scholarly journals Online technique for isotope and mixing ratios of CH<sub>4</sub>, N<sub>2</sub>O, Xe and mixing ratios of organic trace gases on a single ice core sample

2014 ◽  
Vol 7 (8) ◽  
pp. 2645-2665 ◽  
Author(s):  
J. Schmitt ◽  
B. Seth ◽  
M. Bock ◽  
H. Fischer

Abstract. Firn and polar ice cores enclosing trace gas species offer a unique archive to study changes in the past atmosphere and in terrestrial/marine source regions. Here we present a new online technique for ice core and air samples to measure a suite of isotope ratios and mixing ratios of trace gas species on a single sample. Isotope ratios are determined on methane, nitrous oxide and xenon with reproducibilities for ice core samples of 0.15‰ for δ13C–CH4, 0.22‰ for δ15N–N2O, 0.34‰ for δ18O–N2O, and 0.05‰ per mass difference for δ136Xe for typical concentrations of glacial ice. Mixing ratios are determined on methane, nitrous oxide, xenon, ethane, propane, methyl chloride and dichlorodifluoromethane with reproducibilities of 7 ppb for CH4, 3 ppb for N2O, 70 ppt for C2H6, 70 ppt for C3H8, 20 ppt for CH3Cl, and 2 ppt for CCl2F2. However, the blank contribution for C2H6 and C3H8 is large in view of the measured values for Antarctic ice samples. The system consists of a vacuum extraction device, a preconcentration unit and a gas chromatograph coupled to an isotope ratio mass spectrometer. CH4 is combusted to CO2 prior to detection while we bypass the oven for all other species. The highly automated system uses only ~ 160 g of ice, equivalent to ~ 16 mL air, which is less than previous methods. The measurement of this large suite of parameters on a single ice sample is new and key to understanding phase relationships of parameters which are usually not measured together. A multi-parameter data set is also key to understand in situ production processes of organic species in the ice, a critical issue observed in many organic trace gases. Novel is the determination of xenon isotope ratios using doubly charged Xe ions. The attained precision for δ136Xe is suitable to correct the isotopic ratios and mixing ratios for gravitational firn diffusion effects, with the benefit that this information is derived from the same sample. Lastly, anomalies in the Xe mixing ratio, δXe/air, can be used to detect melt layers.

2014 ◽  
Vol 7 (3) ◽  
pp. 2017-2069 ◽  
Author(s):  
J. Schmitt ◽  
B. Seth ◽  
M. Bock ◽  
H. Fischer

Abstract. Polar ice cores enclosing trace gas species offer a unique archive to study changes in the past atmosphere and in terrestrial/marine source regions. Here we present a new online technique for ice core and air samples to measure a suite of isotope ratios and mixing ratios of trace gas species on a single small sample. Isotope ratios are determined on methane, nitrous oxide and xenon with reproducibilities for ice core samples of 0.15‰ for δ13C-CH4, 0.22‰ for δ15N-N2O, 0.34 ‰ for δ18O-N2O, and 0.05‰ for δ136Xe. Mixing ratios are determined on methane, nitrous oxide, xenon, ethane, propane, methyl chloride and dichloro-difluoromethane with reproducibilities of 7 ppb for CH4, 3 ppb for N2O, 50 ppt for 136Xe, 70 ppt for C2H6, 70 ppt for C3H8, 20 ppt for CH3Cl, and 2 ppt for CCl2F2. The system consists of a vacuum extraction device, a preconcentration unit and a gas chromatograph coupled to an isotope ratio mass spectrometer. CH4 is combusted to CO2 prior to detection while we bypassed the oven for all other species. The highly automated system uses only ~160 g ice, equivalent to ~16 mL air, which is less than previous methods. This large suite of parameters on a single ice sample is new and helpful to study phase relationships of parameters which are usually not measured together. A multi-parameter dataset is also key to understand in situ production processes of organic species in the ice, a critical issue observable in many organic trace gases. Novel is the determination of xenon isotope ratios using doubly charged Xe ions. The attained precision for δ136Xe is suitable to correct the isotopic ratios and mixing ratios for gravitational firn effects, with the benefit that this information is derived from the same sample. Lastly, anomalies in the Xe mixing ratio, δXe/air, can be used to detect melt layers.


