenic GHG fluxes in megacities.

Nitrous oxide (N2O) is an important greenhouse gas contributing both to global radiative forcing and ozone depletion. Though N2O emissions are largely derived from agricultural activities, urban sources of N2O also contribute significantly to anthropogenic emissions, but are not well understood and difficult to quantify. This study employs a top-down approach to derive urban N2O emissions for the Los Angeles megacity using a unique dataset from a mountaintop remote sensing instrument, which has been observing greenhouse gas mixing ratios in LA since 2011. CLARS-FTS observations yield a weighted mean of 15.0 ? 0.1 ppb excess XN2O above background in the LA basin from 2013 to 2019. Time series of XN2Oxs show a seasonal cycle with a peak-to-peak amplitude of 5.6 ? 2.5 ppb, where greater XN2Oxs values are observed during the winter/spring and minima occur in late summer/early fall. A tracer-tracer ratio method is applied using XN2Oxs and XCO2,xs observations to estimate top-down N2O emissions for the LA basin during 2013?2018. Estimated monthly emissions range from 6 to 19 Gg N2O per month and exhibit a similar seasonal cycle to that observed in XN2Oxs. Estimated annual emissions fall within the range 124?144 Gg per year for the years 2014?2018. These top-down annual estimates are roughly 3 times the official statewide bottom-up inventory for the same time period, but consistent considering uncertainties with other top-down estimates for the LA basin. The discrepancy between top-down emission estimates and the statewide bottom-up inventory highlights the difficulty in constraining N2O emissions, especially for an urban environment.

A full diurnal measurement of stratospheric column NO2 has been made over the Jet Propulsion Laboratory's Table Mountain Facility (TMF) located in the mountains above Los Angeles, California, USA (2.286 km above mean sea level, 34.38∘ N, 117.68∘ W). During a representative week in October 2018, a grating spectrometer measured the telluric NO2 absorptions in direct solar and lunar spectra. The stratospheric column NO2 is retrieved using a modified minimum-amount Langley extrapolation, which enables us to accurately treat the non-constant NO2 diurnal cycle abundance and the effects of tropospheric pollution near the measurement site. The measured 24 h cycle of stratospheric column NO2 on clean days agrees with a 1-D photochemical model calculation, including the monotonic changes during daytime and nighttime due to the exchange with the N2O5 reservoir and the abrupt changes at sunrise and sunset due to the activation or deactivation of the NO2 photodissociation. The observed daytime NO2 increasing rate is (1.34±0.24)×1014 cm−2 h−1. The observed NO2 in one of the afternoons during the measurement period was much higher than the model simulation, implying the influence of urban pollution from nearby counties. A 24 h back-trajectory analysis shows that the wind first came from inland in the northeast and reached southern Los Angeles before it turned northeast and finally arrived at TMF, allowing it to pick up pollutants from Riverside County, Orange County, and downtown Los Angeles.

Atmospheric isotopologues of water vapor (e.g., HDO) are important tracers for understanding Earth’s hydrological cycles. Most remote sensing measurements of these isotopologues, however, are colum...

Characterization of aerosol vertical distribution in the planetary boundary layer (PBL) using passive remote sensing requires advances in the current state of the art. To quantify the performance of various passive sensor designs within a common framework we developed an aerosol climatology of the Los Angeles basin and applied observing system simulation experiments (OSSEs) to estimate the information content retrievable from a variety of sensors measuring reflected near-infrared solar radiation. In addition to simulating current and planned satellite sensors, we also characterize the sensitivity of the California Laboratory for Atmospheric Remote Sensing - Fourier Transform Spectrometer (CLARS-FTS), located at Mt. Wilson (1.67 km above sea level), which is utilized in this work as a testbed for aerosol profiling remote sensing. We estimate the impacts of spectral coverage, radiance and polarization, spectral resolution, signal to noise ratio (SNR), and number of viewing angles on the information content and retrieval uncertainties of aerosol profiles in the PBL. We found that by adding high spectral resolution (full-width half-maximum of 3 cm(-1) or better), polarimetric measurements with a SNR of at least 212 to radiance measurements with SNR of 300 for both O-2 A and (1)Delta bands, the degrees of freedom for signal (DOFS) of a single CLARS-FTS measurement is raised from 2.1 to 2.8. This improvement is sufficient to simultaneously quantify three key parameters: aerosol optical depth, aerosol peak height, and aerosol layer thickness in the PBL. Current satellite-borne instruments (OCO-2, OCO-3, TEMPO, TROPOMI, and EPIC) and planned instruments (TEMPO, MicroCarb, SPEXone, and MAIA), individually provide a DOFS <= 2.25, which is insufficient to simultaneously quantify all three aerosol profiling parameters in the PBL. Joint radiometric and polarimetric measurements of the O-2 A and B bands with 3 cm(-1) spectral resolution, SNR of 500 for radiance and 353 for polarization, acquired at three viewing angles, can provide sufficient sensitivity to retrieve the three aerosol parameters simultaneously. The inclusion of high spectral resolution radiometric and polarimetric measurements reduces the required number of viewing angles, which is advantageous when the multiangular data are acquired with a pointable instrument. In this case a larger number of viewing angles reduces the spatial coverage that can be achieved for a given target.

