--------------------------------------------------------------------- Atmospheric Carbon Dioxide Dry Air Mole Fractions from the NOAA GML Carbon Cycle Cooperative Global Air Sampling Network, 1968-2020 Version: 2021-07-30 -------------------------------------------------------------------- CONTENTS 1. Data source and contacts 2. Use of data 2.1 Citation 3. Reciprocity 4. Warnings 5. Update notes 6. Introduction 7. DATA - General Comments 7.1 DATA - Sampling Locations 7.2 DATA - File Name Description 7.3 DATA - File Types 7.4 DATA - Content 7.5 DATA - QC Flags 8. Data retrieval 9. References -------------------------------------------------------------------- 1. DATA SOURCE AND CONTACTS National Oceanic and Atmospheric Administration (NOAA) Global Monitoring Laboratory (GML) Carbon Cycle Greenhouse Gases (CCGG) Correspondence concerning these data should be directed to: Edward J. Dlugokencky or Xin (Lindsay) Lan NOAA Global Monitoring Laboratory 325 Broadway, R/GML-1 Boulder, CO 80305 U.S.A. email: Xin.Lan@noaa.gov Ed.Dlugokencky@noaa.gov Pieter.Tans@noaa.gov -------------------------------------------------------------------- 2. USE OF DATA These data are made freely available to the public and the scientific community in the belief that their wide dissemination will lead to greater understanding and new scientific insights. The availability of these data does not constitute publication of the data. NOAA relies on the ethics and integrity of the user to ensure that GML receives fair credit for their work. If the data are obtained for potential use in a publication or presentation, GML should be informed at the outset of the nature of this work. If the GML data are essential to the work, or if an important result or conclusion depends on the GML data, co-authorship may be appropriate. This should be discussed at an early stage in the work. Manuscripts using the GML data should be sent to GML for review before they are submitted for publication so we can ensure that the quality and limitations of the data are accurately represented. 2.1 CITATION Please reference these data as Dlugokencky, E.J., J.W. Mund, A.M. Crotwell, M.J. Crotwell, and K.W. Thoning (2021), Atmospheric Carbon Dioxide Dry Air Mole Fractions from the NOAA GML Carbon Cycle Cooperative Global Air Sampling Network, 1968-2020, Version: 2021-07-30, https://doi.org/10.15138/wkgj-f215 -------------------------------------------------------------------- 3. RECIPROCITY Use of these data implies an agreement to reciprocate. Laboratories making similar measurements agree to make their own data available to the general public and to the scientific community in an equally complete and easily accessible form. Modelers are encouraged to make available to the community, upon request, their own tools used in the interpretation of the GML data, namely well documented model code, transport fields, and additional information necessary for other scientists to repeat the work and to run modified versions. Model availability includes collaborative support for new users of the models. -------------------------------------------------------------------- 4. WARNINGS Every effort is made to produce the most accurate and precise measurements possible. However, we reserve the right to make corrections to the data based on recalibration of standard gases or for other reasons deemed scientifically justified. We are not responsible for results and conclusions based on use of these data without regard to this warning. -------------------------------------------------------------------- 5. UPDATE NOTES +++++++++++++++++++++++++++++++ Lab-wide notes: 2011-10-07 We introduced the term "measurement group", which identifies the group within NOAA and Institute of Arctic and Alpine Research (INSTAAR) University of Colorado Boulder that made the measurement. We can now have multiple groups measuring some of the same trace gas species in our discrete samples. Measurement groups within NOAA and INSTAAR are ccgg: NOAA Carbon Cycle Greenhouse Gases group (CCGG) hats: NOAA Halocarbons and other Atmospheric Trace Species group (HATS) arl: INSTAAR Atmospheric Research Laboratory (ARL) sil: INSTAAR Stable Isotope Laboratory (SIL) curl: INSTAAR Laboratory for Radiocarbon Preparation and Research (CURL) We also changed the file naming convention (see section "DATA - FILE NAME DESCRIPTION"). +++++++++++++++++++++++++++++++ Project-specific notes: 2021-07-29 In 2020, the COVID-19 pandemic impacted flask shipping and sampling frequency at many sites causing isolated gaps and some delayed processing into the 2nd half of 2021. In spite of this, network sampling coverage remained reasonably good throughout the year. 2021-07-28 In 2020, the covid-19 pandemic impacted flask shipping and sampling frequency differently for different sites. For the most part and thanks to everyone's efforts, the network sampling coverage remained quite good in 2020. Several sites still have samples from 2020 on site and they will be analyzed once received. 