Intimately tracking NO2 pollution over the New York City - Long Island Sound land-water continuum: An integration of shipboard, airborne, satellite observations, and models.

Nitrogen dioxide (NO2) pollution remains a serious global problem, particularly near highly populated urbanized coasts that face increasing challenges with climate change. Yet, the combined impact of urban emissions, pollution transport, and complex meteorology on the spatiotemporal dynamics of NO2 along heterogeneous urban coastlines remains poorly characterized. Here, we integrated measurements from different platforms - boats, ground-based networks, aircraft, and satellites - to characterize total column NO2 (TCNO2) dynamics across the land-water continuum in the New York metropolitan area, the most populous area in the United States that often experiences the highest national NO2 levels. Measurements were conducted during the 2018 Long Island Sound Tropospheric Ozone Study (LISTOS), with a main goal to extend surface measurements beyond the coastline - where ground-based air-quality monitoring networks abruptly stop - and over the aquatic environment where peaks in air pollution often occur. Satellite TCNO2 from TROPOMI correlated strongly with Pandora surface measurements (r = 0.87, N = 100) both over land and water. Yet, TROPOMI overall underestimated TCNO2 (MPD = -12%) and missed peaks in NO2 pollution caused by rush hour emissions or pollution accumulation during sea breezes. Aircraft retrievals were in excellent agreement with Pandora (r = 0.95, MPD = -0.3%, N = 108). Stronger agreement was found between TROPOMI, aircraft, and Pandora over land, while over water satellite, and to a lesser extent aircraft, retrievals underestimated TCNO2 particularly in the highly dynamic New York Harbor environment. Combined with model simulations, our shipborne measurements uniquely captured rapid transitions and fine-scale features in NO2 behavior across the New York City - Long Island Sound land-water continuum, driven by the complex interplay of human activity, chemistry, and local scale meteorology. These novel datasets provide critical information for improving satellite retrievals, enhancing air quality models, and informing management decisions, with important implications for the health of diverse communities and vulnerable ecosystems along this complex urban coastline.

Declines and peaks in NO2 pollution during the multiple waves of the COVID-19 pandemic in the New York metropolitan area.

The COVID-19 pandemic created an extreme natural experiment in which sudden changes in human behavior and economic activity resulted in significant declines in nitrogen oxide (NO x ) emissions, immediately after strict lockdowns were imposed. Here we examined the impact of multiple waves and response phases of the pandemic on nitrogen dioxide (NO2) dynamics and the role of meteorology in shaping relative contributions from different emission sectors to NO2 pollution in post-pandemic New York City. Long term (> 3.5 years), high frequency measurements from a network of ground-based Pandora spectrometers were combined with TROPOMI satellite retrievals, meteorological data, mobility trends, and atmospheric transport model simulations to quantify changes in NO2 across the New York metropolitan area. The stringent lockdown measures after the first pandemic wave resulted in a decline in top-down NO x emissions by approx. 30% on top of long-term trends, in agreement with sector-specific changes in NO x emissions. Ground-based measurements showed a sudden drop in total column NO2 in spring 2020, by up to 36% in Manhattan and 19%-29% in Queens, New Jersey (NJ), and Connecticut (CT), and a clear weakening (by 16%) of the typical weekly NO2 cycle. Extending our analysis to more than a year after the initial lockdown captured a gradual recovery in NO2 across the NY/NJ/CT tri-state area in summer and fall 2020, as social restrictions eased, followed by a second decline in NO2 coincident with the second wave of the pandemic and resurgence of lockdown measures in winter 2021. Meteorology was not found to have a strong NO2 biassing effect in New York City after the first pandemic wave. Winds, however, were favorable for low NO2 conditions in Manhattan during the second wave of the pandemic, resulting in larger column NO2 declines than expected based on changes in transportation emissions alone. Meteorology played a key role in shaping the relative contributions from different emission sectors to NO with low-speed (< 5 ms-1) SW-SE winds enhancing contributions from the high-emitting power-generation sector in NJ and Queens and driving particularly high NO2 pollution episodes in Manhattan, even during - and despite - the stringent early lockdowns. These results have important implications for air quality management in New York City, and highlight the value of high resolution NO2 measurements in assessing the effects of rapid meteorological changes on air quality conditions and the effectiveness of sector-specific NO x emission control strategies.

Volatile chemical product emissions enhance ozone and modulate urban chemistry.

