The Development and Application of a New High Precision GC-IRMS Technique for N2O-Free Isotopic Analysis of Atmospheric CO2

<p>A new GC-IRMS technique has been developed for isotopic and mixing ratio analysis of atmospheric CO2. The technique offers for the first time, N2O-free, high precision (<0.05 [per mil]) analysis of d13C and d18O from small whole-air samples. On-line GC separation of CO2 and N2O from these small samples is combined with IRMS under elevated ion source pressures. A specialised open split interface is an integral part of the inlet system and ensures a continuous flow of either sample gas or pure helium to the IRMS. The analysis, including all flushing, uses a total of 45 ml of an air sample collected at ambient pressure. Of this, three 0.5 ml aliquots are injected onto the GC column, each providing [approximately] 0.8 nmol CO2 in the IRMS source. At this sample size, d13C precision obtained is at the theoretical shot-noise limit. Demonstrated precisions for d13C, d18O, and CO2 mixing ratio (all measured simultaneously)are 0.02 [per mil], 0.04 [per mil] and 0.4 ppm respectively. The initial results from an inter calibration exercise with Atmospheric Research at the Commonwealth Scientific and Industrial Research Organisation (CSIRO), Australia achieved the International Atomic Energy Agency (IAEA) target precision for d13C. During this exercise, agreement for d18O and CO2 mixing ratio was outside the IAEA and World Meteorological Organization (WMO) target precisions for these species, however, when the measurement uncertainties of the two laboratories were considered, the differences were not significant. An inter comparison program using air samples collected at Baring Head, New Zealand and Cape Grim, Australia was also established with CSIRO and d13C, d18O and CO2 mixing ratio showed excellent agreement when combined measurement uncertainties were considered. Further inter comparisons with the Carbon Cycle Group at the National Oceanic and Atmospheric Administration Climate Monitoring and Diagnostics Laboratory (NOAA CMDL), the Institute of Arctic and Alpine Research (INSTAAR), and Scripps Institution of Oceanography (SIO) were also established. No significant differences for d13C were observed during these inter comparison programs. Therefore, these preliminary measurements suggest that the current situation between these laboratories for d13C comparisons from whole-air in glass flasks may be improved compared to the 1995 IAEA inter comparison from whole-air in high-pressure cylinders. Following these inter calibration and inter comparison exercises, temporal and spatial variations in the mixing ratio and isotopic composition of atmospheric CO2 were determined over a large region of the Pacific Ocean to demonstrate the successful use of the GC-IRMS technique. Temporal variations were observed at long-term monitoring sites in the Southern Hemisphere (Baring Head, Cape Grim, and Arrival Heights, Ross Island, Antarctica). Seasonal cycles of CO2 mixing ratio and d13C, with amplitudes of [approximately] 1 ppm and [approximately] 0.05 [per mil] respectively, were measured at Baring Head. A decline in d13C of [approximately] -0.1 [per mil]/year was observed at Arrival Heights between 1997 and 1999. Spatial variations in the Pacific Ocean were investigated by shipboard sampling programs between [approximately] 62 degrees S and [approximately] 32 degrees N. These data were consistent with a Southern Ocean sink between [approximately] 43 degrees S and [approximately] 57 degrees S. In addition, inter hemispheric gradients of d13C and CO2 mixing ratio in March and September 1998 were determined and the position and intensity of the SPCZ and ITCZ were important for the strength of these inter hemispheric gradients. Measurements performed during an upper tropospheric flight from New Zealand, to Antarctica show elevated CO2 levels and depleted d13C compared to samples obtained in the marine boundary layer over this region. A small-scale application of the technique measured soil-respired CO2 in a New Zealand Mountain Beech forest from 150 ml sample flasks that were filled to ambient pressure. These measurements determined a difference between the d13C source signature from the young and old trees of [approximately] 0.3 [per mil], which was in the correct direction but of smaller magnitude than that expected. The small sample requirements of the GC-IRMS technique ease sample collection logistics for varied research. Since initial results from an inter calibration exercise with CSIRO obtain the IAEA target precision for d13C and the technique has demonstrated its ability to successfully monitor atmospheric CO2 species from small whole-air samples, without contamination by atmospheric N2O or the use of cryogen, the technique will be a powerful tool in global carbon cycle research.</p>

