A Gradient-Descent Optimization of CO2-CO-NOx Emissions over the Paris Megacity─The Case of the First SARS-CoV-2 Lockdown.

Urban greenhouse gas emissions monitoring is essential to assessing the impact of climate mitigation actions. Using atmospheric continuous measurements of air quality and carbon dioxide (CO2), we developed a gradient-descent optimization system to estimate emissions of the city of Paris. We evaluated our joint CO2-CO-NOx optimization over the first SARS-CoV-2 related lockdown period, resulting in a decrease in emissions by 40% for NOx and 30% for CO2, in agreement with preliminary estimates using bottom-up activity data yet lower than the decrease estimates from Bayesian atmospheric inversions (50%). Before evaluating the model, we first provide an in-depth analysis of three emission data sets. A general agreement in the totals is observed over the region surrounding Paris (known as Île-de-France) since all the data sets are constrained by the reported national and regional totals. However, the data sets show disagreements in their sector distributions as well as in the interspecies ratios. The seasonality also shows disagreements among emission products related to nonindustrial stationary combustion (residential and tertiary combustion). The results presented in this paper show that a multispecies approach has the potential to provide sectoral information to monitor CO2 emissions over urban areas enabled by the deployment of collocated atmospheric greenhouse gases and air quality monitoring stations.

Temperature extremes of 2022 reduced carbon uptake by forests in Europe.

The year 2022 saw record breaking temperatures in Europe during both summer and fall. Similar to the recent 2018 drought, close to 30% (3.0 million km2) of the European continent was under severe summer drought. In 2022, the drought was located in central and southeastern Europe, contrasting the Northern-centered 2018 drought. We show, using multiple sets of observations, a reduction of net biospheric carbon uptake in summer (56-62 TgC) over the drought area. Specific sites in France even showed a widespread summertime carbon release by forests, additional to wildfires. Partial compensation (32%) for the decreased carbon uptake due to drought was offered by a warm autumn with prolonged biospheric carbon uptake. The severity of this second drought event in 5 years suggests drought-induced reduced carbon uptake to no longer be exceptional, and important to factor into Europe's developing plans for net-zero greenhouse gas emissions that rely on carbon uptake by forests.

Seven-year monitoring of mercury in wet precipitation and atmosphere at the Amsterdam Island GMOS station.

Mercury (Hg) fate and transport research requires more effort to obtain a deep knowledge of its biogeochemical cycle, particularly in the Southern Hemisphere and Tropics that are still missing of distributed monitoring sites. Continuous monitoring of atmospheric Hg concentrations and trend worldwide is relevant for the effectiveness evaluation of the Minamata Convention on Mercury (MCM) actions. In this context, Gaseous Elemental Mercury (GEM) and total mercury (THg) in precipitations were monitored from 2013 to 2019 at the Amsterdam Island Observatory (AMS - 37°48'S, 77°34'E) to provide insights into the Hg pathway in the remote southern Indian Ocean, also considering ancillary dataset of Rn-222, CO2, CO, and CH4. GEM average concentration was 1.06 ± 0.07 ng m-3, with a slight increase during the austral winter due to both higher wind speed over the surface ocean and contributions from southern Africa. In wet depositions, THg average concentration was 2.39 ± 1.17 ng L-1, whereas the annual flux averaged 2.04 ± 0.80 µg m-2 year-1. In general, both GEM and Volume-Weighted Mean Concentration (VWMC) of THg did not show an increasing/decreasing trend over the seven-year period, suggesting a substantial lack of evolution about emission of Hg reaching AMS. Air masses Cluster Analysis and Potential Source Contribution Function showed that oceanic evasion was the main Hg contributor at AMS, while further contributions were attributable to long-range transport events from southern Africa, particularly when the occurrence of El Niño increased the frequency of wildfires.

A twenty year record of greenhouse gases in the Eastern Mediterranean atmosphere.