2019-07-15 Surface flask event data is now provided in self describing NetCDF and ASCII text formats with improved metadata. See section 7.3 for details. We will provide a zip download of legacy text formatted files for a transitional period. Monthly means data continues to be provided in text format. 2017-07-27 Method codes and sample locations were edited for accuracy. Edited sites are: ZEP, BKT, OXK, CGO, RPB, ASC, CHR, ICE, KEY, KUM, and TAP 2016-08-26 Latitude and longitude were adjusted for 3 sites: ALT Old: 82.4508 -62.5056 205.00 200.00 New: 82.4508 -62.5072 195.00 190.00 TAC Old: 52.5178 1.1389 236.00 56.00 New: 52.5177 1.1386 236.00 56.00 ZEP Old: 78.9067 11.8889 479.00 474.00 New: 78.9067 11.8883 479.00 474.00 Collaborator name corrected for UTA: Old: U.S. National Weather Service [NWS] New: Beth Anderson/NWS Cooperative Observer 2016-07-07 Incorrect sample dates from Ulaan Uul, Mogolia (UUM) from 20 Aug. 2013 through 30 Sept. 2015 were corrected on 13 May 2016. 2016-07-07 Since 24 Jan 2015, air samples from Negev Desert, Isreal (WIS) are collected at 29.9731N, 35.0567E, 156 masl; the old location was 30.8595N, 34.7809E, 482 masl. 2016-07-07 Since 03 Dec 2015, sampling in Natal, Brazil (NAT) was moved from 5.5147S, 35.2603W, 20 masl to 5.7952S, 35.1853W, 87 masl. 2015-11-20 Updated the content and format of event files to include elevation in meters above sea level (masl) and sample collection intake height in meters above ground level (magl). Elevation plus collection intake height equals altitude, which has always been included in the NOAA distribution. In adding these 2 fields, the event number column has moved. The new format is described in Sections 7.3 and 7.4. Users may find minor changes (from earlier distributions) to reported monthly mean values for the beginning months of data records. These changes are due to minor corrections to our curve fitting methods as first described by Thoning et al. (JGR,1989). 2015-08-03 The 3-letter site identification code for Ushuaia, Argentina (TDF) was changed to USH to be consistent with the WMO GAWSIS. 2013-08-27 Coordinates of some of the sample locations have changed. These changes improve the specified location based on new information. Changes tend to be minor and do not necessarily reflect a change in the actual sampling location. 2011-10-01 The data file format has been modified to include the measurement group and, additionally, the sample collection and analysis times now include second information (e.g., 2011 03 15 23 06 12). See section 7.3 for details. 2010-10-01 The format of the NOAA ESRL data records has been changed to include an estimate of the uncertainty associated with each measurement. The determination of the estimate is trace gas specific and described in section 6 (INTRODUCTION). +++++++++++++++++++++++++++++++ Parameter-specific notes: 2021-02-08 CO2 measurements from flask-air samples were recalculated onto the X2019 CO2 mole fraction scale by first reassigning all standards used on the CO2 analysis sytems to X2019. CO2 values on X2019 from air samples were caluclated by reprocessing the original raw files (i.e., files with raw analyzer output (typically voltages)) with the updated assignments for the standards. A detailed description of the scale revision from X2007 to X2019 is given in Hall et al. (2020), but the main reasons were to correct biases caused by CO2 absorption by O-rings in the manometric calibration system and to correct a virial coefficient used in the calculation. The magnitiude of the differences between X2019 and X2007 varies with CO2 abundance, and is typically between 0.1 and 0.2 ppm. Some differences from the late-2000s and early-2010s are larger (up to ~0.3 ppm) because of a mis-assigned standard on the system used to transfer the scale to working standards. Measurements prior to ~1980 from early analytical systems (instrument codes LR1 and LR2) could not be reprocessed onto X2019; they remain on a CO2 scale originally developed at Scripps Institution of Oceanography. 2020-07-15 Based on comparison with in situ measurements at SPO and SYO (from National Institute of Polar Research, Japan), a storage correction was applied to flask-air samples measured for CO2. The correction is ~0.2 ppm/yr at SPO and 0.08 ppm/yr at SYO. Uncertainty for the correction has not yet been determined and applied to the measurement uncertainty, but it is estimated to be ~0.05 ppm. 2018-07-30 1. Uncertainties (68% c.i.) were estimated for all CO2 measurements. Uncertainity entries of -999.99 occur when a reasonable uncertainty could not be calculated. 2. In 2017, began using N.. to flag samples not meeting pair agreement criterion. 