The Development and Application of a New High Precision GC-IRMS Technique for N2O-Free Isotopic Analysis of Atmospheric CO2

<p>A new GC-IRMS technique has been developed for isotopic and mixing ratio analysis of atmospheric CO2. The technique offers for the first time, N2O-free, high precision (<0.05 [per mil]) analysis of d13C and d18O from small whole-air samples. On-line GC separation of CO2 and N2O from these small samples is combined with IRMS under elevated ion source pressures. A specialised open split interface is an integral part of the inlet system and ensures a continuous flow of either sample gas or pure helium to the IRMS. The analysis, including all flushing, uses a total of 45 ml of an air sample collected at ambient pressure. Of this, three 0.5 ml aliquots are injected onto the GC column, each providing [approximately] 0.8 nmol CO2 in the IRMS source. At this sample size, d13C precision obtained is at the theoretical shot-noise limit. Demonstrated precisions for d13C, d18O, and CO2 mixing ratio (all measured simultaneously)are 0.02 [per mil], 0.04 [per mil] and 0.4 ppm respectively. The initial results from an inter calibration exercise with Atmospheric Research at the Commonwealth Scientific and Industrial Research Organisation (CSIRO), Australia achieved the International Atomic Energy Agency (IAEA) target precision for d13C. During this exercise, agreement for d18O and CO2 mixing ratio was outside the IAEA and World Meteorological Organization (WMO) target precisions for these species, however, when the measurement uncertainties of the two laboratories were considered, the differences were not significant. An inter comparison program using air samples collected at Baring Head, New Zealand and Cape Grim, Australia was also established with CSIRO and d13C, d18O and CO2 mixing ratio showed excellent agreement when combined measurement uncertainties were considered. Further inter comparisons with the Carbon Cycle Group at the National Oceanic and Atmospheric Administration Climate Monitoring and Diagnostics Laboratory (NOAA CMDL), the Institute of Arctic and Alpine Research (INSTAAR), and Scripps Institution of Oceanography (SIO) were also established. No significant differences for d13C were observed during these inter comparison programs. Therefore, these preliminary measurements suggest that the current situation between these laboratories for d13C comparisons from whole-air in glass flasks may be improved compared to the 1995 IAEA inter comparison from whole-air in high-pressure cylinders. Following these inter calibration and inter comparison exercises, temporal and spatial variations in the mixing ratio and isotopic composition of atmospheric CO2 were determined over a large region of the Pacific Ocean to demonstrate the successful use of the GC-IRMS technique. Temporal variations were observed at long-term monitoring sites in the Southern Hemisphere (Baring Head, Cape Grim, and Arrival Heights, Ross Island, Antarctica). Seasonal cycles of CO2 mixing ratio and d13C, with amplitudes of [approximately] 1 ppm and [approximately] 0.05 [per mil] respectively, were measured at Baring Head. A decline in d13C of [approximately] -0.1 [per mil]/year was observed at Arrival Heights between 1997 and 1999. Spatial variations in the Pacific Ocean were investigated by shipboard sampling programs between [approximately] 62 degrees S and [approximately] 32 degrees N. These data were consistent with a Southern Ocean sink between [approximately] 43 degrees S and [approximately] 57 degrees S. In addition, inter hemispheric gradients of d13C and CO2 mixing ratio in March and September 1998 were determined and the position and intensity of the SPCZ and ITCZ were important for the strength of these inter hemispheric gradients. Measurements performed during an upper tropospheric flight from New Zealand, to Antarctica show elevated CO2 levels and depleted d13C compared to samples obtained in the marine boundary layer over this region. A small-scale application of the technique measured soil-respired CO2 in a New Zealand Mountain Beech forest from 150 ml sample flasks that were filled to ambient pressure. These measurements determined a difference between the d13C source signature from the young and old trees of [approximately] 0.3 [per mil], which was in the correct direction but of smaller magnitude than that expected. The small sample requirements of the GC-IRMS technique ease sample collection logistics for varied research. Since initial results from an inter calibration exercise with CSIRO obtain the IAEA target precision for d13C and the technique has demonstrated its ability to successfully monitor atmospheric CO2 species from small whole-air samples, without contamination by atmospheric N2O or the use of cryogen, the technique will be a powerful tool in global carbon cycle research.</p>

