Atmospheric CFC-11 Research Articles

Atmospheric CFC-11 and CCl4: A free calibration standard for PTR-MS

Proton-transfer-reaction mass spectrometry (PTR-MS) is an analytical technique used to monitor volatile organic compounds in real-time. For quantitative analysis, compounds of interest are typically calibrated using gas standards, but PTR-MS is quantitative to uncalibrated compounds if the mass-dependent transmission is well defined. However, long-term measurements are challenging due to the drift in transmission over time. Performing frequent calibrations helps, but the methods are time-consuming and tedious, often leading to instruments being under-calibrated. Here we show the use of long-lived and globally monitored compounds in the atmosphere as a tool to constrain the transmission between calibrations. The major ion of trichlorofluromethane (CFC-11) and carbon tetrachloride (CCl4) is found at the mass-to-charge ratio (m/z) 116.9, which we propose using to retrieve the transmission of a PTR-MS. We determined the pseudo-reaction rate constants of CFC-11 and CCl4 to be 0.82 × 10−9 ± 0.05 × 10−9 cm3 s−1 molecule−1, and 1.65 × 10−9 ± 0.08 × 10−9 cm3 s−1 molecule−1, respectively. The method introduced here can improve data quality and accuracy, especially for long-term atmospheric measurements.

Retrieval of atmospheric CFC-11 and CFC-12 from high-resolution FTIR observations at Hefei and comparisons with other independent datasets

Abstract. Synthetic halogenated organic chlorofluorocarbons (CFCs) play an important role in stratospheric ozone depletion and contribute significantly to the greenhouse effect. In this work, the mid-infrared solar spectra measured by ground-based high-resolution Fourier transform infrared spectroscopy (FTIR) were used to retrieve atmospheric CFC-11 (CCl3F) and CFC-12 (CCl2F2) at Hefei, China. The CFC-11 columns observed from January 2017 to December 2020 and CFC-12 columns from September 2015 to December 2020 show a similar annual decreasing trend and seasonal cycle, with an annual rate of -0.47±0.06 % yr−1 and -0.68±0.03 % yr−1, respectively. So the decline rate of CFC-11 is significantly lower than that of CFC-12. CFC-11 total columns were higher in summer, and CFC-12 total columns were higher in summer and autumn. Both CFC-11 and CFC-12 total columns reached the lowest in spring. Further, FTIR data of NDACC (Network for the Detection of Atmospheric Composition Change) candidate station Hefei were compared with the ACE-FTS (Atmospheric Chemistry Experiment Fourier transform spectrometer) satellite data, WACCM (Whole Atmosphere Community Climate Model) data, and the data from other NDACC-IRWG (InfraRed Working Group) stations (St. Petersburg, Jungfraujoch, and Réunion). The mean relative difference between the vertical profiles observed by FTIR and ACE-FTS is -5.6±3.3 % and 4.8±0.9 % for CFC-11 and CFC-12 for an altitude of 5.5 to 17.5 km, respectively. The results demonstrate that our FTIR data agree relatively well with the ACE-FTS satellite data. The annual decreasing rate of CFC-11 measured from ACE-FTS and calculated by WACCM is -1.15±0.22 % yr−1 and -1.68±0.18 % yr−1, respectively. The interannual decreasing rates of atmospheric CFC-11 obtained from ACE-FTS and WACCM data are higher than that from FTIR observations. Also, the annual decreasing rate of CFC-12 from ACE-FTS and WACCM is -0.85±0.15 % yr−1 and -0.81±0.05 % yr−1, respectively, close to the corresponding values from the FTIR measurements. The total columns of CFC-11 and CFC-12 at the Hefei and St. Petersburg stations are significantly higher than those at the Jungfraujoch and Réunion (Maïdo) stations, and the two values reached the maximum in local summer or autumn and the minimum in local spring or winter at the four stations. The seasonal variability at the three stations in the Northern Hemisphere is higher than that at the station in the Southern Hemisphere.