Decades of air quality improvements have substantially reduced the motor vehicle emissions of volatile organic compounds (VOCs). Today, volatile chemical products (VCPs) are responsible for half of the petrochemical VOCs emitted in major urban areas. We show that VCP emissions are ubiquitous in US and European cities and scale with population density. We report significant VCP emissions for New York City (NYC), including a monoterpene flux of 14.7 to 24.4 kg ⋅ d-1 ⋅ km-2 from fragranced VCPs and other anthropogenic sources, which is comparable to that of a summertime forest. Photochemical modeling of an extreme heat event, with ozone well in excess of US standards, illustrates the significant impact of VCPs on air quality. In the most populated regions of NYC, ozone was sensitive to anthropogenic VOCs (AVOCs), even in the presence of biogenic sources. Within this VOC-sensitive regime, AVOCs contributed upwards of ∼20 ppb to maximum 8-h average ozone. VCPs accounted for more than 50% of this total AVOC contribution. Emissions from fragranced VCPs, including personal care and cleaning products, account for at least 50% of the ozone attributed to VCPs. We show that model simulations of ozone depend foremost on the magnitude of VCP emissions and that the addition of oxygenated VCP chemistry impacts simulations of key atmospheric oxidation products. NYC is a case study for developed megacities, and the impacts of VCPs on local ozone are likely similar for other major urban regions across North America or Europe.

Regional characteristics of NO2 column densities from Pandora observations during the MAPS-Seoul campaign.

Vertical column density (VCD) of nitrogen dioxide (NO2) was measured using Pandora spectrometers at six sites on the Korean Peninsula during the Megacity Air Pollution Studies-Seoul (MAPS-Seoul) campaign from May to June 2015. To estimate the tropospheric NO2 VCD, the stratospheric NO2 VCD from the Ozone Monitoring Instrument (OMI) was subtracted from the total NO2 VCD from Pandora. European Centre for Medium-Range Weather Forecasts (ECMWF) reanalysis wind data was used to analyze variations in tropospheric NO2 VCD caused by wind patterns at each site. The Yonsei/SEO site was found to have the largest tropospheric NO2 VCD (1.49 DU on average) from a statistical analysis of hourly tropospheric NO2 VCD measurements. At rural sites, remarkably low NO2 VCDs were observed. However, a wind field analysis showed that trans-boundary transport and emissions from domestic sources lead to an increase in tropospheric NO2 VCD at NIER/BYI and KMA/AMY, respectively. At urban sites, high NO2 VCD values were observed under conditions of low wind speed, which were influenced by local urban emissions. Tropospheric NO2 VCD at HUFS/Yongin increases under conditions of significant transport from urban area of Seoul according to a correlation analysis that considers the transport time lag. Significant diurnal variations were found at urban sites during the MAPS-Seoul campaign, but not at rural sites, indicating that it is associated with diurnal patterns of NO2 emissions from dense traffic.

Comparison of Near-surface NO2 Pollution with Pandora Total Column NO2 during the Korea-United States Ocean Color (KORUS OC) Campaign.

Near-surface air quality (AQ) observations over coastal waters are scarce, a situation that limits our capacity to monitor pollution events at land-water interfaces. Satellite measurements of total column (TC) nitrogen dioxide (NO2) observations are a useful proxy for combustion sources but the once daily snapshots available from most sensors are insufficient for tracking the diurnal evolution and transport of pollution. Ground-based remote sensors like the Pandora Spectrometer Instrument (PSI) that have been developed to verify space-based total column NO2 and other trace gases are being tested for routine use as certified AQ monitors. The KORUS-OC (Korea-United States Ocean Color) cruise aboard the R/V Onnuri in May-June 2016 represented an opportunity to study AQ near the South Korean coast, a region affected by both local/regional and long-distance pollution sources. Using PSI data in direct-sun mode and in situ sensors for shipboard ozone, CO and NO2, we explore, for the first time, relationships between TC NO2 and surface AQ in this coastal region. Three case studies illustrate the value of the PSI as well as complexities in the surface-column NO2 relationship caused by varying meteorological conditions. Case Study 1 (25-26 May 2016) exhibited a high correlation of surface NO2 to TC NO2 measured by both PSI and Aura's Ozone Monitoring Instrument (OMI) but two other cases displayed poor relationships between in situ and TC NO2 due to decoupling of pollution layers from the surface. With suitable interpretation the PSI TC NO2 measurement demonstrates good potential for working with upcoming geostationary satellites to advance diurnal tracking of pollution.

Evaluating the impact of spatial resolution on tropospheric NO2 column comparisons within urban areas using high-resolution airborne data.