Twenty years of CO2, CH4 and CO greenhouse gas atmospheric concentration measurements at Finokalia station on Crete in the Eastern Mediterranean region are presented. This dataset is the longest in the Eastern Mediterranean, based on bi-weekly grab sampling since 2002 and continuous observations since June 2014. CO2 concentrations increase by 2.4 ppm·y-1 since 2002, in agreement with the general north hemisphere trend as derived by worldwide NOAA observations. CH4 showed a mean increasing trend of 7.5 ppb·y-1 since 2002, a rate that has accelerated since 2018 (12.4 ppb·y-1). In contrast, CO has decreased by 1.6 ppb·y-1 since 2002, which resulted from a strong decrease until 2017 (2.5 ppb·y-1), followed by a small increase in the last 3 years (0.2 ppb·y-1). Both CO2 and CH4 present maxima during winter and minima during summer, in general agreement with the observations at the ICOS stations in Europe. CO also presents the highest values in winter and the lowest values in summer during June, while a secondary maximum is seen in August, which can be attributed to open fires that often occur in the area during this period. The mean summertime diurnal cycles of CH4 and CO agree with a 24-h mean OH radical concentration of the order of 0.3-1 × 107 molecules·cm-3 over the region, in general agreement with the only existing in-situ observations at Finokalia for 2001.

Wetland emission and atmospheric sink changes explain methane growth in 2020.

Atmospheric methane growth reached an exceptionally high rate of 15.1 ± 0.4 parts per billion per year in 2020 despite a probable decrease in anthropogenic methane emissions during COVID-19 lockdowns1. Here we quantify changes in methane sources and in its atmospheric sink in 2020 compared with 2019. We find that, globally, total anthropogenic emissions decreased by 1.2 ± 0.1 teragrams of methane per year (Tg CH4 yr-1), fire emissions decreased by 6.5 ± 0.1 Tg CH4 yr-1 and wetland emissions increased by 6.0 ± 2.3 Tg CH4 yr-1. Tropospheric OH concentration decreased by 1.6 ± 0.2 per cent relative to 2019, mainly as a result of lower anthropogenic nitrogen oxide (NOx) emissions and associated lower free tropospheric ozone during pandemic lockdowns2. From atmospheric inversions, we also infer that global net emissions increased by 6.9 ± 2.1 Tg CH4 yr-1 in 2020 relative to 2019, and global methane removal from reaction with OH decreased by 7.5 ± 0.8 Tg CH4 yr-1. Therefore, we attribute the methane growth rate anomaly in 2020 relative to 2019 to lower OH sink (53 ± 10 per cent) and higher natural emissions (47 ± 16 per cent), mostly from wetlands. In line with previous findings3,4, our results imply that wetland methane emissions are sensitive to a warmer and wetter climate and could act as a positive feedback mechanism in the future. Our study also suggests that nitrogen oxide emission trends need to be taken into account when implementing the global anthropogenic methane emissions reduction pledge5.

Simultaneous Monitoring of Atmospheric CH4, N2O, and H2O Using a Single Gas Sensor Based on Mid-IR Quartz-Enhanced Photoacoustic Spectroscopy.

An optical sensor based on external-cavity quantum cascade laser (EC-QCL) was developed for simultaneous triple-species monitoring of CH4, N2O, and H2O vapor using off-beam quartz-enhanced photoacoustic spectroscopy (OB-QEPAS). The EC-QCL wavelength was scanned over three neighboring absorption lines of CH4 (1260.81 cm-1), N2O (1261.06 cm-1), and H2O vapor (1261.58 cm-1) by tuning the grating of the EC-QCL with a piezoelectric actuator. Molecular relaxation effects impacting the generation of the QEPAS signals resulting from light absorption by CH4 and N2O molecules were investigated in the mid-infrared region near 8 µm. A theoretical model was introduced for the mid-infrared region, including the beneficial influence of water vapor. An enhancement of the QEPAS signals by a factor of 3 for CH4 in air and of 20% for N2O in air was observed in humidified samples compared to that in dry samples. The QEPAS measurement was scaled by the calibrated reference spectrometers; detection limits of 98 ppbv for CH4, 12 ppbv for N2O, and 750 ppmv for H2O vapor were obtained with a 1σ signal-to-noise ratio (SNR = 1) in humidified gas mixtures. Real-time Kalman filtering was applied to improve the measurement precision by a factor of approximately 4 while keeping the same temporal resolution, leading to measurement precisions of 60 ppbv for CH4, 10 ppbv for N2O, and 0.07% for H2O in the measurements of 1.99 ppmv CH4 and 312 ppbv N2O humidified with 2.8% H2O vapor, with a 1 s lock-in amplifier time constant and an equivalent bandwidth of 0.1 Hz.

Carbonyl sulfide (COS) emissions in two agroecosystems in central France.