CFC-11 measurements in China, Nepal, Pakistan, Saudi Arabia and South Korea (1998–2018): Urban, landfill fire and garbage burning sources

Environmental context The production and consumption of chlorofluorocarbons (CFCs) is regulated under the Montreal Protocol and its amendments, due to their role in stratospheric ozone depletion. Global atmospheric levels of CFC-11 did not decline as rapidly as expected during 2012–2018, in large part due to emissions from eastern China. In order to further clarify global CFC-11 emissions, this work provides a rare set CFC-11 measurements from understudied countries and sources throughout Asia (1998–2018). Abstract Trichlorofluoromethane (CFC-11) is an ozone-depleting substance whose production and consumption are regulated under the Montreal Protocol. Global atmospheric CFC-11 levels declined less quickly than expected during 2012–2018, largely because of ongoing emissions from eastern Asia. Satellite measurements suggest additional CFC-11 hotspots in the Arabian Peninsula and north India/Nepal. Here we present CFC-11 levels measured in dozens of Asian cities during 1998–2018, including China and Pakistan before the 2010 phaseout of CFC-11, and China, Nepal, Pakistan, Saudi Arabia and South Korea after the phaseout. Surface measurements of CFCs in Nepal, Pakistan and Saudi Arabia are very rare, and these surveys provide important observational constraints from understudied regions. During pre-phaseout campaigns, higher CFC-11 levels were measured in Beijing than Karachi, despite much higher overall volatile organic compound (VOC) levels in Karachi. During post-phaseout campaigns, average CFC-11 levels were higher in inland Shandong Province and Seoul (1.11–1.23× background) than in western Saudi Arabia, Lahore and Kathmandu (1.02–1.11× background), despite higher levels of other VOCs in the latter regions. While China is known to emit excess CFC-11, elevated CFC-11 levels in Seoul, especially during stagnant meteorological conditions, suggest local emissions in 2015–2016. Rough emission estimates suggest that South Korea is likely a relatively minor global source of excess CFC-11. Hotspot CFC-11 levels were measured from a landfill fire in Mecca (average of 1.8× background) and from garbage burning in Nepal (1.5× background). Because garbage burning and open burning in dumps are common practices, further investigation of CFC-11 emissions at dumps and landfills worldwide is encouraged to determine their global impact.

On the effects of the ocean on atmospheric CFC-11 lifetimes and emissions

The ocean is a reservoir for CFC-11, a major ozone-depleting chemical. Anthropogenic production of CFC-11 dramatically decreased in the 1990s under the Montreal Protocol, which stipulated a global phase out of production by 2010. However, studies raise questions about current overall emission levels and indicate unexpected increases of CFC-11 emissions of about 10 Gg ⋅ yr-1 after 2013 (based upon measured atmospheric concentrations and an assumed atmospheric lifetime). These findings heighten the need to understand processes that could affect the CFC-11 lifetime, including ocean fluxes. We evaluate how ocean uptake and release through 2300 affects CFC-11 lifetimes, emission estimates, and the long-term return of CFC-11 from the ocean reservoir. We show that ocean uptake yields a shorter total lifetime and larger inferred emission of atmospheric CFC-11 from 1930 to 2075 compared to estimates using only atmospheric processes. Ocean flux changes over time result in small but not completely negligible effects on the calculated unexpected emissions change (decreasing it by 0.4 ± 0.3 Gg ⋅ yr-1). Moreover, it is expected that the ocean will eventually become a source of CFC-11, increasing its total lifetime thereafter. Ocean outgassing should produce detectable increases in global atmospheric CFC-11 abundances by the mid-2100s, with emission of around 0.5 Gg ⋅ yr-1; this should not be confused with illicit production at that time. An illustrative model projection suggests that climate change is expected to make the ocean a weaker reservoir for CFC-11, advancing the detectable change in the global atmospheric mixing ratio by about 5 yr.

An unexpected and persistent increase in global emissions of ozone-depleting CFC-11.