2016-07-07 We discovered a small leak in the intake line of the portable sampler at Vestmannaeyjar, Iceland (ICE) that affected CO2. All samples from 1 July 2009 through 28 June 2016 were flagged N.. for CO2. 2012-08-03 Corrections for drifting reference gas cylinders have been applied to all samples measured on the following instruments through the specified date. Instrument ID Analysis Date L3 thru 2009-10 L8 thru 2010-06 L10 thru 2010-10 2011-10-13 Discrete (flask) CO2 mole fractions from 1980 to 2006 have all been recalculated to bring them onto the WMO X2007 Mole Fraction Scale (X2007). The data since 2007 were already on the X2007 scale. WMO X2007 is based on repeated manometric measurements of the NOAA primary standards (Zhao et al. 2006) and comparison of those results to similar measurements made over a period of more than 10 years at Scripps Institution of Oceanography. The difference between the X2007 and the previous scales propagated by SIO and NOAA (X83, X87, etc.) is ~0.2 ppm (X2007-previous) in the 1980s, decreasing to ~0.1 ppm in the late 1990s, and to 0.0 ppm by 2006. The recalculation of individual measurements was accomplished by first determining the X2007 values for the reference gases used to measure the air samples and then using those values with the raw data (NDIR voltages) to recompute mole fractions for each sample. 1999-01-01 Corrections have been applied to CO2 mole fractions measured on the flask analysis apparatus in use from July 1987 through April 1998. The corrections are +0.1 ppm to samples measured from July 1987 through 18 November 1993, and +0.24 ppm to samples measured from 19 November 1993 through 10 April 1998. Corrections for drifting reference gas cylinders have been applied to all samples measured during 1995 through April 2008 on system L3 and 1998 through May 2007 on systems S2 and L3. Files obtained previously from this site should be discarded and replaced with the revised files contained in this version. -------------------------------------------------------------------- 6. INTRODUCTION CO2 dry air mole fractions reported in these files were measured by a nondispersive infrared absorption analyzer or cavity ring-down spectrometer (since Aug., 2019) in air samples collected in glass flasks at NOAA GML Carbon Cycle Cooperative Global Air Sampling Network sites. Measurements are reported on the X2019 CO2 mole fraction scale. Calibration procedures are given in Komhyr et al., 1983; Komhyr et al., 1985; Thoning et al., 1987, and Thoning et al., 1995; and Tans et al.,2017. Analysis and interpretation of the data have been reported by Komhyr et al., 1985; Conway et al., 1988; Tans et al., 1989a; Tans et al., 1990, and Conway et al., 1994. The file co2_flask_system.ps is a postscript file explaining the operation of the flask-air analysis system used from July 1987 through April 1998. ------------------------------------------------------------------- 7. DATA - GENERAL COMMENTS Carbon dioxide (CO2) in ambient and standard air samples is detected using a non-dispersive infrared (NDIR) analyzer. The measurement of CO2 in air is made relative to standards whose CO2 mole fraction is determined with high precision and accuracy. Because detector response is non-linear in the range of atmospheric levels, ambient samples are bracketed during analysis by a set of standards used to calibrate detector response. Measurements are reported in units of micromol/mol (10^-6 mol CO2 per mol of dry air or parts per million (ppm)). In August, 2019, we switched from a NDIR to a Cavity Ring-Down Spectrometer that analyzes CH4 and CO2. The analyzer is calibrated off-line with a suite of standards once per month relative to a dry, natural air, reference in a high-pressure cylinder. All air samples are measured relative the same reference, and CH4 and CO2 values in measured samples are calculated based on their ratio to the reference. Repeatability of the analyzer, based on repeated analysis of air from a high-pressure cylinder, is ~0.02 ppm (1 sigma). Measurements are directly traceable to the WMO X2019 CO2 in air mole fraction scale. Uncertainties of the CO2 measurements are now included. Key components of it are our ability to propagate the WMO XCO2 scale to working standards, the repeatability of the analyzers used for sample measurement, and agreement between pairs of samples collected simultaneously. Zhao and Tans (2006) determined that the internal consistency of working standards is +/- 0.02 ppm (68% confidence interval). The typical repeatability of the analyzers, based on repeated measurements of natural air from a cylinder, is +/- 0.03 ppm. Average agreement between pairs of samples flushed in series across the entire sampling network is +/- 0.07 ppm. 7.1 DATA - SAMPLING LOCATIONS For a summary of sampling locations, please visit https://gml.noaa.gov/dv/site/?program=ccgg. Note: Data for all species may not be available for all sites listed in the table. To view near real-time data, manipulate and compare data, and create custom graphs, please visit https://gml.noaa.gov/dv/iadv/. ------------------------------------------------------------------- 7.2 DATA - FILE NAME DESCRIPTION Encoded into each file name are the parameter (trace gas identifier); sampling site; sampling project; laboratory ID number; measurement group; and optional qualifiers that further define the file contents. All file names use the following naming scheme: 1 2 3 4 5 [parameter]_[site]_[project]_[lab ID number]_[measurement group]_[optional 6 7 qualifiers].