Carbonyl sulfide (COS) fluxes simulated by vegetation and soil component models, both implemented in the ORCHIDEE land surface model, were evaluated against field observations at two agroecosystems in central France. The dynamics of a biogenic process not yet accounted for by this model, i.e., COS emissions from croplands, was examined in the context of three independent and complementary approaches. First, during the growing seasons of 2019 and 2020, monthly variations in the nighttime ratio of vertical mole fraction gradients of COS and carbon dioxide measured between 5 and 180 m height (GradCOS/GradCO2), a proxy of the ratio of their respective nocturnal net fluxes, were monitored at a rural tall tower site near Orléans (i.e., a "profile vs. model" approach). Second, field observations of COS nocturnal fluxes, obtained by the Radon Tracer Method (RTM) at a sub-urban site near Paris, were used for that same purpose (i.e., a "RTM vs. model" approach of unaccounted biogenic emissions). This site has observations going back to 2014. Third, during the growing seasons of 2019, 2020 and 2021, horizontal mole fraction gradients of COS were calculated from downwind-upwind surveys of wheat and rapeseed crops as a proxy of their respective exchange rates at the plot scale (i.e., a "crop based" comparative approach). The "profile vs. model" approach suggests that the nocturnal net COS uptake gradually weakens during the peak growing season and recovers from August on. The "RTM vs. model" approach suggests that there exists a biogenic source of COS, the intensity of which culminates in late June early July. Our "crop based" comparative approach demonstrates that rapeseed crops shift from COS uptake to emission in early summer during the late stages of growth (ripening and senescence) while wheat crops uptake capacities lower markedly. Hence, rapeseed appears to be a much larger source of COS than wheat at the plot scale. Nevertheless, compared to current estimates of the largest COS sources (i.e., marine and anthropogenic emissions), agricultural emissions during the late stages of growth are of secondary importance.

Assessing the Effectiveness of an Urban CO2 Monitoring Network over the Paris Region through the COVID-19 Lockdown Natural Experiment.

The Paris metropolitan area, the largest urban region in the European Union, has experienced two national COVID-19 confinements in 2020 with different levels of restrictions on mobility and economic activity, which caused reductions in CO2 emissions. To quantify the timing and magnitude of daily emission reductions during the two lockdowns, we used continuous atmospheric CO2 monitoring, a new high-resolution near-real-time emission inventory, and an atmospheric Bayesian inverse model. The atmospheric inversion estimated the changes in fossil fuel CO2 emissions over the Greater Paris region during the two lockdowns, in comparison with the same periods in 2018 and 2019. It shows decreases by 42-53% during the first lockdown with stringent measures and by only 20% during the second lockdown when traffic reduction was weaker. Both lockdown emission reductions are mainly due to decreases in traffic. These results are consistent with independent estimates based on activity data made by the city environmental agency. We also show that unusual persistent anticyclonic weather patterns with north-easterly winds that prevailed at the start of the first lockdown period contributed a substantial drop in measured CO2 concentration enhancements over Paris, superimposed on the reduction of urban CO2 emissions. We conclude that atmospheric CO2 monitoring makes it possible to identify significant emission changes (>20%) at subannual time scales over an urban region.

Strong Southern Ocean carbon uptake evident in airborne observations.

The Southern Ocean plays an important role in determining atmospheric carbon dioxide (CO2), yet estimates of air-sea CO2 flux for the region diverge widely. In this study, we constrained Southern Ocean air-sea CO2 exchange by relating fluxes to horizontal and vertical CO2 gradients in atmospheric transport models and applying atmospheric observations of these gradients to estimate fluxes. Aircraft-based measurements of the vertical atmospheric CO2 gradient provide robust flux constraints. We found an annual mean flux of ­0.53 ± 0.23 petagrams of carbon per year (net uptake) south of 45°S during the period 2009­2018. This is consistent with the mean of atmospheric inversion estimates and surface-ocean partial pressure of CO2 (Pco2)­based products, but our data indicate stronger annual mean uptake than suggested by recent interpretations of profiling float observations.

Spring enhancement and summer reduction in carbon uptake during the 2018 drought in northwestern Europe.