The Montreal Protocol was designed to protect the stratospheric ozone layer by enabling reductions in the abundance of ozone-depleting substances such as chlorofluorocarbons (CFCs) in the atmosphere1-3. The reduction in the atmospheric concentration of trichlorofluoromethane (CFC-11) has made the second-largest contribution to the decline in the total atmospheric concentration of ozone-depleting chlorine since the 1990s 1 . However, CFC-11 still contributes one-quarter of all chlorine reaching the stratosphere, and a timely recovery of the stratospheric ozone layer depends on a sustained decline in CFC-11 concentrations 1 . Here we show that the rate of decline of atmospheric CFC-11 concentrations observed at remote measurement sites was constant from 2002 to 2012, and then slowed by about 50 per cent after 2012. The observed slowdown in the decline of CFC-11 concentration was concurrent with a 50 per cent increase in the mean concentration difference observed between the Northern and Southern Hemispheres, and also with the emergence of strong correlations at the Mauna Loa Observatory between concentrations of CFC-11 and other chemicals associated with anthropogenic emissions. A simple model analysis of our findings suggests an increase in CFC-11 emissions of 13 ± 5 gigagrams per year (25 ± 13 per cent) since 2012, despite reported production being close to zero 4 since 2006. Our three-dimensional model simulations confirm the increase in CFC-11 emissions, but indicate that this increase may have been as much as 50 per cent smaller as a result of changes in stratospheric processes or dynamics. The increase in emission of CFC-11 appears unrelated to past production; this suggests unreported new production, which is inconsistent with the Montreal Protocol agreement to phase out global CFC production by 2010.

The SPARC Data Initiative: comparisons of CFC-11, CFC-12, HF and SF<sub>6</sub> climatologies from international satellite limb sounders

Abstract. A quality assessment of the CFC-11 (CCl3F), CFC-12 (CCl2F2), HF, and SF6 products from limb-viewing satellite instruments is provided by means of a detailed intercomparison. The climatologies in the form of monthly zonal mean time series are obtained from HALOE, MIPAS, ACE-FTS, and HIRDLS within the time period 1991–2010. The intercomparisons focus on the mean biases of the monthly and annual zonal mean fields and aim to identify their vertical, latitudinal and temporal structure. The CFC evaluations (based on MIPAS, ACE-FTS and HIRDLS) reveal that the uncertainty in our knowledge of the atmospheric CFC-11 and CFC-12 mean state, as given by satellite data sets, is smallest in the tropics and mid-latitudes at altitudes below 50 and 20 hPa, respectively, with a 1σ multi-instrument spread of up to ±5 %. For HF, the situation is reversed. The two available data sets (HALOE and ACE-FTS) agree well above 100 hPa, with a spread in this region of ±5 to ±10 %, while at altitudes below 100 hPa the HF annual mean state is less well known, with a spread ±30 % and larger. The atmospheric SF6 annual mean states derived from two satellite data sets (MIPAS and ACE-FTS) show only very small differences with a spread of less than ±5 % and often below ±2.5 %. While the overall agreement among the climatological data sets is very good for large parts of the upper troposphere and lower stratosphere (CFCs, SF6) or middle stratosphere (HF), individual discrepancies have been identified. Pronounced deviations between the instrument climatologies exist for particular atmospheric regions which differ from gas to gas. Notable features are differently shaped isopleths in the subtropics, deviations in the vertical gradients in the lower stratosphere and in the meridional gradients in the upper troposphere, and inconsistencies in the seasonal cycle. Additionally, long-term drifts between the instruments have been identified for the CFC-11 and CFC-12 time series. The evaluations as a whole provide guidance on what data sets are the most reliable for applications such as studies of atmospheric transport and variability, model–measurement comparisons and detection of long-term trends. The data sets will be publicly available from the SPARC Data Centre and through PANGAEA (doi:10.1594/PANGAEA.849223).

Transit time distributions and oxygen utilization rates in the Northeast Pacific Ocean from chlorofluorocarbons and sulfur hexafluoride

