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In this study, we demonstrate the utility of available correlative measurements of carbon species to identify regional and local air mass characteristics as well as their associated source types. In particular, we combine different regression techniques and enhancement ratio algorithms with carbon monoxide (CO), carbon dioxide (CO 2), and methane (CH 4) total column abundance from 11 sites of the Total Carbon Column Observing Network (TCCON) to infer relative contributions of regional and local sources to each of these sites. The enhancement ratios provide a viable alternative to univariate measures of relationships between the trace gases that are insufficient in capturing source-type and transport signatures. Regional enhancements are estimated from the difference between bivariate regressions across a specific time window of observed total abundance of these species (BERr for bulk enhancement regression ratio) and inferred anomalies (AERr for anomaly enhancement regression ratio) associated with a site-specific background. Since BERr and AERr represent the bulk and local species enhancement ratio, respectively, its difference simply represents the site-specific regional component of these ratios. We can then compare these enhancements for CO 2 and CH 4 with CO to differentiate between combustion and non-combustion air masses. Our results show that while the regional and local influences in enhancements vary across sites, dominant characteristics are found to be consistent with previous studies over these sites and with bottom-up anthropogenic and fire emission inventories. The site in Pasadena shows a dominant local influence (> 60 %) across all species enhancement ratios, which appear to come from a mixture of biospheric and combustion activities. In contrast, Anmyeondo shows more regionally influenced (> 60 %) air masses associated with high-temperature and/or biofuel combustion activities. Ascension Island appears to only show a large regional influence (> 80 %) on CO / CO 2 and CO / CH 4 , which is indicative of transported and combustion-related CO from the nearby African region, consistent with a sharp rise in column CO (3.51 ± 0.43 % ppb yr -1) at this site. These methods have important applications to source analysis using spaceborne column retrievals of these species. [ABSTRACT FROM AUTHOR]

Atmospheric mercury (Hg) observations in the lower free troposphere (LFT) can give important insights into Hg redox chemistry and can help constrain Hg background concentrations on a regional level. Relatively continuous sampling of LFT air, inaccessible to most ground-based stations, can be achieved at high-altitude observatories. However, such high-altitude observatories are rare, especially in the Southern Hemisphere (SH), and atmospheric Hg in the SH LFT is unconstrained. To fill this gap, we continuously measured gaseous elemental mercury (GEM; hourly) and reactive mercury (RM; integrated over ∼ 6–14 d) for 9 months at Maïdo mountain observatory (2160 m a.s.l.) on remote Réunion Island (21.1 ∘ S, 55.5 ∘ E) in the tropical Indian Ocean. GEM exhibits a marked diurnal variation characterized by a midday peak (mean: 0.95 ng m -3 ; SD: 0.08 ng m -3) and a nighttime low (mean: 0.78 ng m -3 ; SD: 0.11 ng m -3). We find that this diurnal variation is likely driven by the interplay of important GEM photo-reemission from the islands' vegetated surfaces (i.e. vegetation + soil) during daylight hours (8–22 ng m -2 h -1), boundary layer influences during the day, and predominant LFT influences at night. We estimate GEM in the LFT based on nighttime observations in particularly dry air masses and find a notable seasonal variation, with LFT GEM being lowest from December to March (mean 0.66 ng m -3 ; SD: 0.07 ng m -3) and highest from September to November (mean: 0.79 ng m -3 ; SD: 0.09 ng m -3). Such a clear GEM seasonality contrasts with the weak seasonal variation reported for the SH marine boundary layer but is in line with modeling results, highlighting the added value of continuous Hg observations in the LFT. Maïdo RM is 10.6 pg m -3 (SD: 5.9 pg m -3) on average, but RM in the cloud-free LFT might be about twice as high, as weekly–biweekly sampled RM observations are likely diluted by low-RM contributions from the boundary layer and clouds. [ABSTRACT FROM AUTHOR]