First ground-based FTIR observations of HFC-23 at Rikubetsu, Japan, and Syowa Station, Antarctica

We have developed a procedure for retrieving atmospheric abundances of HFC-23 (CHF3) with a ground-based Fourier transform infrared spectrometer (FTIR) and analysed the spectra observed at Rikubetsu, Japan (43.5° N, 143.8° E), and at Syowa Station, Antarctica (69.0° S, 39.6° E). The FTIR retrievals were carried out with the SFIT4 retrieval program, and the two spectral windows of 1138.5–1148.0 cm−1 and 1154.0–1160.0 cm−1 in the overlapping ν2 and ν5 vibrational-rotational transition bands of HFC-23 were used to avoid strong H2O absorption features. We considered O3, N2O, CH4, H2O, HDO, CFC-12 (CCl2F2), HCFC-22 (CHClF2), PAN (CH3C(O)OONO2), HCFC-141b (CH3CCl2F), and HCFC-142b (CH3CClF2) as interfering species. Vertical profiles of H2O, HDO, and CH4 are preliminarily retrieved with other independent spectral windows because these profiles may induce large uncertainties in the HFC-23 retrieval. Each HFC-23 retrieval has only one piece of vertical information with sensitivity to HFC-23 in the troposphere and the lower stratosphere. The retrieval errors mainly arise from the systematic uncertainties of the spectroscopic parameters used to obtain the HFC-23, H2O, HDO, and CH4 abundances. For comparison between FTIR-retrieved HFC-23 total columns and surface dry-air mole fractions provided by AGAGE (Advanced Global Atmospheric Gases Experiment), the FTIR-retrieved HFC-23 dry-air column-averaged mole fractions (XHFC-23) were calculated. The FTIR-retrieved XHFC-23 at Rikubetsu and Syowa Station have negative biases compared to AGAGE datasets. The trend derived from the FTIR-retrieved XHFC-23 data at Rikubetsu for December to February (DJF) data over the 1997–2010 period is 0.817 ± 0.087 ppt (parts per trillion) year−1, which is in good agreement with the trend derived from the annual global mean datasets of the AGAGE 12-box model for the same period (0.820 ± 0.011 ppt year−1). The trend of the FTIR-retrieved XHFC-23 data at Rikubetsu for DJF data over the 2007–2020 period is 0.894 ± 0.099 ppt year−1, which is smaller than the trend in the AGAGE in-situ measurements at Trinidad Head (41.1° N, 124.2° W) for the 2007–2019 period (0.984 ± 0.002 ppt year−1). The trend computed from the XHFC-23 datasets at Syowa Station over the 2007–2016 period is 0.823 ± 0.075 ppt year−1, which is consistent with that derived from the AGAGE in-situ measurements at Cape Grim (40.7° S, 144.7° E) for the same period (0.874 ± 0.002 ppt year−1). Although there are systematic biases on the FTIR-retrieved XHFC-23 at both sites, these results indicate that ground-based FTIR observations have the capability to monitor the trend of atmospheric HFC-23.

Trends and emissions of six perfluorocarbons in the Northern Hemisphere and Southern Hemisphere

Perfluorocarbons (PFCs) are potent greenhouse gases with global warming potentials up to several thousand times greater than CO2 on a 100-year time horizon. The lack of any significant sinks for PFCs means that they have long atmospheric lifetimes of the order of thousands of years. Anthropogenic production is thought to be the only source for most PFCs. Here we report an update on the global atmospheric abundances of the following PFCs, most of which have for the first time been analytically separated according to their isomers: c-octafluorobutane (c-C4F8), n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14), and n-hexadecafluoroheptane (n-C7F16). Additionally, we report the first data set on the atmospheric mixing ratios of perfluoro-2-methylpentane (i-C6F14). The existence and significance of PFC isomers have not been reported before, due to the analytical challenges of separating them. The time series spans a period from 1978 to the present. Several data sets are used to investigate temporal and spatial trends of these PFCs: time series of air samples collected at Cape Grim, Australia, from 1978 to the start of 2018; a time series of air samples collected between July 2015 and April 2017 at Tacolneston, UK; and intensive campaign-based sampling collections from Taiwan. Although the remote “background” Southern Hemispheric Cape Grim time series indicates that recent growth rates of most of these PFCs are lower than in the 1990s, we continue to see significantly increasing mixing ratios that are between 6 % and 27 % higher by the end of 2017 compared to abundances measured in 2010. Air samples from Tacolneston show a positive offset in PFC mixing ratios compared to the Southern Hemisphere baseline. The highest mixing ratios and variability are seen in air samples from Taiwan, which is therefore likely situated much closer to PFC sources, confirming predominantly Northern Hemispheric emissions for most PFCs. Even though these PFCs occur in the atmosphere at levels of parts per trillion molar or less, their total cumulative global emissions translate into 833 million metric tonnes of CO2 equivalent by the end of 2017, 23 % of which has been emitted since 2010. Almost two-thirds of the CO2 equivalent emissions within the last decade are attributable to c-C4F8, which currently also has the highest emission rates that continue to grow. Sources of all PFCs covered in this work remain poorly constrained and reported emissions in global databases do not account for the abundances found in the atmosphere.