Depth profiles of dissolved chlorofluorocarbon-11 (CFC-11) and sulfur hexafluoride (SF6) were measured during a September 2008 cruise in the Northeast Pacific Ocean. For each water sample, the two tracers were used in concert to estimate likely mean ages and widths of parameterized 1-D transit time distributions (TTDs). In shallow waters (<250m), the TTDs’ mean ages were relatively loosely constrained due to the slow decrease of atmospheric CFC-11 since 1994. In the main thermocline (25.0–26.6σθ, ∼300–550m), the CFC-11/SF6 tracer pair constrained TTDs’ mean ages to within±10%. Deeper than 26.8σθ (∼600m), SF6 levels in 2008 were too low for the CFC-11/SF6 tracer pair to constrain the TTDs’ mean ages. Within the main thermocline of the subtropical North Pacific Ocean (20°–37°N along 152°W), the TTDs’ mean ages were used to estimate Oxygen Utilization Rates (OURs) of ∼11μmolkg−1yr−1 on 25.0–25.5σθ (∼160m), attenuating to very low rates (0.12μmolkg−1yr−1) by 26.8–27.0σθ (∼600m). Depth integration of the in-situ OURs implied an average carbon remineralization rate of 1.7±0.3molCm−2yr−1 in this region and depth range, somewhat lower than other independent estimates. Along the 152°W section, depth integrating the apparent OURs implied carbon remineralization rates of 2.5–3.5molCm−2yr−1 from 20°N to 30°N, 3.5–4.0molCm−2yr−1 from 30°N to 40°N, and 2–2.7molCm−2yr−1 north of 45°N.

In-situ measurement of atmospheric CFC-11 at the Shangdianzi Global Atmosphere Watch (GAW) Regional Station

An in-situ GC-ECD system was used to measure halocarbons at Shangdianzi (SDZ) GAW regional station. In this paper, we reported observational results of atmospheric CFC-11 (CCl3F) mixing ratios from April 2007 to March 2008. The CFC-11 time series showed large variability. Approximately 62% observed values were filtered as non-background data. The median, 10% and 90% percentiles of CFC-11 background mixing ratios were 245.4 ppt (10−12 mol/mol), 244.6 ppt and 246.1 ppt, respectively; whereas those of non-background CFC-11 mixing ratios were 254.7, 246.6 and 272.1 ppt, respectively. Significant differences in background and non-background CFC-11 mixing ratios were observed between summer and autumn, mainly because of the CFC-11 stored in foam being prone to atmospheric release in hot seasons. Comparison of the SDZ data with the five AGAGE stations suggested agreement with mid-high latitude Northern Hemisphere stations MHD, THD and RPB. The SDZ data were higher than that of Southern Hemisphere stations CGO and SMO. Higher CFC-11 mixing ratios measured in different seasons were always associated with winds from the W-WSW-SW sector, indicating that the airflow coming from this wind sector has a positive contribution to CFC-11concentrations. The CFC-11 mixing ratios were higher in autumn and summer than in spring and winter, in which its mixing ratios were very close to the atmospheric background level. This was happened especially when airflow originated from the NNE-NE-ENE-E sector, indicating the air masses coming from these wind directions was relatively clean.

Interannual variability of CFC-11 absorption by the ocean: an offline model study

The global ocean Chlorofluorocarbon (CFC-11) was simulated in an offline model driven by re-analysis ocean currents in order to identify the mechanisms of interannual to interdecadal variability of air–sea CFC fluxes. The model was forced with the observed anthropogenic perturbations of atmospheric CFC-11 from the post industrial period (1938) following the OCMIP-II flux protocols along with the observed winds from 1960 to 1999 in the formulation of surface gas exchanges. The model ocean CFC-11 inventories, at the end of 1990s, accounted approximately 1% of the total atmospheric CFC-11, which is consistent with the corresponding observations. The mid-to-high latitude oceans were venue for strong (weak) oceanic sinks (sources) of CFC-11 during the winter (summer) months. The Southern Ocean (south of 40°S) and the North Atlantic (north of 35°N) provided two largest sinks of CFC-11, through which 31.4 and 14.6% of the global ocean CFC-11 entered, respectively. The eastern tropical Pacific Ocean exhibited large interannual variability of CFC-11 flux with a strong (weak) sink during La Nina (El Nino) years and represented 36% of the global CFC-11 flux variability. The North Atlantic and Southern Ocean were found as regions of large sink efficiency: a capacity to sink more CFC than outsource, although it reduced by 80 and 70%, respectively, in the last 40 years compared to 1960. The sink to source ratio of global ocean CFC-11 fluxes were reduced from 90 to 50% in the last 40 years. This indicates a saturation of CFC in the above-thermocline subsurface that makes the upper ocean less efficient in absorbing CFC in recent decades. A positive trend in CFC sink is now limited to the Southern Ocean, central tropical Pacific and western boundary current regions which possess active upwelling of old water with long time since last atmospheric contact. However, a globally averaged trend was a reduced CFC-11 sink, by emitting 30% of the total ocean CFC-11 that was absorbed during last 40 years.

