First Atmospheric Measurements and Emission Estimates of HFO-1336mzz(Z).

For the past few years, short-lived unsaturated halocarbons have been marketed as environmentally friendly replacements for long-lived halogenated greenhouse gases and ozone-depleting substances. The phase-in of unsaturated halocarbons for various applications, such as refrigeration and foam blowing, can be tracked by their emergence and increase in the atmosphere. We present the first atmospheric measurements of the hydrofluoroolefin (HFO) HFO-1336mzz(Z) ((Z)-1,1,1,4,4,4-hexafluoro-2-butene, cis-CF3CH═CHCF3), a newly used unsaturated hydrofluorocarbon. HFO-1336mzz(Z) has been detected in >90% of all measurements since 2018 during multi-month campaigns at three Swiss and one Dutch location. Since 2019, it is found in ∼30% of all measurements that run continuously at the Swiss high-altitude Jungfraujoch station. During pollution events, mole fractions of up to ∼10 ppt were observed. Based on our measurements, Swiss and Dutch emissions were estimated at 2-7 Mg yr-1 (2019-2021) and 30 Mg yr-1 (2022), respectively. Modeled spatial emission distributions only partly conform to population density in both countries. Monitoring the presence of new unsaturated halocarbons in the atmosphere is crucial since long-term effects of their degradation products are still debated. Furthermore, the production of HFOs involves climate-active substances, which may leak to the atmosphere─in the case of HFO-1336mzz(Z), for example, the ozone-depleting CFC-113a (CF3CCl3).

Automated fragment formula annotation for electron ionisation, high resolution mass spectrometry: application to atmospheric measurements of halocarbons.

BACKGROUND: Non-target screening consists in searching a sample for all present substances, suspected or unknown, with very little prior knowledge about the sample. This approach has been introduced more than a decade ago in the field of water analysis, together with dedicated compound identification tools, but is still very scarce for indoor and atmospheric trace gas measurements, despite the clear need for a better understanding of the atmospheric trace gas composition. For a systematic detection of emerging trace gases in the atmosphere, a new and powerful analytical method is gas chromatography (GC) of preconcentrated samples, followed by electron ionisation, high resolution mass spectrometry (EI-HRMS). In this work, we present data analysis tools to enable automated fragment formula annotation for unknown compounds measured by GC-EI-HRMS. RESULTS: Based on co-eluting mass/charge fragments, we developed an innovative data analysis method to reliably reconstruct the chemical formulae of the fragments, using efficient combinatorics and graph theory. The method does not require the presence of the molecular ion, which is absent in [Formula: see text]40% of EI spectra. Our method has been trained and validated on >50 halocarbons and hydrocarbons, with 3-20 atoms and molar masses of 30-330 g mol[Formula: see text], measured with a mass resolution of approx. 3500. For >90% of the compounds, more than 90% of the annotated fragment formulae are correct. Cases of wrong identification can be attributed to the scarcity of detected fragments per compound or the lack of isotopic constraint (no minor isotopocule detected). CONCLUSIONS: Our method enables to reconstruct most probable chemical formulae independently from spectral databases. Therefore, it demonstrates the suitability of EI-HRMS data for non-target analysis and paves the way for the identification of substances for which no EI mass spectrum is registered in databases. We illustrate the performances of our method for atmospheric trace gases and suggest that it may be well suited for many other types of samples. The L-GPL licenced Python code is released under the name ALPINAC for ALgorithmic Process for Identification of Non-targeted Atmospheric Compounds.

Unexpected nascent atmospheric emissions of three ozone-depleting hydrochlorofluorocarbons.