Trends and Emissions of Six Perfluorocarbons in the Northern and Southern Hemisphere

Perfluorocarbons (PFCs) are potent greenhouse gases with Global Warming Potentials up to several thousand times greater than CO2 on a 100-year time horizon. The lack of any significant sinks for PFCs means that they have long atmospheric lifetimes on the order of thousands of years. Anthropogenic production is thought to be the only source for most PFCs. Here we report an update on the global atmospheric abundances of the following PFCs, most of which have for the first time been separated according to their isomers: c-octafluorobutane (c-C4F8), n-decafluorobutane (n-C4F10), n-dodecafluoropentane (n-C5F12), n-tetradecafluorohexane (n-C6F14), and n-hexadecafluoroheptane (n-C7F16). Additionally, we report the first data set on the atmospheric mixing ratios of perfluoro(2-methylpentane) (i-C6F14). The existence and significance of PFC isomers has not been reported before, due to the analytical challenges of separating them. The time series spans a period from 1978 to the present. Several datasets are used to investigate temporal and spatial trends of these PFCs: time series of air samples collected at Cape Grim, Australia, from 1978 to the start of 2018; a time series of air samples collected between July 2015 and April 2017 at Tacolneston, UK; and intensive campaign-based sampling collections from Taiwan. Although the remote background Southern Hemispheric Cape Grim time series indicates that recent growth rates of most of these PFCs are lower than in the 1990s, we continue to see significantly increasing mixing ratios that are between 6 % to 27 % higher by the end of 2017 compared to abundances measured in 2010. Air samples from Tacolneston show a positive offset in PFC mixing ratios compared to the Southern Hemisphere baseline. The highest mixing ratios and variability are seen in air samples from Taiwan, which is therefore likely situated much closer to PFC sources, confirming predominantly Northern Hemispheric emissions for most PFCs. Even though these PFCs occur in the atmosphere at levels of parts per trillion molar or less, their total cumulative global emissions translate into 833 million metric tonnes of CO2 equivalent by the end of 2017, 23 % of which has been emitted in the last eight years. Almost two-thirds of the CO2 equivalent emissions are attributable to c-C4F8, which currently also has the highest emission rates that continue to grow. Despite this, the sources of all PFCs covered in this work remain poorly constrained and reported emissions in global databases do not account for the abundances found in the atmosphere.

Abundances, emissions, and loss processes of the long-lived and potent greenhouse gas octafluorooxolane (octafluorotetrahydrofuran, <i>c</i>-C₄F₈O) in the atmosphere

The first observations of octafluorooxolane (octafluorotetrahydrofuran, c-C4F8O), a persistent greenhouse gas, in the atmosphere are reported. In addition, a complimentary laboratory study of its most likely atmospheric loss processes and infrared absorption spectrum and global warming potential (GWP) are reported. First atmospheric measurements of c-C4F8O are provided from the Cape Grim Air Archive (41° S, Tasmania, Australia, 1978–present), supplemented by two firn air samples from Antarctica, in situ measurements of ambient air at Aspendale, Victoria (38° S), and a few archived air samples from the Northern Hemisphere. Atmospheric abundances in the Southern Hemisphere have reached 74 ppq (parts per quadrillion, femtomol mol-1 in dry air) by 2017. However its growth rate has decreased from a maximum in 2004 of 4.3 ppq yr-1 to