Design and Validation of an Offline Oceanic Tracer Transport Model for a Carbon Cycle Study

Abstract An offline passive tracer transport model with self-operating diagnostic-mode vertical mixing and horizontal diffusion parameterizations is used with assimilated ocean currents to find the chlorofluorocarbon (CFC-11) cycle in oceans. This model was developed at the National Institute for Environmental Studies (NIES) under the carbon cycle research project inside the Greenhouse Gas Observing Satellite (GOSAT) modeling group. The model borrows offline fields from precalculated monthly archives of assimilated ocean currents, temperature, and salinity, and it evolves a prognostic passive tracer with prescribed surface forcing. The model’s performance is validated by simulating the CFC-11 cycle in the ocean starting from the preindustrial period (1938) with observed anthropogenic perturbations of atmospheric CFC-11 to comply with the Ocean Carbon-Cycle Model Intercomparison Project Phase-2 (OCMIP-2) flux protocol. The model results are compared with ship observations as well as the results of candidate models of OCMIP-2 and a performance is assessed. The model simulates the deep-ventilation processes in the Atlantic Ocean appreciably well and yields a good agreement in the column inventory of the CFC-11 amplitude and phase compared to the observation. The statistical skill test shows that this model outperforms other candidate models of OCMIP-2 because of its higher resolution and assimilated offline input feeding, and it shows a potential role in improving transport calculation in the ocean with cost-effective computation.

Background monitoring and long-range transport of atmospheric CFC-11 and CFC-12 at Kosan, Korea.

The background concentrations of atmospheric CFC-11 and CFC-12 were monitored to assess their impact on stratospheric ozone depletion and global warming from September 1995 to March 1999 at Kosan, Korea, located at eastern margin of the Asian Continent. The concentrations of atmospheric CFC-11 at Kosan have decreased slightly, at a rate of -2.5 pptv yr(-1), over the period in response to the Montreal Protocol. The CFC-12 mixing ratio at Kosan continues to increase in the atmosphere at a rate of 5.7 pptv yr(-1) despite international regulations, because of its extreme atmosphere persistence. Recent trends of these two chlorofluorocarbons at Kosan, Korea were concordant with those of the northern hemispheric background monitored unit at Mauna Loa, Hawaii. The maximum seasonal mean mixing ratios of CFC-11 and CFC-12 at Kosan, Korea, were 270 +/- 4 pptv in the spring and 538 +/- 9 pptv in the winter, and the corresponding seasonal minima were 267 +/- 7 and 529 +/- 12 pptv. This occurred in the summer and was due to southeasterly winds from the northwestern Pacific Ocean. By performing a three-day isentropic backward trajectory analysis, it was shown that air masses at Kosan, and with the exception of summer, mainly originated from central and northern China. In particular, the mixing ratios of these two contaminant species are closely related with their air mass trajectories.

Chlorofluorocarbons in the western North Pacific in 1993 and formation of North Pacific intermediate water

Chlorofluorocarbons (CFC-11 and CFC-12) in the intermediate water having σθ between 26.4 and 27.2 were determined at 75 stations in the western North Pacific north of 20°N and west of 175.5°E in 1993. The intermediate water of 26.4–26.6σθ was almost saturated with respect to the present atmospheric CFC-11 in the zone between 35 and 45°N around the subarctic front. Furthermore, the ratios of CFC-11/CFC-12 of the water were also of those formed after 1975. These suggest that the upper intermediate water (26.4–26.6σθ) was recently formed by cooling and sinking of the surface water not by mixing with old waters. The water below the isopycnal surface of 26.8σθ contained less CFCs and the area containing higher CFCs around the subarctic front was greatly reduced. However, the CFC age of the lower intermediate water (26.8–27.2σθ) in the zone around the subarctic front was not old, suggesting that the water was formed by diapycnal mixing of the water ventilated with the atmosphere with old waters not containing appreciable CFCs, probably the Pacific Deep Water. The southward spreading rate decreased with depth and it was one sixth of its eastward spreading rate of the North Pacific Intermediate Water (NPIW).