The launch of the Visible Infrared Imaging Radiometer Suite (VIIRS) on board the Sumo-NPP satellite in 2011 ushered in a new era of using visible light and shortwave radiation at night to characterize aerosol and fire distributions from space. In order to exploit the full range of unprecedented observational capabilities of VIIRS, we have developed a nighttime shortwave radiative transfer model capability in the UNified and Linearized Radiative Transfer Model (UNL-VRTM). This capability is based on the use of additional source functions to treat illumination from the Moon, from fires, and from artificial lights. We have applied this model to address fundamental questions associated with the VIIRS sensing of aerosol and fire at night. Detailed description of model developments and validation (either directly with surface measurements of lunar spectra or indirectly through cross validation) are presented. Our analysis reveals that: (a) when convolution with the broad-range (500-900 nm) relative spectral response (RSR) function of the VIIRS Day-Night Band (DNB) is omitted, AOD retrieval from the DNB have uncertainties up to a factor of two in conditions with low or moderate AOD (<0.5 in mid-visible); (b) using a wavelength independent spectrum for the surface illumination source can lead to an AOD bias of -10% over surfaces illuminated by light-emitting diodes and fluorescent lamps, and -30% illuminated by high-pressure sodium lamps; and (c) a DNB-equivalent narrow band for AOD retrieval over the surfaces illuminated by the three types of bulbs studied in this paper is found to be centered at 585 nm at which the look-up table can be generated for AOD retrieval from DNB. Furthermore, while uncertainty in AOD retrievals from the DNB decreases as AOD increases, fire characterization can be affected by AOD; for a smoke-scenario AOD of 2.0, the DNB and SWIR (1.6 mu m) radiances can be reduced by 50% depending on the fire area fraction and temperature within VIIRS pixel. DNB is overall more sensitive to smaller and cooler fires than SWIR and can be used to retrieve AOD over bright surfaces. Finally, three-dimensional (3D) radiative transfer effects and the non-collimated nature of most artificial light sources are neglected in this 1D radiative transfer (plane-parallel) model, resulting in possibly large uncertainties (e.g., the inability to reproduce side-illumination of clouds by city lights) that should be studied in future.

Atmospheric carbon monoxide (CO) is an effective tracer for monitoring atmospheric transport processes and for detecting pollution sources of anthropogenic origin. However, very few observation systems exist that are capable of providing measurements with high spatial and temporal resolution to identify hotspots for emission control purposes. Here we introduce a mountain-top remote sensing observatory, the California Laboratory for Atmospheric Remote Sensing (CLARS), for mapping the enhancement of CO column-averaged mixing ratio (XCO) over the Los Angeles (LA) megacity. Compared to conventional observation network, CLARS is unique in the following ways: (1) it mimics a geostationary satellite observatory for LA with approximately hourlyand kilometer-scale mapping capability; (2) the free tropospheric background atmosphere is simultaneously measured; and (3) the measurements are highly sensitive to anthropogenic emissions due to the long light path along the planetary boundary layer (PBL). The CO slant column density and XCO are retrieved from reflected sunlight measurements in the 2.3 mu m CO band and the 1.27 mu m oxygen (O2) band. Data filtering and corrections for aerosol scattering and geometric effects are then implemented to derive the XCO enhancement, which is the XCO excess in the PBL compared to the background value. In the LA megacity, the XCO enhancement shows a distinctive diurnal cycle primarily driven by changes in anthropogenic emissions and sea-breeze circulation. Such diurnal patterns can be reproduced by the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The enhancement also shows a significant weekly cycle resulting from the weekly pattern in anthropogenic CO emissions. On average, the XCO enhancements on Sunday and Saturday are 16.1% and 4.4%, respectively, lower than weekday values. The weekly XCO enhancement patterns also show high correlation with traffic counts. A seasonal pattern of XCO enhancement with high (low) spatial contrast in summer (winter), resulting from changing sea-breeze circulation, can be observed. These diurnal, weekly, and seasonal patterns of XCO enhancement serve as tracers of the atmospheric pulse of the LA megacity. The CLARS observatory can serve as a testbed for future geostationary missions to track anthropogenic emissions in cities.

