Climatology and Atmospheric Chemistry of Non-Methane Hydrocarbon Emissions over the North Atlantic.

European Geosciences Union (EGU), General Assembly. Viena, Austria, 07 - 12 April 2013.Non-methane hydrocarbons (NMHC) covering the C2 to C7 volatility range have been monitored at the Pico Mountain Observatory, Pico Island, Azores, Portugal, since 2004. The Observatory is located at 2225 m a.s.l. in the caldera of the Pico Mountain volcano, and during most times receives lower free tropospheric air that has been transported across the North Atlantic. The 7-year NMHC record has been analyzed for seasonal behavior of photochemical processing, atmospheric transport time, and source region using ratios of NMHC species as indicators of photochemical aging and HYSPLIT model outputs. Transport conditions resulting in elevated and low NMHC conditions were specifically studied to investigate seasonal pollution transport in the North Atlantic region

Climatology and atmospheric chemistry of the non-methane hydrocarbons ethane and propane over the North Atlantic

A record spanning ten years of non-methane hydrocarbon (NMHC) data from the Pico Mountain Observatory (PMO), Pico Island, Azores, Portugal, was analyzed for seasonal NMHC behavior, atmospheric processing, and trends, focusing on ethane and propane. The location of this site in the central North Atlantic, at an elevation of 2225 m asl, allows these data to be used to investigate the background conditions and pollution transport events occurring in the lower free North Atlantic troposphere. The quantity ln([propane]/[ethane]) was used as an indicator of both photochemical processing and a marker for the occurrence of pollution transport events detected at the station. The Pico data were compared with three other continuous NMHC data sets from sites bordering the North Atlantic, i.e. the Global Atmospheric Watch (GAW) stations at Summit, Greenland, Hohenpeisssenberg, Germany, and Cape Verde, using ln([propane]/[ethane]) results as an indicator for the degree of photochemical processing (aging) seen in the data. Comparisons of these three data sets showed some significant differences in the seasonal background and range of observed values. The statistical distribution of binned monthly data was determined, and individual sample events were then scaled to the monthly median observed value. Back trajectories, determined by the HYSPLIT model were used to investigate the geographic origin of the observed trace gases as a function of the degree of photochemical processing. Results show that PMO samples have been subjected to a diversity of air transport and aging, from highly processed air to freshly emitted air throughout the year, and in particular during summer months. The predominant air transport is from North America, with only occasional influence from continental areas located east and southeast (Europe and Africa). The available record was found to be too variable and still too short to allow deciphering NMHC trends from the data. Ethane and propane measurements at the PMO were compared with the MOZART-4 atmospheric chemistry and transport model at the appropriate time and location. The model was found to yield good agreement in the description of the lower range of atmospheric mole fractions observed, of the seasonal cycle, and the regional oxidation chemistry. However, ethane and propane enhancements in transport events were underestimated, indicating that after the 3 days of synoptic transport to PMO the spatial extent of plumes frequently is smaller than the 2.8x2.8 (300 km) model grid resolution

Estimating the atmospheric concentration of Criegee intermediates and their possible interference in a FAGE-LIF instrument

We analysed the extensive dataset from the HUMPPA-COPEC 2010 and the HOPE 2012 field campaigns in the boreal forest and rural environments of Finland and Germany, respectively, and estimated the abundance of stabilised Criegee intermediates (SCIs) in the lower troposphere. Based on laboratory tests, we propose that the background OH signal observed in our IPI-LIF-FAGE instrument during the aforementioned campaigns is caused at least partially by SCIs. This hypothesis is based on observed correlations with temperature and with concentrations of unsaturated volatile organic compounds and ozone. Just like SCIs, the background OH concentration can be removed through the addition of sulfur dioxide. SCIs also add to the previously underestimated production rate of sulfuric acid. An average estimate of the SCI concentration of similar to 5.0 x 10(4) molecules cm(-3) (with an order of magnitude uncertainty) is calculated for the two environments. This implies a very low ambient concentration of SCIs, though, over the boreal forest, significant for the conversion of SO2 into H2SO4. The large uncertainties in these calculations, owing to the many unknowns in the chemistry of Criegee intermediates, emphasise the need to better understand these processes and their potential effect on the self-cleaning capacity of the atmosphere.Peer reviewe

The fingerprint of the summer 2018 drought in Europe on ground-based atmospheric CO2 measurements

During the summer of 2018, a widespread drought developed over Northern and Central Europe. The increase in temperature and the reduction of soil moisture have influenced carbon dioxide (CO2) exchange between the atmosphere and terrestrial ecosystems in various ways, such as a reduction of photosynthesis, changes in ecosystem respiration, or allowing more frequent fires. In this study, we characterize the resulting perturbation of the atmospheric CO2 seasonal cycles. 2018 has a good coverage of European regions affected by drought, allowing the investigation of how ecosystem flux anomalies impacted spatial CO2 gradients between stations. This density of stations is unprecedented compared to previous drought events in 2003 and 2015, particularly thanks to the deployment of the Integrated Carbon Observation System (ICOS) network of atmospheric greenhouse gas monitoring stations in recent years. Seasonal CO2 cycles from 48 European stations were available for 2017 and 2018.The UK sites were funded by the UK Department of Business, Energy and Industrial Strategy (formerly the Department of Energy and Climate Change) through contracts TRN1028/06/2015 and TRN1537/06/2018. The stations at the ClimaDat Network in Spain have received funding from the ‘la Caixa’ Foundation, under agreement 2010-002624