Global and regional atmospheric measurements and modeling can play key roles in discovering and quantifying unexpected nascent emissions of environmentally important substances. We focus here on three hydrochlorofluorocarbons (HCFCs) that are restricted by the Montreal Protocol because of their roles in stratospheric ozone depletion. Based on measurements of archived air samples and on in situ measurements at stations of the Advanced Global Atmospheric Gases Experiment (AGAGE) network, we report global abundances, trends, and regional enhancements for HCFC-132b ([Formula: see text]), which is newly discovered in the atmosphere, and updated results for HCFC-133a ([Formula: see text]) and HCFC-31 ([Formula: see text]ClF). No purposeful end-use is known for any of these compounds. We find that HCFC-132b appeared in the atmosphere 20 y ago and that its global emissions increased to 1.1 Gg⋅y-1 by 2019. Regional top-down emission estimates for East Asia, based on high-frequency measurements for 2016-2019, account for ∼95% of the global HCFC-132b emissions and for ∼80% of the global HCFC-133a emissions of 2.3 Gg⋅y-1 during this period. Global emissions of HCFC-31 for the same period are 0.71 Gg⋅y-1 Small European emissions of HCFC-132b and HCFC-133a, found in southeastern France, ceased in early 2017 when a fluorocarbon production facility in that area closed. Although unreported emissive end-uses cannot be ruled out, all three compounds are most likely emitted as intermediate by-products in chemical production pathways. Identification of harmful emissions to the atmosphere at an early stage can guide the effective development of global and regional environmental policy.

Long-term Observations of Atmospheric Halogenated Organic Trace Gases.

CFCs (chlorofluorocarbons) and other strong ozone-depleting halogenated organic trace gases were used in numerous industrial, household and agriculture applications. First atmospheric measurements of CFCs were performed in the 1970s, well ahead of the detection of the ozone hole in the 1980s. The continuous observation of these ozone-depleting substances (ODSs) is crucial for monitoring their global ban within the Montreal Protocol. In addition, also HFCs (fluorinated hydrocarbons) are measured, which were introduced as substitutes of ODSs and are potent greenhouse gases. Since 2000, Empa continuously measures more than 50 halogenated trace gases at the high-Alpine station of Jungfraujoch (3850 m asl) as part of the global AGAGE network (Advanced Global Atmospheric Gases Experiment). Jungfraujoch is the highest location worldwide where such measurements are performed, and the site where several of these compounds were measured in the atmosphere for the first time. The measurements at Jungfraujoch and at other globally well-positioned sites serve as an early warning system, i. e. before potentially harmful halogenated organic substances can accumulate and detrimentally affect the natural environment.

Recent Trends in Stratospheric Chlorine From Very Short-Lived Substances.

Very short-lived substances (VSLS), including dichloromethane (CH2Cl2), chloroform (CHCl3), perchloroethylene (C2Cl4), and 1,2-dichloroethane (C2H4Cl2), are a stratospheric chlorine source and therefore contribute to ozone depletion. We quantify stratospheric chlorine trends from these VSLS (VSLCltot) using a chemical transport model and atmospheric measurements, including novel high-altitude aircraft data from the NASA VIRGAS (2015) and POSIDON (2016) missions. We estimate VSLCltot increased from 69 (±14) parts per trillion (ppt) Cl in 2000 to 111 (±22) ppt Cl in 2017, with >80% delivered to the stratosphere through source gas injection, and the remainder from product gases. The modeled evolution of chlorine source gas injection agrees well with historical aircraft data, which corroborate reported surface CH2Cl2 increases since the mid-2000s. The relative contribution of VSLS to total stratospheric chlorine increased from ~2% in 2000 to ~3.4% in 2017, reflecting both VSLS growth and decreases in long-lived halocarbons. We derive a mean VSLCltot growth rate of 3.8 (±0.3) ppt Cl/year between 2004 and 2017, though year-to-year growth rates are variable and were small or negative in the period 2015-2017. Whether this is a transient effect, or longer-term stabilization, requires monitoring. In the upper stratosphere, the modeled rate of HCl decline (2004-2017) is -5.2% per decade with VSLS included, in good agreement to ACE satellite data (-4.8% per decade), and 15% slower than a model simulation without VSLS. Thus, VSLS have offset a portion of stratospheric chlorine reductions since the mid-2000s.