The angle-dependent scattering effect of aerosols in the atmosphere not only influences climate through radiative forcing effects but also impacts trace gas remote sensing by modifying the path of radiation through the atmosphere. The aerosol phase function, which characterizes the angular signature of scattering, has been continuously monitored from ground-based and space-borne observations. However, the range of scattering angles these instruments can sample is very limited. Here, we report multi-year measurements from a mountain-top remote sensing instrument: the California Laboratory for Atmospheric Remote Sensing Fourier Transform Spectrometer (CLARS-FTS), which overlooks the Los Angeles megacity. The observational geometries of CLARS-FTS provide a wide range of scattering angles, from about 20° (forward) to about 140° (backward), which is larger than the range provided by any existing aerosol remote sensing instrument. We then quantify the aerosol angular scattering effect using the O2 ratio, which is the ratio of retrieved O2 Slant Column Density (SCD) to geometric O2 SCD. The O2 ratio quantifies the light path modification due to aerosol scattering, with a value of 1 representing an aerosol-free scenario. The lower the O2 ratio value than 1, the stronger the aerosol loading. CLARS-FTS measurements are highly sensitive to the angular scattering effect of aerosols in the Los Angeles (LA) urban atmosphere, due to the long light path going through the boundary layer and the wide range of observational angles. The differences in aerosol scattering between different surface reflection points targeted by CLARS-FTS can be explained by differences in their angular scattering geometries. The correlation between measurements at different targets can be used to quantify the strength of the angular dependence of the aerosol phase function. Applying the correlation technique to CLARS-FTS measurements, we find that, from 2011 to 2018, there is no significant trend in the aerosol phase function in the LA megacity. Overall, this study provides a practical observing strategy for quantifying the angular dependence of aerosol scattering in urban atmospheres that could potentially contribute towards improved greenhouse gas remote sensing in megacities.

Absorption of solar radiation by water vapor in the near‐UV region is a poorly understood but important issue in atmospheric science. To better understand water vapor near‐UV absorption, we constructed a cavity ring‐down spectrometer with bandwidth of 5 cm −1 (~0.05 nm) and obtained water vapor absorption cross sections at 1‐nm increments in the 290‐ to 350‐nm region. Water vapor displays structured absorption over this range with maximum and minimum cross sections of 8.4 × 10 −25 and 1.6 × 10 −25 cm 2 /molecule. Major water vapor absorption bands were observed at 293–295, 307–313, 319, 321–322, and 325 nm, with cross‐section values higher than 4.0 × 10 −25 cm 2 /molecule. To obtain further insight into major water vapor absorption bands, we measured water vapor absorption cross sections at 0.05‐nm intervals in the 292‐ to 296‐nm, 306‐ to 314‐nm, and 317‐ to 326‐nm region. Field UV residual spectra not only exhibited increased attenuation at higher atmospheric water vapor loadings but also showed structures suggested by the laboratory water vapor absorption spectrum. Spaceborne UV radiance spectra have spectral structures resembling the differential cross‐section spectrum constructed from the laboratory wavelength‐dependent water vapor absorption cross sections presented here. Incorporating water vapor absorption cross‐section data into a radiative transfer model yielded an estimated energy budget of 0.26 W/m 2 for the standard U.S. atmosphere and 0.76 W/m 2 for the tropics. This shows that water vapor near‐UV absorption is an important contributor for climate simulation and ozone retrievals.