Preparation and analysis of zero gases for the measurement of trace VOCs in air monitoring

Air quality observations are performed globally to monitor the status of the atmosphere and its level of pollution and to assess mitigation strategies. Regulations of air quality monitoring programmes in various countries demand high-precision measurements for harmful substances often at low trace concentrations. These requirements can only be achieved by using high-quality calibration gases including high-purity zero gas. For volatile organic compound (VOC) observations, zero gas is defined as being hydrocarbon-free and can be, for example, purified air, nitrogen or helium. It is essential for the characterisation of the measurement devices and procedures, for instrument operation as well as for calibrations. Two commercial and one self-built gas purifiers were tested for their VOC removal efficiency following a standardised procedure. The tested gas purifiers included one adsorption cartridge with an inorganic media and two types of metal catalysts. A large range of VOCs were investigated, including the most abundant species typically measured at air monitoring stations. Both catalysts were able to remove a large range of VOCs whilst the tested adsorption cartridge was not suitable to remove light compounds up to C4. Memory effects occurred for the adsorption cartridge when exposed to higher concentration. This study emphasises the importance of explicitly examining a gas purifier for its intended application before applying it in the field

Reversal of global atmospheric ethane and propane trends largely due to US oil and natural gas production

Non-methane hydrocarbons such as ethane are important precursors to tropospheric ozone and aerosols. Using data from a global surface network and atmospheric column observations we show that the steady decline in ethane concentrations that began in the 1970s halted between 2005 and 2010 in most of the Northern Hemisphere, and has since reversed. We calculate a yearly increase in ethane emissions in the Northern Hemisphere of 0.42 (+/-0.19) Tg/yr between mid-2009 and mid-2014. The largest increases in ethane and for the shorter-lived propane are seen over the central and eastern USA, with a spatial distribution that suggests North American oil and natural gas development as the primary source of increasing emissions. By including other co-emitted oil and natural gas non-methane hydrocarbons, we estimate a Northern Hemisphere total non-methane hydrocarbon yearly emission increase of 1.2 (+/-0.8) Tg/yr. Atmospheric chemical transport modelling suggests that these emissions could augment summertime mean surface ozone by several nanomoles per mole near oil and natural gas production regions. Methane/ethane oil and natural gas emission ratios suggest a significant increase in associated methane emissions; however, this increase is inconsistent with observed leak rates in production regions and changes in methane’s global isotopic ratio

A Reversal of Long-term Global Trends in Atmospheric Ethane and Propane from North American Oil and Natural Gas Emissions Language :English

info:eu-repo/semantics/nonPublishe

Technical Note: Formal blind intercomparison of OH measurements: results from the international campaign HoxComp

Hydroxyl radicals (OH) are the major oxidizing species in the troposphere. Because of their central importance, absolute measurements of their concentrations are needed to validate chemical mechanisms of atmospheric models. The extremely low and highly variable concentrations in the troposphere, however, make measurements of OH difficult. Three techniques are currently used worldwide for tropospheric observations of OH after about 30~years of technical developments: Differential Optical Laser Absorption Spectroscopy (DOAS), Laser-Induced Fluorescence Spectroscopy (LIF), and Chemical Ionisation Mass Spectrometry (CIMS). Even though many measurement campaigns with OH data were published, the question of accuracy and precision is still under discussion.<br> <br> Here, we report results of the first formal, blind intercomparison of these techniques. Six OH instruments (4~LIF, 1~CIMS, 1~DOAS) participated successfully in the ground-based, international HOxComp campaign carried out in Jülich, Germany, in summer 2005. Comparisons were performed for three days in ambient air (3~LIF, 1 CIMS) and for six days in the atmosphere simulation chamber SAPHIR (3~LIF, 1~DOAS). All instruments were found to measure tropospheric OH concentrations with high sensitivity and good time resolution. The pairwise correlations between different data sets were linear and yielded high correlation coefficients (<i>r</i><sup>2</sup>=0.75−0.96). Excellent absolute agreement was observed for the instruments at the SAPHIR chamber, yielding slopes between 1.01 and 1.13 in the linear regressions. In ambient air, the slopes deviated from unity by factors of 1.06 to 1.69, which can partly be explained by the stated instrumental accuracies. In addition, sampling inhomogeneities and calibration problems have apparently contributed to the discrepancies. The absolute intercepts of the linear regressions did not exceed 0.6×10<sup>6</sup> cm<sup>−3</sup>, mostly being insignificant and of minor importance for daytime observations of OH. No relevant interferences with respect to ozone, water vapour, NO<sub>x</sub> and peroxy radicals could be detected. The HOxComp campaign has demonstrated that OH can be measured reasonably well by current instruments, but also that there is still room for improvement of calibrations

Multi-laboratory compilation of atmospheric methane data for the year 2021; obspack_ch4_1_NRT_v4.0_2022-03-03

This product is constructed using the Observation Package (ObsPack) framework [Masarie et al., 2014; www.earth-syst-sci-data.net/6/375/2014/]. The framework is designed to bring together atmospheric greenhouse gas (GHG) observations from a variety of sampling platforms, prepare them with specific applications in mind, and package and distribute them in a self-consistent and well-documented product. ObsPack products are intended to support GHG budget studies and represent a new generation of cooperative value-added GHG data products