2014 ◽  
Vol 7 (9) ◽  
pp. 10059-10107
Author(s):  
M. J. Alvarado ◽  
V. H. Payne ◽  
K. E. Cady-Pereira ◽  
J. D. Hegarty ◽  
S. S. Kulawik ◽  
...  

Abstract. Errors in the spectroscopic parameters used in the forward radiative transfer model can introduce altitude-, spatially-, and temporally-dependent biases in trace gas retrievals. For well-mixed trace gases such as methane, where the variability of tropospheric mixing ratios is relatively small, reducing such biases is particularly important. We use aircraft observations from all five missions of the HIAPER Pole-to-Pole Observations (HIPPO) of the Carbon Cycle and Greenhouse Gases Study to evaluate the impact of updates to spectroscopic parameters for methane (CH4), water vapor (H2O), and nitrous oxide (N2O) on thermal infrared retrievals of methane from the NASA Aura Tropospheric Emission Spectrometer (TES). We find that updates to the spectroscopic parameters for CH4 result in a substantially smaller mean bias in the retrieved CH4 when compared with HIPPO observations. After an N2O-based correction, the bias in TES methane upper tropospheric representative values for measurements between 50° S and 50° N decreases from 56.9 to 25.7 ppbv, while the bias in the lower tropospheric representative value increases only slightly (from 27.3 to 28.4 ppbv). For retrievals with less than 1.6 DOFS, the bias is reduced from 26.8 to 4.8 ppbv. We also find that updates to the spectroscopic parameters for N2O reduce the errors in the retrieved N2O profile.


2010 ◽  
Vol 10 (1) ◽  
pp. 1631-1657 ◽  
Author(s):  
M. Aydin ◽  
S. A. Montzka ◽  
M. O. Battle ◽  
M. B. Williams ◽  
W. De Bruyn ◽  
...  

Abstract. In this study, we report the first measurements of CFC-12 (CCl2F2) in air extracted from shallow ice cores along with firn air CFC-12 measurements from three Antarctic sites. The firn air data are consistent with the known atmospheric history of CFC-12. In contrast, the ice core samples collected near the firn-ice transition exhibit anomalously high CFC-12 levels. Together, the ice core and firn air data provide evidence for presence of modern air entrapped in shallow ice core samples. We propose that this is due to closure of open pores after drilling, entrapping modern air and resulting in elevated CFC-12 mixing ratios. Our measurements reveal the presence of open porosity below the depth at which firn air samples can be collected and demonstrate how the composition of bubble air in shallow ice cores can be altered during the post-drilling period through purely physical processes. These results have implications for investigations involving trace gas composition of bubbles in shallow ice cores.


2009 ◽  
Vol 2 (5) ◽  
pp. 2689-2705
Author(s):  
Z. Wang ◽  
J. E. Mak

Abstract. A new simultaneous analysis technique for stable isotope ratios (δ13C and δ18O) of atmospheric carbon monoxide (CO) from ice core samples and small air samples is presented, based on an on-line cryogenic vacuum extraction followed by continuous-flow isotope ratio mass spectrometry (CF-IRMS). The CO extraction system includes two multi-loop cryogenic cleanup traps, a chemical oxidant for oxidation to CO2, a cryogenic collection trap, a cryofocusing unit, purification by gas chromatography, and subsequent injection into a Finnigan Delta Plus IRMS. Analytical precision of 0.2‰(±1σ) for δ13C and 0.6‰(±1σ) for δ18O can be obtained for 100 mL (STP) air sample with CO mixing ratio ranging from 60 to 140 ppbv (~268–625 pmol CO). Six South Pole ice core samples with depth ranging from 133 to 177 m are also processed for CO isotope analysis based on a wet extraction line attached to the above cryogenic vacuum system. This is the first report on measuring isotope ratios of CO in ice core samples.


2010 ◽  
Vol 10 (11) ◽  
pp. 5135-5144 ◽  
Author(s):  
M. Aydin ◽  
S. A. Montzka ◽  
M. O. Battle ◽  
M. B. Williams ◽  
W. J. De Bruyn ◽  
...  