Reconciling reported and unreported HFC emissions with atmospheric observations.

We infer global and regional emissions of five of the most abundant hydrofluorocarbons (HFCs) using atmospheric measurements from the Advanced Global Atmospheric Gases Experiment and the National Institute for Environmental Studies, Japan, networks. We find that the total CO2-equivalent emissions of the five HFCs from countries that are required to provide detailed, annual reports to the United Nations Framework Convention on Climate Change (UNFCCC) increased from 198 (175-221) Tg-CO2-eq ⋅ y(-1) in 2007 to 275 (246-304) Tg-CO2-eq ⋅ y(-1) in 2012. These global warming potential-weighted aggregated emissions agree well with those reported to the UNFCCC throughout this period and indicate that the gap between reported emissions and global HFC emissions derived from atmospheric trends is almost entirely due to emissions from nonreporting countries. However, our measurement-based estimates of individual HFC species suggest that emissions, from reporting countries, of the most abundant HFC, HFC-134a, were only 79% (63-95%) of the UNFCCC inventory total, while other HFC emissions were significantly greater than the reported values. These results suggest that there are inaccuracies in the reporting methods for individual HFCs, which appear to cancel when aggregated together.

First observations of the fourth generation synthetic halocarbons HFC-1234yf, HFC-1234ze(E), and HCFC-1233zd(E) in the atmosphere.

Halogenated alkenes are a class of anthropogenic substances, which replace ozone-depleting substances and long-lived greenhouse gases in the foam-blowing, refrigeration, and solvent sectors. We report the first multiyear atmospheric measurements of the hydrofluorocarbons HFC-1234yf (2,3,3,3-tetrafluoroprop-1-ene, CF3CF═CH2), and HFC-1234ze(E) (E-1,3,3,3-tetrafluoroprop-1-ene trans-CF3CH═CHF), and the hydrochlorofluorocarbon HCFC-1233zd(E) (E-1-chloro-3,3,3-trifluoroprop-1-ene trans-CF3CH═CHCl) from the high altitude observatory at Jungfraujoch and from urban Dubendorf (Switzerland). When observations started in 2011 HFC-1234yf was undetectable at Jungfraujoch (mole fractions <0.003 ppt, parts-per-trillion, 10(-12)) but since then the percentage of measurements with detectable mole fractions has steadily increased to 4.5% in 2014. By contrast, in 2014 HFC-1234ze(E) was detectable in half of our samples at Jungfraujoch and in all samples at Dubendorf demonstrating the wide use of this compound within the air mass footprints of the stations. Our back trajectory analysis for the Jungfraujoch observations suggests high emission strength of HFC-1234ze(E) in the Belgium/Netherlands region. HCFC-1233zd(E) is present at very low mole fractions (typically <0.03 ppt) at both stations, and features pronounced seasonality and a general absence of pollution events during our 2013-2014 measurements. This is indicative of the presence of significant emissions from source locations outside the footprints of the two stations. Based on a simple one-box model calculation we estimate globally increasing HCFC-1233zd(E) emissions from 0.2 Gg yr(-1) in 2013 to 0.5 Gg yr(-1) for 2014.

Comparison of halocarbon measurements in an atmospheric dry whole air sample.