We analysed gross primary productivity (GPP), total ecosystem respiration (TER) and the resulting net ecosystem exchange (NEE) of carbon dioxide (CO2) by the terrestrial biosphere during the summer of 2018 through observed changes across the Integrated Carbon Observation System (ICOS) network, through biosphere and inverse modelling, and through remote sensing. Highly correlated yet independently-derived reductions in productivity from sun-induced fluorescence, vegetative near-infrared reflectance, and GPP simulated by the Simple Biosphere model version 4 (SiB4) suggest a 130-340 TgC GPP reduction in July-August-September (JAS) of 2018. This occurs over an area of 1.6 × 106 km2 with anomalously low precipitation in northwestern and central Europe. In this drought-affected area, reduced GPP, TER, NEE and soil moisture at ICOS ecosystem sites are reproduced satisfactorily by the SiB4 model. We found that, in contrast to the preceding 5 years, low soil moisture is the main stress factor across the affected area. SiB4's NEE reduction by 57 TgC for JAS coincides with anomalously high atmospheric CO2 observations in 2018, and this is closely matched by the NEE anomaly derived by CarbonTracker Europe (52 to 83 TgC). Increased NEE during the spring (May-June) of 2018 (SiB4 -52 TgC; CTE -46 to -55 TgC) largely offset this loss, as ecosystems took advantage of favourable growth conditions. This article is part of the theme issue 'Impacts of the 2018 severe drought and heatwave in Europe: from site to continental scale'.

A top-down approach of sources and non-photosynthetic sinks of carbonyl sulfide from atmospheric measurements over multiple years in the Paris region (France).

Carbonyl sulfide (COS) has been proposed as a proxy for carbon dioxide (CO2) taken up by plants at the leaf and ecosystem scales. However, several additional production and removal processes have been identified which could complicate its use at larger scales, among which are soil uptake, dark uptake by plants, and soil and anthropogenic emissions. This study evaluates the significance of these processes at the regional scale through a top-down approach based on atmospheric COS measurements at Gif-sur-Yvette (GIF), a suburban site near Paris (France). Over a period of four and a half years, hourly measurements at 7 m above ground level were performed by gas chromatography and combined with 222Radon measurements to calculate nocturnal COS fluxes using the Radon-Tracer Method. In addition, the vertical distribution of COS was investigated at a second site, 2 km away from GIF, where a fast gas analyzer deployed on a 100 m tower for several months during winter 2015-2016 recorded mixing ratios at 3 heights (15, 60 and 100 m). COS appears to be homogeneously distributed both horizontally and vertically in the sampling area. The main finding is that the area is a persistent COS sink even during wintertime episodes of strong pollution. Nighttime net uptake rates ranged from -1.5 to -32.8 pmol m-2 s-1, with an average of -7.3 ± 4.5 pmol m-2 s-1 (n = 253). However, episodes of biogenic emissions happened each year in June-July (11.9 ± 6.2 pmol m-2 s-1, n = 24). Preliminary analyses of simulated footprints of source areas influencing the recorded COS data suggest that long-range transport of COS from anthropogenic sources located in Benelux, Eastern France and Germany occasionally impacts the Paris area during wintertime. These production and removal processes may limit the use of COS to assess regional-scale CO2 uptake in Europe by plants through inverse modeling.

Hydrogeological control on carbon dioxide input into the atmosphere of the Chauvet-Pont d'Arc cave.

Carbon dioxide (CO2) concentration (CDC) is an essential parameter of underground atmospheres for safety and cave heritage preservation. In the Chauvet cave (South France), a world heritage site hosting unique paintings dated 36,000 years BP, a high-sensitivity monitoring, ongoing since 1997, revealed: 1) two compartments with a spatially uniform CDC, a large volume (A) (40,000 to 80,000 m3) with a mean value of 2.20 ± 0.01% vol. in 2016, and a smaller remote room (B) (2000 m3), with a higher mean value of 3.42 ± 0.01%; 2) large CDC annual variations with peak-to-peak amplitude of 2% and 1.6% in A and B, respectively; 3) long-term changes, with an increase of CDC and of its annual amplitude since 1997, then faster since 2013, reaching a maximum of 4.4% in B in 2017, decreasing afterwards. While a large effect of seasonal ventilation is ruled out, monitoring of seepage at two dripping points indicated that the main control of CDC seasonal reduction was transient infiltration. During periods of water deficit, calculated from surface temperature and rainfall, CDC systematically increased. The carbon isotopic composition of CO2, correlated with water excess, is consistent with a time-varying component of CO2 seeping from above. The CO2 flux, which is the primary driver of CDC in A and B, inferred using box modelling, was found to confirm the relationship between water excess and reduced CO2 flux into A, compatible with a more constant flux into B. A buoyancy-driven horizontal CO2 flow model in the vadose zone, hindered by water infiltration, is proposed. Similarly, pluri-annual and long-term CDC changes can likely be attributed to variations of water excess, but also to increasing vegetation density above the cave. As CDC controls the carbonate geochemistry, an increased variability of CDC raises concern for the preservation of the Chauvet cave paintings.