Determining the link between hygroscopicity and composition for semi-volatile aerosol species

Internally and externally mixed aerosols present significant challenges in assessing the hygroscopicity of each aerosol component. This study presents a new sampling technique which uses differences in volatility to separate mixtures and directly examine their respective composition and hygroscopic contribution. A shared thermodenuder and unheated bypass line are continuously cycled between an aerosol mass spectrometer and a volatility and hygroscopicity tandem differential mobility analyser, allowing real-time comparative analysis of heated and unheated aerosol properties. Measurements have been taken of both chamber-generated secondary organic aerosol and coastal marine aerosol at Cape Grim, Australia, to investigate system performance under diverse conditions. Despite rapidly changing aerosol properties and the need to restrict analysis to a narrow size range, the former experiment separated the hygroscopic influences of ammonium sulfate and two distinct organic components with similar oxygen to carbon ratios but different volatilities. Analysis of the marine aerosol revealed an external mixture of non-sea-salt sulfates and sea spray aerosol, which likely shared similar volatile fractions composed of sulfuric acid and a non-hygroscopic organic component.

Determining the link between hygroscopicity and composition for semi-volatile aerosol species

Internally and externally mixed aerosols present significant challenges in assessing the hygroscopicity of each aerosol component. This study presents a new sampling technique which uses differences in volatility to separate mixtures and directly examine their respective composition and hygroscopic contribution. A shared thermodenuder and unheated bypass line are continuously cycled between an aerosol mass spectrometer and a volatility and hygroscopicity tandem differential mobility analyser, allowing real-time comparative analysis of heated and unheated aerosol properties. Measurements have been taken of both chamber-generated secondary organic aerosol and coastal marine aerosol at Cape Grim, Australia, to investigate system performance under diverse conditions. Despite rapidly changing aerosol properties and the need to restrict analysis to a narrow size-range, the former experiment separated the hygroscopic influences of ammonium sulfate and two distinct organic components with similar oxygen to carbon ratios but different volatilities. Analysis of the marine aerosol revealed an external mixture of non-sea salt sulfates and sea spray aerosol, both of which likely shared similar volatile fractions composed of sulfuric acid and a non-hygroscopic organic component.

Sixty years of radiocarbon dioxide measurements at Wellington, New Zealand: 1954–2014

We present 60 years of Δ14CO2 measurements from Wellington, New Zealand (41° S, 175° E). The record has been extended and fully revised. New measurements have been used to evaluate the existing record and to replace original measurements where warranted. This is the earliest direct atmospheric Δ14CO2 record and records the rise of the 14C bomb spike and the subsequent decline in Δ14CO2 as bomb 14C moved throughout the carbon cycle and increasing fossil fuel CO2 emissions further decreased atmospheric Δ14CO2. The initially large seasonal cycle in the 1960s reduces in amplitude and eventually reverses in phase, resulting in a small seasonal cycle of about 2 ‰ in the 2000s. The seasonal cycle at Wellington is dominated by the seasonality of cross-tropopause transport and differs slightly from that at Cape Grim, Australia, which is influenced by anthropogenic sources in winter. Δ14CO2 at Cape Grim and Wellington show very similar trends, with significant differences only during periods of known measurement uncertainty. In contrast, similar clean-air sites in the Northern Hemisphere show a higher and earlier bomb 14C peak, consistent with a 1.4-year interhemispheric exchange time. From the 1970s until the early 2000s, the Northern and Southern Hemisphere Δ14CO2 were quite similar, apparently due to the balance of 14C-free fossil fuel CO2 emissions in the north and 14C-depleted ocean upwelling in the south. The Southern Hemisphere sites have shown a consistent and marked elevation above the Northern Hemisphere sites since the early 2000s, which is most likely due to reduced upwelling of 14C-depleted and carbon-rich deep waters in the Southern Ocean, although an underestimate of fossil fuel CO2 emissions or changes in biospheric exchange are also possible explanations. This developing Δ14CO2 interhemispheric gradient is consistent with recent studies that indicate a reinvigorated Southern Ocean carbon sink since the mid-2000s and suggests that the upwelling of deep waters plays an important role in this change.