[file type] 1. [parameter] Identifies the measured parameter or trace gas species. (ex) co2 Carbon dioxide ch4 Methane co2c13 d13C (co2) merge more than one parameter 2. [site] Identifies the sampling site code. (ex) brw pocn30 car amt 3. [project] Identifies sampling platform and strategy. (ex) surface-flask surface-pfp surface-insitu aircraft-pfp aircraft-insitu tower-insitu 4. [lab ID number] A numeric field that identifies the sampling laboratory (1,2,3, ...). NOAA GML is lab number 1 (see http://www.esrl.noaa.gov/gmd/ccgg/obspack/labinfo.html). 5. [measurement group] Identifies the group within NOAA GML or INSTAAR that makes the actual measurement. See Section 5 (UPDATE NOTES) for details. (ex) ccgg hats arl sil 6. [optional qualifiers] Optional qualifier(s) may indicate data subsetting or averaging. Multiple qualifiers are delimited by an underscore (_). A more detailed description of the file contents is included within each data file. (ex) event All measurement results for all collected samples (discrete (flask) data only). month Computed monthly averages all collected samples (discrete (flask) data only). hour_#### Computed hourly averages for the specified 4-digit year (quasi-continuous data only) HourlyData Computed hourly averages for entire record (quasi-continuous data only) DailyData Computed daily averages for entire record (quasi-continuous data only) MonthlyData Computed monthly averages for entire record (quasi-continuous data only) 7. [file type] File format (netCDF, ASCII text). (ex) txt ASCII text file nc netCDF4 file ------------------------------------------------------------------- 7.3 DATA - FILE TYPE We now provide some NOAA Global Monitoring Laboratory measurements in two unique file formats (netCDF and ASCII text). The Network Common Data Form (NetCDF) is a self-describing, machine-independent data format that supports creation, access, and sharing of array-oriented scientific data. To learn more about netCDF and how to read netCDF files, please visit http://www.unidata.ucar.edu. The ASCII text file is derived directly from the netCDF file. The text file is also self-describing and can be viewed using any text editor. "Self-describing" means the file includes enough information about the included data (called metadata) that no additional file is required to understand the structure of the data and how to read and use the data. ------------------------------------------------------------------- 7.4 DATA - CONTENT All (ASCII text and netCDF) files are located in "ftp://aftp.cmdl.noaa.gov/data/trace_gases/co2/flask/surface/". Files are named as follows (see Section 7.2 for details): co2_[site]_surface-flask_1_ccgg_event.[file type] ------------------------------------------------------------------- 7.5 QC FLAGS NOAA GML uses a 3-column quality control flag where each column is defined as follows: column 1 REJECTION flag. An alphanumeric other than a period (.) in the FIRST column indicates a sample with obvious problems during collection or analysis. This measurement should not be interpreted. column 2 SELECTION flag. An alphanumeric other than a period (.) in the SECOND column indicates a sample that is likely valid but does not meet selection criteria determined by the goals of a particular investigation. column 3 INFORMATION flag. An alphanumeric other than a period (.) in the THIRD column provides additional information about the collection or analysis of the sample. WARNING: A "P" in the 3rd column of the QC flag indicates the measurement result is preliminary and has not yet been carefully examined by the PI. The "P" flag is removed once the quality of the measurement has been assessed. Samples are collected in pairs, the pair difference is calculated, and samples with a pair difference greater than 0.5 ppm ("bad pairs") are flagged. Through 1988 one or both members of a bad pair were sometimes retained if they fell within +/- 3 residual standard deviations from a fitted curve. From 1989 to the present, both members of bad pairs have been automatically rejected. Retained and rejected flasks are flagged as follows: Flag Description RETAINED ... (3 periods) good pair (D <= 0.5 ppm) ..H high member of bad