This proof‐of‐concept study demonstrates that methane (CH4) emissions from natural gas (NG) and agriculture can be disentangled using the concept of excess column observations. A network of cost‐effective sensors measured excess column‐averaged dry‐air mole fractions for CH4 (ΔXCH4), ethane (ΔXC2H6 as NG tracer), and ammonia (ΔXNH3 from agriculture) in the Denver‐Julesburg Basin during March 2015. ΔXCH4 varied up to 17 ppb and was >3 times higher with winds from directions where NG is produced. The ΔXCH4 variance is explained by variations in the C2H6‐NH3 tracer pair, attributing 63 ± 17% to NG, 25 ± 10% to agriculture, and 12 ± 12% to other sources. The ratios ΔXC2H6/ΔXCH4 (16 ± 2%; indicates wet NG) and ΔXNH3/ΔXCH4 (43 ± 12%) were compatible with in situ measured ratios. Excess columns are independent of boundary layer height, characterize gases in the open atmosphere, are inherently calibrated, average over extended spatial scales, and provide a complementary perspective to quantify and attribute CH4 emissions on regional scales. Plain Language Summary: Methane is the second most important anthropogenic greenhouse gas. Knowledge about methane sources is increasingly relevant as energy production continues to shift toward natural gas and becomes complicated by collocated emissions from natural gas production and agriculture due to shared land use. There is a need for methods to better decouple emissions from multiple sources that contribute to local enhancements in methane, which are small compared to the regional methane background concentrations, and depend on atmospheric transport and planetary boundary layer height. In this study, we show that the concept of collocated excess column measurements of methane and chemical tracers shows great promise as a viable approach to disentangle methane emissions from multiple sources by means of cost‐effective networks of ground‐based sensors. Excess columns are independent of boundary layer height, which makes quantification and source attribution of methane more straightforward. Key Points: Methane emissions from natural gas and agriculture can be separated using the concept of excess column measurements of source tracersColumn integrals over boundary layer height are complementary to in situ methods and useful to quantify and source apportion methane on regional scalesNatural gas sources dominate over agricultural and other sources, but the latter are relatively more important when excess CH4 is smaller than 5 ppb [ABSTRACT FROM AUTHOR]

In a 3.5-year long study, the long-term performance of a mobile, solar absorption Bruker EM27/SUN spectrometer, used for greenhouse gas observations, is checked with respect to a co-located reference Bruker IFS 125HR spectrometer, which is part of the Total Carbon Column Observing Network (TCCON). We find that the EM27/SUN is stable on timescales of several years; the drift per year between the EM27/SUN and the official TCCON product is 0.02 ppmv for X CO2 and 0.9 ppbv for X CH4 , which is within the 1 σ precision of the comparison, 0.6 ppmv for X CO2 and 4.3 ppbv for X CH4. The bias between the two data sets is 3.9 ppmv for X CO2 and 13.0 ppbv for X CH4. In order to avoid sensitivity-dependent artifacts, the EM27/SUN is also compared to a truncated IFS 125HR data set derived from full-resolution TCCON interferograms. The drift is 0.02 ppmv for X CO2 and 0.2 ppbv for X CH4 per year, with 1 σ precisions of 0.4 ppmv for X CO2 and 1.4 ppbv for X CH4 , respectively. The bias between the two data sets is 0.6 ppmv for X CO2 and 0.5 ppbv for X CH4. With the presented long-term stability, the EM27/SUN qualifies as an useful supplement to the existing TCCON network in remote areas. To achieve consistent performance, such an extension requires careful testing of any spectrometers involved by application of common quality assurance measures. One major aim of the COllaborative Carbon Column Observing Network (COCCON) infrastructure is to provide these services to all EM27/SUN operators. In the framework of COCCON development, the performance of an ensemble of 30 EM27/SUN spectrometers was tested and found to be very uniform, enhanced by the centralized inspection performed at the Karlsruhe Institute of Technology prior to deployment. Taking into account measured instrumental line shape parameters for each spectrometer, the resulting average bias across the ensemble with respect to the reference EM27/SUN used in the long-term study in X CO2 is 0.20 ppmv, while it is 0.8 ppbv for X CH4. The average standard deviation of the ensemble is 0.13 ppmv for X CO2 and 0.6 ppbv for X CH4. In addition to the robust metric based on absolute differences, we calculate the standard deviation among the empirical calibration factors. The resulting 2 σ uncertainty is 0.6 ppmv for X CO2 and 2.2 ppbv for X CH4. As indicated by the executed long-term study on one device presented here, the remaining empirical calibration factor deduced for each individual instrument can be assumed constant over time. Therefore the application of these empirical factors is expected to further improve the EM27/SUN network conformity beyond the scatter among the empirical calibration factors reported above. [ABSTRACT FROM AUTHOR]

NASA's Orbiting Carbon Observatory-2 (OCO-2) has been measuring carbon dioxide column-averaged dryair mole fraction, XCO2 , in the Earth's atmosphere for over 2 years. In this paper, we describe the comparisons between the first major release of the OCO-2 retrieval algorithm (B7r) and XCO2 from OCO-2's primary ground-based validation network: the Total Carbon Column Observing Network (TCCON). The OCO-2 XCO2 retrievals, after filtering and bias correction, agree well when aggregated around and coincident with TCCON data in nadir, glint, and target observation modes, with absolute median differences less than 0.4 ppm and RMS differences less than 1.5 ppm. After bias correction, residual biases remain. These biases appear to depend on latitude, surface properties, and scattering by aerosols. It is thus crucial to continue measurement comparisons with TCCON to monitor and evaluate the OCO-2 XCO2 data quality throughout its mission. [ABSTRACT FROM AUTHOR]