Abstract. In this study, we report measurements of CFC-12 (CCl2F2) in firn air and in air extracted from shallow ice cores from three Antarctic sites. The firn air data are consistent with the known atmospheric history of CFC-12. In contrast, some of the ice core samples collected near the firn-ice transition exhibit anomalously high CFC-12 levels. Together, the ice core and firn air data provide evidence for the presence of modern air entrapped in the shallow ice core samples that likely contained open pores at the time of collection. We propose that this is due to closure of the open pores after drilling, entrapping modern air and resulting in elevated CFC-12 mixing ratios. Our results reveal that open porosity can exist below the maximum depth at which firn air samples can be collected, particularly at sites with lower accumulation rates. CFC-12 measurements demonstrate that post-drilling closure of open pores can lead to a change in the composition of bubble air in shallow ice cores through purely physical processes. The results have implications for investigations involving trace gas composition of bubbles in shallow ice cores collected near the firn-ice transition.


2010 ◽  
Vol 3 (5) ◽  
pp. 1307-1317 ◽  
Author(s):  
Z. Wang ◽  
J. E. Mak

Abstract. We present a new analysis technique for stable isotope ratios (δ13C and δ18O) of atmospheric carbon monoxide (CO) from ice core samples. The technique is an online cryogenic vacuum extraction followed by continuous-flow isotope ratio mass spectrometry (CF-IRMS); it can also be used with small air samples. The CO extraction system includes two multi-loop cryogenic cleanup traps, a chemical oxidant for oxidation to CO2, a cryogenic collection trap, a cryofocusing unit, gas chromatography purification, and subsequent injection into a Finnigan Delta Plus IRMS. Analytical precision of 0.2‰ (±1δ) for δ13C and 0.6‰ (±1δ) for δ18O can be obtained for 100 mL (STP) air samples with CO mixing ratios ranging from 60 ppbv to 140 ppbv (~268–625 pmol CO). Six South Pole ice core samples from depths ranging from 133 m to 177 m were processed for CO isotope analysis after wet extraction. To our knowledge, this is the first measurement of stable isotopes of CO in ice core air.


2019 ◽  
Author(s):  
Heiko Bozem ◽  
Peter Hoor ◽  
Daniel Kunkel ◽  
Franziska Köllner ◽  
Johannes Schneider ◽  
...  

Abstract. The springtime composition of the Arctic lower troposphere is to a large extent controlled by transport of mid-latitude air masses into the Arctic, whereas during the summer precipitation and natural sources play the most important role. Within the Arctic region, there exists a transport barrier, known as the polar dome, which results from sloping isentropes. The polar dome, which varies in space and time, exhibits a strong influence on the transport of air masses from mid-latitudes, enhancing it during winter and inhibiting it during summer. Furthermore, a definition for the location of the polar dome boundary itself is quite sparse in the literature. We analyzed aircraft based trace gas measurements in the Arctic during two NETCARE airborne field camapigns (July 2014 and April 2015) with the Polar 6 aircraft of Alfred Wegener Institute Helmholtz Center for Polar and Marine Research (AWI), Bremerhaven, Germany, covering an area from Spitsbergen to Alaska (134° W to 17° W and 68° N to 83° N). For the spring (April 2015) and summer (July 2014) season we analyzed transport regimes of mid-latitude air masses travelling to the high Arctic based on CO and CO2 measurements as well as kinematic 10-day back trajectories. The dynamical isolation of the high Arctic lower troposphere caused by the transport barrier leads to gradients of chemical tracers reflecting different local chemical life times and sources and sinks. Particularly gradients of CO and CO2 allowed for a trace gas based definition of the polar dome boundary for the two measurement periods with pronounced seasonal differences. For both campaigns a transition zone rather than a sharp boundary was derived. For July 2014 the polar dome boundary was determined to be 73.5° N latitude and 299–303.5 K potential temperature, respectively. During April 2015 the polar dome boundary was on average located at 66–68.5° N and 283.5–287.5 K. Tracer-tracer scatter plots and probability density functions confirm different air mass properties inside and outside of the polar dome for the July 2014 and April 2015 data set. Using the tracer derived polar dome boundaries the analysis of aerosol data indicates secondary aerosol formation events in the clean summertime polar dome. Synoptic-scale weather systems frequently disturb this transport barrier and foster exchange between air masses from midlatitudes and polar regions. During the second phase of the NETCARE 2014 measurements a pronounced low pressure system south of Resolute Bay brought inflow from southern latitudes that pushed the polar dome northward and significantly affected trace gas mixing ratios in the measurement region. Mean CO mixing ratios increased from 77.9 ± 2.5 ppbv to 84.9 ± 4.7 ppbv from the first period to the second period. At the same time CO2 mixing ratios significantly dropped from 398.16 ± 1.01 ppmv to 393.81 ± 2.25 ppmv. We further analysed processes controlling the recent transport history of air masses within and outside the polar dome. Air masses within the spring time polar dome mainly experienced diabatic cooling while travelling over cold surfaces. In contrast air masses in the summertime polar dome were diabatically heated due to insolation. During both seasons air masses outside the polar dome slowly descended into the Arctic lower troposphere from above caused by radiative cooling. The ascent to the middle and upper troposphere mainly took place outside the Arctic, followed by a northward motion. Our results demonstrate the successful application of a tracer based diagnostic to determine the location of the polar dome boundary.


