Validation of the Swiss methane emission inventory by atmospheric observations and inverse modelling

Atmospheric inverse modelling has the potential to provide observation-based estimates of greenhouse gas emissions at the country scale, thereby allowing for an independent validation of national emission inventories. Here, we present a regional-scale inverse modelling study to quantify the emissions of methane (CH₄) from Switzerland, making use of the newly established CarboCount-CH measurement network and a high-resolution Lagrangian transport model. In our reference inversion, prior emissions were taken from the "bottom-up" Swiss Greenhouse Gas Inventory (SGHGI) as published by the Swiss Federal Office for the Environment in 2014 for the year 2012. Overall we estimate national CH₄ emissions to be 196 ± 18 Gg yr⁻¹ for the year 2013 (1σ uncertainty). This result is in close agreement with the recently revised SGHGI estimate of 206 ± 33 Gg yr⁻¹ as reported in 2015 for the year 2012. Results from sensitivity inversions using alternative prior emissions, uncertainty covariance settings, large-scale background mole fractions, two different inverse algorithms (Bayesian and extended Kalman filter), and two different transport models confirm the robustness and independent character of our estimate. According to the latest SGHGI estimate the main CH₄ source categories in Switzerland are agriculture (78 %), waste handling (15 %) and natural gas distribution and combustion (6 %). The spatial distribution and seasonal variability of our posterior emissions suggest an overestimation of agricultural CH₄ emissions by 10 to 20 % in the most recent SGHGI, which is likely due to an overestimation of emissions from manure handling. Urban areas do not appear as emission hotspots in our posterior results, suggesting that leakages from natural gas distribution are only a minor source of CH₄ in Switzerland. This is consistent with rather low emissions of 8.4 Gg yr⁻¹ reported by the SGHGI but inconsistent with the much higher value of 32 Gg yr⁻¹ implied by the EDGARv4.2 inventory for this sector. Increased CH₄ emissions (up to 30 % compared to the prior) were deduced for the north-eastern parts of Switzerland. This feature was common to most sensitivity inversions, which is a strong indicator that it is a real feature and not an artefact of the transport model and the inversion system. However, it was not possible to assign an unambiguous source process to the region. The observations of the CarboCount-CH network provided invaluable and independent information for the validation of the national bottom-up inventory. Similar systems need to be sustained to provide independent monitoring of future climate agreements.

Historic records of organic compounds from a high Alpine glacier: influences of biomass burning, anthropogenic emissions, and dust transport

Historic records of α-dicarbonyls (glyoxal, methylglyoxal), carboxylic acids (C6–C12 dicarboxylic acids, pinic acid, p-hydroxybenzoic acid, phthalic acid, 4-methylphthalic acid), and ions (oxalate, formate, calcium) were determined with annual resolution in an ice core from Grenzgletscher in the southern Swiss Alps, covering the time period from 1942 to 1993. Chemical analysis of the organic compounds was conducted using ultra-high-performance liquid chromatography (UHPLC) coupled to electrospray ionization high-resolution mass spectrometry (ESI-HRMS) for dicarbonyls and long-chain carboxylic acids and ion chromatography for short-chain carboxylates. Long-term records of the carboxylic acids and dicarbonyls, as well as their source apportionment, are reported for western Europe. This is the first study comprising long-term trends of dicarbonyls and long-chain dicarboxylic acids (C6–C12) in Alpine precipitation. Source assignment of the organic species present in the ice core was performed using principal component analysis. Our results suggest biomass burning, anthropogenic emissions, and transport of mineral dust to be the main parameters influencing the concentration of organic compounds. Ice core records of several highly correlated compounds (e.g., p-hydroxybenzoic acid, pinic acid, pimelic, and suberic acids) can be related to the forest fire history in southern Switzerland. P-hydroxybenzoic acid was found to be the best organic fire tracer in the study area, revealing the highest correlation with the burned area from fires. Historical records of methylglyoxal, phthalic acid, and dicarboxylic acids adipic acid, sebacic acid, and dodecanedioic acid are comparable with that of anthropogenic emissions of volatile organic compounds (VOCs). The small organic acids, oxalic acid and formic acid, are both highly correlated with calcium, suggesting their records to be affected by changing mineral dust transport to the drilling site.