Inter-comparison of 2 microm Heterodyne Differential Absorption Lidar, Laser Diode Spectrometer, LICOR NDIR analyzer and flasks measurements of near-ground atmospheric CO2 mixing ratio.

Remote sensing and in situ instruments are presented and compared in the same location for accurate CO(2) mixing ratio measurements in the atmosphere: (1) a 2.064 microm Heterodyne DIfferential Absorption Lidar (HDIAL), (2) a field deployable infrared Laser Diode Spectrometer (LDS) using new commercial diode laser technology at 2.68 microm, (3) LICOR NDIR analyzer and (4) flasks. LDS, LICOR and flasks measurements were made in the same location, LICOR and flasks being taken as reference. Horizontal HDIAL measurements of CO(2) absorption using aerosol backscatter signal are reported. Using new spectroscopic data in the 2 microm band and meteorological sensor measurements, a mean CO(2) mixing ratio is inferred by the HDIAL in a 1 km long path above the 15m height location of the CO(2) in situ sensors. We compare HDIAL and LDS measurements with the LICOR data for 30 min of time averaging. The mean standard deviation of the HDIAL and the LDS CO(2) mixing ratio results are 3.3 ppm and 0.89 ppm, respectively. The bias of the HDIAL and the LDS measurements are -0.54 ppm and -0.99 ppm, respectively.

Weak northern and strong tropical land carbon uptake from vertical profiles of atmospheric CO2.

Measurements of midday vertical atmospheric CO2 distributions reveal annual-mean vertical CO2 gradients that are inconsistent with atmospheric models that estimate a large transfer of terrestrial carbon from tropical to northern latitudes. The three models that most closely reproduce the observed annual-mean vertical CO2 gradients estimate weaker northern uptake of -1.5 petagrams of carbon per year (Pg C year(-1)) and weaker tropical emission of +0.1 Pg C year(-1) compared with previous consensus estimates of -2.4 and +1.8 Pg C year(-1), respectively. This suggests that northern terrestrial uptake of industrial CO2 emissions plays a smaller role than previously thought and that, after subtracting land-use emissions, tropical ecosystems may currently be strong sinks for CO2.

Saturation of the southern ocean CO2 sink due to recent climate change.

Based on observed atmospheric carbon dioxide (CO2) concentration and an inverse method, we estimate that the Southern Ocean sink of CO2 has weakened between 1981 and 2004 by 0.08 petagrams of carbon per year per decade relative to the trend expected from the large increase in atmospheric CO2. We attribute this weakening to the observed increase in Southern Ocean winds resulting from human activities, which is projected to continue in the future. Consequences include a reduction of the efficiency of the Southern Ocean sink of CO2 in the short term (about 25 years) and possibly a higher level of stabilization of atmospheric CO2 on a multicentury time scale.

Atmospheric O2, CO2 and delta13C measurements from aircraft sampling over Griffin Forest, Perthshire, UK.

Regular vertical aircraft sampling has been performed in the lower troposphere above Griffin Forest, near Aberfeldy, Perthshire, UK (56 degrees 37'N, 3 degrees 47'W), between February 2003 and May 2004, for analysis of O2/N2, CO2 and delta13C of CO2. We sampled flasks between 800 and 3100 m above sea level. The peak-to-peak amplitude of the seasonal cycle of O2/N2 decreases from 171 per meg at 800 m to 113 per meg at 3100 m. Furthermore, the seasonal cycle is shifted from low to high altitudes with a lag of about 1 month. The same features are observed for CO2 with a decrease in the peak-to-peak amplitude of the seasonal cycle from 17.6 ppm at 800 m to 11.4 ppm at 3100 m. The vertical profiles show decreasing O2/N2 ratios in summer and increasing O2/N2 ratios in wintertime with increasing sampling height, due to surface exchange of oxygen with the land biosphere and the ocean. The O2:CO2 exchange ratios of the vertical profiles vary between -1.5 and -2.4 mol O2/mol CO2.