2015 ◽  
Vol 15 (21) ◽  
pp. 30473-30509
Author(s):  
E. Schlosser ◽  
B. Stenni ◽  
M. Valt ◽  
A. Cagnati ◽  
J. G. Powers ◽  
...  

Abstract. At the East Antarctic deep ice core drilling site Dome C, daily precipitation measurements have been initiated in 2006 and are being continued until today. The amounts and stable isotope ratios of the precipitation samples as well as crystal types are determined. Within the measuring period, the two years 2009 and 2010 showed striking contrasting temperature and precipitation anomalies, particularly in the winter seasons. The reasons for these anomalies and their relation to stable isotope ratios are analysed using data from the mesoscale atmospheric model WRF (Weather Research and Forecasting Model) run under the Antarctic Mesoscale Prediction System (AMPS). 2009 was relatively warm and moist due to frequent warm air intrusions connected to amplification of Rossby waves in the circumpolar westerlies, whereas the winter of 2010 was extremely dry and cold. It is shown that while in 2010 a strong zonal atmospheric flow was dominant, in 2009 an enhanced meridional flow prevailed, which increased the meridional transport of heat and moisture onto the East Antarctic plateau and led to a number of high-precipitation/warming events at Dome C. This was also evident in a positive (negative) SAM index and a negative (positive) ZW3 index during the winter months of 2010 (2009). Changes in the frequency or seasonality of such event-type precipitation can lead to a strong bias in the air temperature derived from stable water isotopes in ice cores.


2021 ◽  
Author(s):  
Simone M. Pieber ◽  
Dac-Loc Nguyen ◽  
Hendryk Czech ◽  
Stephan Henne ◽  
Nicolas Bukowiecki ◽  
...  