pair; retained ..L low member of bad pair; retained ..I sample has also been measured by another lab as part of an intercomparison experiment SELECTED .X. flagged automatically as an outlier, greater than 3 sigma from a fitted curve .Z. flagged manually as an outlier (this is necessary to prevent distortion of the curve used for automated data selection) REJECTED +.. high member of bad pair; rejected -.. low member of bad pair; rejected *.. off scale or broken flask; rejected N.. rejected due to error in sampling or analysis A.. rejected due to error in analysis T.. sample collected as part of a methods test; not used in data analysis The retained values comprise the data set that we feel best represents the CO2 distribution in the remote, well-mixed global or regional troposphere. These are the values we use to calculate long-term trends and interannual and seasonal variations in our studies of the global carbon cycle. It is possible, and even likely, that some of the values flagged as not representative of background conditions are valid measurements, but represent poorly mixed air masses influenced by local or regional anthropogenic sources or strong local biospheric sources or sinks. Users of these data should be aware that data selection is a difficult but necessary aspect of the analysis and interpretation of atmospheric trace gas data sets, and the specific data selection scheme used may be determined by the goals of a particular investigation. ------------------------------------------------------------------- 8. DATA RETRIEVAL Users may transfer individual files from a directory or may choose to transfer a single zipped file. Zipped files contain the README file and either netCDF files or ASCII text files depending on the zipped file name. (ex) co2_mlo_surface-flask_1_ASCIItext.zip To transfer a zipped file, use the following steps from the ftp prompt: 1. ftp> binary ! set transfer mode to binary 2. ftp> get filename.zip ! transfer the file 3. ftp> bye ! leave ftp 4. $ unzip filename.zip ! uncompress your local copy ------------------------------------------------------------------- 9. REFERENCES Ballantyne, A. P., C. B. Alden, J. B. Miller, P. Tans and J. W. C. White, (2012), Increase in observed net carbon dioxide uptake by land and oceans during the past 50 years, Nature, 488, 7409, , 10.1038/nature11299 Conway, T.J., P.P. Tans, L.S. Waterman, K.W. Thoning, D.R. Kitzis, K.A. Masarie, and N. Zhang, 1994, Evidence for interannual variability of the carbon cycle from the NOAA/CMDL global air sampling network, J. Geophys. Res.,99, 22831-22855. Conway, T.J., P. Tans, L.S. Waterman, K.W. Thoning, K.A. Masarie, and R.H. Gammon, 1988, Atmospheric carbon dioxide measurements in the remote global troposphere, 1981-1984, Tellus, 40B, 81-115. Komhyr, W.D., L.S. Waterman, and W.R. Taylor, 1983, Semiautomatic nondispersive infrared analyzer apparatus for CO2 air sample analyses, J. Geophys. Res., 88, 1315-1322. Komhyr, W.D., R.H. Gammon, T.B. Harris, L.S. Waterman, T.J. Conway, W.R. Taylor, and K.W. Thoning, 1985, Global atmospheric CO2 distribution and variations from 1968-1982 NOAA/GMCC CO2 flask sample data, J. Geophys. Res., 90, 5567-5596. Tans, P.P., T.J. Conway, and T. Nakazawa, 1989a, Latitudinal distribution of the sources and sinks of atmospheric carbon dioxide from surface observations and an atmospheric transport model, J. Geophys. Res., 94, 5151-5172. Tans, P.P, K.W. Thoning, W.P. Elliott, and T.J. Conway, 1989b, Background atmospheric CO2 patterns from weekly flask samples at Barrow, Alaska: Optimal signal recovery and error esitmates, in NOAA Tech. Memo. (ERL ARL-173). Environmental Research Laboratories, Boulder, CO, 131 pp. Tans, P.P., I.Y. Fung, and T. Takahashi, 1990, Observational constraints on the global atmospheric CO2 budget, Science, 247, 1431-1438. Tans, Pieter P., Andrew M. Crotwell and Kirk W. Thoning, 2017, Abundances of isotopologues and calibration of CO2 greenhouse gas measurements, Atmospheric Measurement Techniques, 10, 7, 2669-2685, 10.5194/amt-10-2669-2017. Thoning, K.W., P. Tans, T.J. Conway, and L.S. Waterman, 1987, NOAA/GMCC calibrations of CO2-in-air reference gases: 1979-1985. NOAA Tech. Memo. (ERL ARL-150). Environmental Research Laboratories, Boulder, CO, 63 pp. Thoning, K.W., P.P. Tans, and W.D. Komhyr, 1989, Atmospheric carbon dioxide at Mauna Loa Observatory 2. Analysis of the NOAA GMCC data, 1974-1985, J. Geophys. Res., 94, 8549-8565. Thoning, K.W., T.J. Conway, N. Zhang, and D. Kitzis, 1995, Analysis system for measurement of CO2 mixing ratios in flask air samples, J. Atmos. and Oceanic Tech., 12, 1349-1356. Zhao, C., and P.P. Tans (2006), Estimating uncertainty of the WMO Mole Fraction Scale for carbon dioxide in air, J. Geophys. Res. 111, D08S09, doi: 10.1029/2005JD006003. -------------------------------------------------------------------