The growing awareness of climate change/global warming, and continuing concerns regarding stratospheric ozone depletion, will require continued measurements and standards for many compounds, in particular halocarbons that are linked to these issues. In order to track atmospheric mole fractions and assess the impact of policy on emission rates, it is necessary to demonstrate measurement equivalence at the highest levels of accuracy for assigned values of standards. Precise measurements of these species aid in determining small changes in their atmospheric abundance. A common source of standards/scales and/or well-documented agreement of different scales used to calibrate the measurement instrumentation are key to understanding many sets of data reported by researchers. This report describes the results of a comparison study among National Metrology Institutes and atmospheric research laboratories for the chlorofluorocarbons (CFCs) dichlorodifluoromethane (CFC-12), trichlorofluoromethane (CFC-11), and 1,1,2-trichlorotrifluoroethane (CFC-113); the hydrochlorofluorocarbons (HCFCs) chlorodifluoromethane (HCFC-22) and 1-chloro-1,1-difluoroethane (HCFC-142b); and the hydrofluorocarbon (HFC) 1,1,1,2-tetrafluoroethane (HFC-134a), all in a dried whole air sample. The objective of this study is to compare calibration standards/scales and the measurement capabilities of the participants for these halocarbons at trace atmospheric levels. The results of this study show agreement among four independent calibration scales to better than 2.5% in almost all cases, with many of the reported agreements being better than 1.0%.

European emissions of halogenated greenhouse gases inferred from atmospheric measurements.

European emissions of nine representative halocarbons (CFC-11, CFC-12, Halon 1211, HCFC-141b, HCFC-142b, HCFC-22, HFC-125, HFC-134a, HFC-152a) are derived for the year 2009 by combining long-term observations in Switzerland, Italy, and Ireland with campaign measurements from Hungary. For the first time, halocarbon emissions over Eastern Europe are assessed by top-down methods, and these results are compared to Western European emissions. The employed inversion method builds on least-squares optimization linking atmospheric observations with calculations from the Lagrangian particle dispersion model FLEXPART. The aggregated halocarbon emissions over the study area are estimated at 125 (106-150) Tg of CO(2) equiv/y, of which the hydrofluorocarbons (HFCs) make up the most important fraction with 41% (31-52%). We find that chlorofluorocarbon (CFC) emissions from banks are still significant and account for 35% (27-43%) of total halocarbon emissions in Europe. The regional differences in per capita emissions are only small for the HFCs, while emissions of CFCs and hydrochlorofluorocarbons (HCFCs) tend to be higher in Western Europe compared to Eastern Europe. In total, the inferred per capita emissions are similar to estimates for China, but 3.5 (2.3-4.5) times lower than for the United States. Our study demonstrates the large benefits of adding a strategically well placed measurement site to the existing European observation network of halocarbons, as it extends the coverage of the inversion domain toward Eastern Europe and helps to better constrain the emissions over Central Europe.

European emissions of HFC-365mfc, a chlorine-free substitute for the foam blowing agents HCFC-141b and CFC-11.

HFC-365mfc (1,1,1,3,3-pentafluorobutane) is an industrial chemical used for polyurethane foam blowing. From early 2003, HFC-365mfc has been commercially produced as a substitute for HCFC-141b, whose use in Europe has been banned since January 2004. We describe the first detection of HFC-365mfc in the atmosphere and report on a 2 year long record at the high Alpine station of Jungfraujoch (Switzerland) and the Atlantic coast station of Mace Head (Ireland). The measurements at Jungfraujoch are used to estimate the central European emissions of HFC-365mfc, HCFC-141b, and CFC-11. For HFC-365mfc, we estimate the central European emissions (Germany, France, Italy, Switzerland, The Netherlands, Belgium, and Luxembourg) in 2003 and 2004 as 400-500 tonnes year(-1). These emissions are about one-third lower on a per capita basis than what we estimate from the Mace Head measurements for the total of Europe. The estimated emissions of HCFC-141b for central Europe are higher (i.e., 7.2-3.5 ktonnes year(-1)) with a decreasing trend in the period from 2000 to 2004. Residual emissions of CFC-11 are estimated at 2.4-4.7 ktonnes year(-1) in the same time period. The Po Valley (northern Italy) appears to be a main source region for HFC-365mfc and for the former blowing agents HCFC-141b and CFC-11. In 2004, the emissions of HFC-365mfc arose from a wider region of Europe, which we attribute to an increased penetration of HFC-365mfc into the European market.