NASA deployed the GeoTASO airborne UV-Visible spectrometer in May-June 2017 to produce high resolution (approximately 250 × 250 m) gapless NO2 datasets over the western shore of Lake Michigan and over the Los Angeles Basin. The results collected show that the airborne tropospheric vertical column retrievals compare well with ground-based Pandora spectrometer column NO2 observations (r2=0.91 and slope of 1.03). Apparent disagreements between the two measurements can be sensitive to the coincidence criteria and are often associated with large local variability, including rapid temporal changes and spatial heterogeneity that may be observed differently by the sunward viewing Pandora observations. The gapless mapping strategy executed during the 2017 GeoTASO flights provides data suitable for averaging to coarser areal resolutions to simulate satellite retrievals. As simulated satellite pixel area increases to values typical of TEMPO, TROPOMI, and OMI, the agreement with Pandora measurements degraded, particularly for the most polluted columns as localized large pollution enhancements observed by Pandora and GeoTASO are spatially averaged with nearby less-polluted locations within the larger area representative of the satellite spatial resolutions (aircraft-to-Pandora slope: TEMPO scale=0.88; TROPOMI scale=0.77; OMI scale=0.57). In these two regions, Pandora and TEMPO or TROPOMI have the potential to compare well at least up to pollution scales of 30×1015 molecules cm-2. Two publicly available OMI tropospheric NO2 retrievals are both found to be biased low with respect to these Pandora observations. However, the agreement improves when higher resolution a priori inputs are used for the tropospheric air mass factor calculation (NASA V3 Standard Product slope = 0.18 and Berkeley High Resolution Product slope=0.30). Overall, this work explores best practices for satellite validation strategies with Pandora direct-sun observations by showing the sensitivity to product spatial resolution and demonstrating how the high spatial resolution NO2 data retrieved from airborne spectrometers, such as GeoTASO, can be used with high temporal resolution ground-based column observations to evaluate the influence of spatial heterogeneity on validation results.

The first evaluation of formaldehyde column observations by improved Pandora spectrometers during the KORUS-AQ field study.

The Korea-United States Air Quality Study (KORUS-AQ) conducted during May-June 2016 offered the first opportunity to evaluate direct-sun observations of formaldehyde (HCHO) total column densities with improved Pandora spectrometer instruments. The measurements highlighted in this work were conducted both in the Seoul megacity area at the Olympic Park site (37.5232° N, 27.1260° E; 26 ma.s.l.) and at a nearby rural site downwind of the city at the Mount Taehwa research forest site (37.3123° N, 127.3106° E; 160ma.s.l.). Evaluation of these measurements was made possible by concurrent ground-based in situ observations of HCHO at both sites as well as overflight by the NASA DC-8 research aircraft. The flights provided in situ measurements of HCHO to characterize its vertical distribution in the lower troposphere (0-5km). Diurnal variation in HCHO total column densities followed the same pattern at both sites, with the minimum daily values typically observed between 6:00 and 7:00 local time, gradually increasing to a maximum between 13:00 and 17:00 before decreasing into the evening. Pandora vertical column densities were compared with those derived from the DC-8 HCHO in situ measured profiles augmented with in situ surface concentrations below the lowest altitude of the DC-8 in proximity to the ground sites. A comparison between 49 column densities measured by Pandora vs. aircraft-integrated in situ data showed that Pandora values were larger by 16% with a constant offset of 0.22DU (Dobson units; R 2 = 0.68). Pandora HCHO columns were also compared with columns calculated from the surface in situ measurements over Olympic Park by assuming a well-mixed lower atmosphere up to a ceilometer-measured mixed-layer height (MLH) and various assumptions about the small residual HCHO amounts in the free troposphere up to the tropopause. The best comparison (slope = 1.03±0.03; intercept = 0.29±0.02DU; and R 2 = 0.78±0.02) was achieved assuming equal mixing within ceilometer-measured MLH combined with an exponential profile shape. These results suggest that diurnal changes in HCHO surface concentrations can be reasonably estimated from the Pandora total column and information on the mixed-layer height. More work is needed to understand the bias in the intercept and the slope relative to columns derived from the in situ aircraft and surface measurements.

Effects of local meteorology and aerosols on ozone and nitrogen dioxide retrievals from OMI and pandora spectrometers in Maryland, USA during DISCOVER-AQ 2011.

An analysis is presented for both ground- and satellite-based retrievals of total column ozone and nitrogen dioxide levels from the Washington, D.C., and Baltimore, Maryland, metropolitan area during the NASA-sponsored July 2011 campaign of Deriving Information on Surface COnditions from Column and VERtically Resolved Observations Relevant to Air Quality (DISCOVER-AQ). Satellite retrievals of total column ozone and nitrogen dioxide from the Ozone Monitoring Instrument (OMI) on the Aura satellite are used, while Pandora spectrometers provide total column ozone and nitrogen dioxide amounts from the ground. We found that OMI and Pandora agree well (residuals within ±25 % for nitrogen dioxide, and ±4.5 % for ozone) for a majority of coincident observations during July 2011. Comparisons with surface nitrogen dioxide from a Teledyne API 200 EU NOx Analyzer showed nitrogen dioxide diurnal variability that was consistent with measurements by Pandora. However, the wide OMI field of view, clouds, and aerosols affected retrievals on certain days, resulting in differences between Pandora and OMI of up to ±65 % for total column nitrogen dioxide, and ±23 % for total column ozone. As expected, significant cloud cover (cloud fraction >0.2) was the most important parameter affecting comparisons of ozone retrievals; however, small, passing cumulus clouds that do not coincide with a high (>0.2) cloud fraction, or low aerosol layers which cause significant backscatter near the ground affected the comparisons of total column nitrogen dioxide retrievals. Our results will impact post-processing satellite retrieval algorithms and quality control procedures.