&lt;p&gt;Open biomass burning (BB) is a globally widespread phenomenon. The fires release pollutants, which are harmful for human and ecosystem health and alter the Earth's radiative balance. Yet, the impact of various types of BB on the global radiative forcing remains poorly constrained concerning greenhouse gas emissions, BB organic aerosol (OA) chemical composition and related light absorbing properties. Fire emissions composition is influenced by multiple factors (e.g., fuel and thereby vegetation-type, fuel moisture, fire temperature, available oxygen). Due to regional variations in these parameters, studies in different world regions are needed. Here we investigate the influence of seasonally recurring BB on trace gas concentration and air quality at the regional Global Atmosphere Watch (GAW) station Pha Din (PDI) in rural Northwestern Vietnam. PDI is located in a sparsely populated area on the top of a hill (1466 m a.s.l.) and is well suited to study the large-scale fires on the Indochinese Peninsula, whose pollution plumes are frequently transported towards the site [1]. We present continuous trace gas observations of CO&lt;sub&gt;2&lt;/sub&gt;, CH&lt;sub&gt;4&lt;/sub&gt;, CO, and O&lt;sub&gt;3&lt;/sub&gt; conducted at PDI since 2014 and interpret the data with atmospheric transport simulations. Annually recurrent large scale BB leads to hourly time-scale peaks CO mixing ratios at PDI of 1000 to 1500 ppb around every April since the start of data collection in 2014. We complement this analysis with carbonaceous PM&lt;sub&gt;2.5 &lt;/sub&gt;chemical composition analyzed during an intensive campaign in March-April 2015. This includes measurements of elemental and organic carbon (EC/OC) and more than 50 organic markers, such as sugars, PAHs, fatty acids and nitro-aromatics [2]. For the intensive campaign, we linked CO, CO&lt;sub&gt;2&lt;/sub&gt;, CH&lt;sub&gt;4&lt;/sub&gt; and O&lt;sub&gt;3&lt;/sub&gt; mixing ratios to a statistical classification of BB events, which is based on OA composition. We found increased CO and O&lt;sub&gt;3&lt;/sub&gt; levels during medium and high BB influence during the intensive campaign. A backward trajectory analysis confirmed different source regions for the identified periods based on the OA cluster. Typically, cleaner air masses arrived from northeast, i.e., mainland China and Yellow sea during the intensive campaign. The more polluted periods were characterized by trajectories from southwest, with more continental recirculation of the medium cluster, and more westerly advection for the high cluster. These findings highlight that BB activities in Northern Southeast Asia significantly enhances the regional OA loading, chemical PM&lt;sub&gt;2.5 &lt;/sub&gt;composition and the trace gases in northwestern Vietnam. The presented analysis adds valuable data on air quality in a region of scarce data availability.&lt;/p&gt;&lt;p&gt;&amp;#160;&lt;/p&gt;&lt;p&gt;&lt;strong&gt;REFERENCES&lt;/strong&gt;&lt;/p&gt;&lt;p&gt;[1] Bukowiecki, N. et al. Effect of Large-scale Biomass Burning on Aerosol Optical Properties at the GAW Regional Station Pha Din, Vietnam. AAQR. 19, 1172&amp;#8211;1187 (2019).&lt;/p&gt;&lt;p&gt;[2] Nguyen, D. L, et al. Carbonaceous aerosol composition in air masses influenced by large-scale biomass burning: a case-study in Northwestern Vietnam. ACPD., https://doi.org/10.5194/acp-2020-1027, in review, 2020.&lt;/p&gt;


2019 ◽  
Vol 12 (8) ◽  
pp. 4149-4169 ◽  
Author(s):  
Jan-Marcus Nasse ◽  
Philipp G. Eger ◽  
Denis Pöhler ◽  
Stefan Schmitt ◽  
Udo Frieß ◽  
...  

Abstract. Over the last few decades, differential optical absorption spectroscopy (DOAS) has been used as a common technique to simultaneously measure abundances of a variety of atmospheric trace gases. Exploiting the unique differential absorption cross section of trace-gas molecules, mixing ratios can be derived by measuring the optical density along a defined light path and by applying the Beer–Lambert law. Active long-path (LP-DOAS) instruments can detect trace gases along a light path of a few hundred metres up to 20 km, with sensitivities for mixing ratios down to ppbv and pptv levels, depending on the trace-gas species. To achieve high measurement accuracy and low detection limits, it is crucial to reduce instrumental artefacts that lead to systematic structures in the residual spectra of the analysis. Spectral residual structures can be introduced by most components of a LP-DOAS measurement system, namely by the light source, in the transmission of the measurement signal between the system components or at the level of spectrometer and detector. This article focuses on recent improvements by the first application of a new type of light source and consequent changes to the optical setup to improve measurement accuracy. Most state-of-the-art LP-DOAS instruments are based on fibre optics and use xenon arc lamps or light-emitting diodes (LEDs) as light sources. Here we present the application of a laser-driven light source (LDLS), which significantly improves the measurement quality compared to conventional light sources. In addition, the lifetime of LDLS is about an order of magnitude higher than of typical Xe arc lamps. The small and very stable plasma discharge spot of the LDLS allows the application of a modified fibre configuration. This enables a better light coupling with higher light throughput, higher transmission homogeneity, and a better suppression of light from disturbing wavelength regions. Furthermore, the mode-mixing properties of the optical fibre are enhanced by an improved mechanical treatment. The combined effects lead to spectral residual structures in the range of 5-10×10-5 root mean square (rms; in units of optical density). This represents a reduction of detection limits of typical trace-gas species by a factor of 3–4 compared to previous setups. High temporal stability and reduced operational complexity of this new setup allow the operation of low-maintenance, automated LP-DOAS systems, as demonstrated here by more than 2 years of continuous observations in Antarctica.


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