These data were produced by NOAA and are not subject to copyright protection in the United States. NOAA waives any potential copyright and related rights in these data worldwide through the Creative Commons Zero 1.0 Universal Public Domain Dedication (CC0 1.0)
CC0 1.0 Universal
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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.
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5. UPDATE NOTES
+++++++++++++++++++++++++++++++
Lab-wide notes:
2011-10-07
We introduced the term "measurement group", which identifies
the group within NOAA or 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)
+++++++++++++++++++++++++++++++
Project-specific notes:
2022-07-21
Dataset is now provided in self describing ObsPack format with improved metadata.
Surface flask event data are available in NetCDF and ASCII text. Surface flask
monthly data are available in ASCII text. Shipboard data binned by 5 or 3 degrees
are now removed from surface flask event data, but still provided in monthly data.
This format change makes some previous notes irrelevant.
+++++++++++++++++++++++++++++++
Parameter-specific notes:
*************************************
January 2013 - Second position flags moved to first and third positions:
Due to confusion resulting from our second position flags, they were
moved to either first or third position. All flags are applied automatically
by code except for '!' hand flags. Please see flagging section for more
information.
May 2014 - Additional first position flags added
To increase the quality of the data, we decided to flag data for which
there was a small sample peak (less than 3 nA) with a first position 'P'
flag. We also decided to flag data for which there was significant (greater
than 0.25 permil) drift in the reference gas with a 'D' flag.
October 2021 - Amount effect correction added for data from 2018-2020.
Third-position 'r' and 'R' flags were introduced to account an amount
effect, where isotope delta values were influenced by differences in peak
size between the sample and standard peak. Third-position 'r' flags were
assigned to all data for which a correction was applied - this includes all
data measured 2018-2020. Third-position 'R' flags were assigned to samples
with a pronounced amount effect, where the difference between the sample and
standard peak size exceeded 2.5 nA. Both 'r' and 'R' flagged data have
expanded uncertainty due to the uncertainty of the data correction
calculation, in addition to the standard analytical uncertainty.
Nov 2022 - Adjustments to flagging
We reduced criteria for flagging peak size from 3 nA to 2 nA. However, we
added a flag starting in 2021 when the peak size is more than 1 nA different
than the standard peak size. This addresses the 'amount effect' that was
previously problematic. We also increased the allowable drift from 0.25
permil to 0.3 permil between standards.
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6. INTRODUCTION
The data files in this archive list measurements of the stable isotopic
composition (13C) of atmospheric methane. The isotopic analysis was
performed at the Stable Isotope Laboratory at the Institute of Arctic and Alpine
Research (INSTAAR) at the University of Colorado Boulder, using samples of air
provided by the NOAA Global Monitoring Laboratory Global Greenhouse Gas
Reference Network.
This release contains data for flask samples beginning in 1998 and
extending through the end of 2022. Data are given for all sites where at
least 18 months of data are available.
The subdirectories txt and nc contain all measurements from flask samples
collected at each site. The txt directory also contains monthly values given
only in those months where there are data, and no interpolation is made for
missing months. All NOAA sites for which CH4 isotope data has been collected
up to 12/31/2022 are included. Data from recently initiated sites will be included
in future releases. See Miller et al., 2002 or Conway et al., 1994 for
details of the sampling network, equipment and procedures.
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7. DATA - GENERAL COMMENTS
Isotope data are reported as isotope delta values: the ratio of minor to
major isotopes relative to a standard. The 'isotope delta' notation is
d13C(CH4) = [ (13C/12C)sam / (13C/12C)std - 1 ]
and is customarily expressed as a multiple of 1000 in units of 'permil'.
The scale for carbon isotopes is the VPDB scale and is realized through
calcite reference materials. Our local realization of the VPDB scale is
through to Dr. Stan Tyler's lab at the University of California Irvine. He
measured d13C-CH4 of methane in air relative to CO2 produced by reaction of
NBS-19.
All of the samples have been analyzed at the Stable Isotope Laboratory at
CU-INSTAAR in Boulder, Colorado, using either a Micromass Optima or Elementar
Isoprime isotope-ratio mass spectrometer coupled to a methane a custom-built
trapping system, a gas chromatograph, and a combustion furnace. Measurement
precision is approximately 0.06 permil for 13C (where 'precision' is taken as
the long term reproducibility of a surveillance cylinder of ambient air.
Current efforts to validate this scale and compare with other labs in the
isotopic community are ongoing. For more information regarding calibrations
of methane-in-air isotopes, see the recent review by Umezawa et al., 2017.
For more information on our methodology, please refer to the following
publications:
Vaughn, B.H., J. Miller, D. F. Ferretti, J. W. C. White 2004: Stable
isotope measurements of atmospheric CO2 and CH4. Handbook of Stable Isotope
Analytical Techniques, vol 1, ch.14, Elsiever, 1248 p.
Miller, J. B., K. A. Mack, R. Dissly, J. W. C. White, E. J. Dlugokencky,
and P. P. Tans 2002: Development of analytical methods and measurements of
13C/12C in atmospheric CH4 from the NOAA Climate Monitoring and Diagnostics
Laboratory Global Air Sampling Network. J Geophys. Res., v107, NO. D13.
In 2013 we added a metric of uncertainty for isotopes of methane. This is
not a "true" calculation of uncertainty in a metrological sense - instead it
is a metric of short- to medium-term reproducibility of a surveillance
cylinder. This air cylinder is well characterized by long-term measurement,
and in addition to tracking our ties to VPDB over the long term, it alerts us
to any problems with the mass spectrometer or extraction system. We use the
standard deviation of ten runs' worth of surveillance cylinder measurements
as the uncertainty metric. Usually four samples are run a day, of which all
but the first are used (due to known irregularities caused by the tank
regulator). For each run, the uncertainty is calculated from data from that
run, regardless of its flagging, and the previous nine runs of unflagged
data. (For example, if the current run is flagged, that surveillance cylinder
data will be used in the uncertainty calculation; however, the next day's run
will not use the flagged data in its uncertainty calculation.) As of Dec
2013, uncertainty is calculated with each run, and has been back-calculated
to 2006.
In May 2017, a post combustion column was added to remove doubly-charged
Kr ions which interferes with measurement of the different masses of CH4-
derived CO2. Extensive tests of cylinders with different CH4/Kr ratios before
and after implementation of the PC column show that there is very little
effect of Krypton on samples with methane mole fraction over 1400 ppb.
A data correction has been applied for all 2018-2020 data to reduce a
positive bias introduced by our sample preparation system. During this time
there was a clog in a valve that caused reduced flow through our methane
trapping system, causing smaller sample peaks in our analyzer, especially in
low-pressure flasks. The difference in peak heights between samples and
standards exacerbated an "amount effect" problem, where the peak height
influenced the measured isotope delta value. With ongoing extensive testing
that began in 2019, we discovered that our amount effect was variable, with
an average of -0.019 permil/nA and a standard deviation of 0.047 permil/nA.
To correct for it, we applied a Monte Carlo approach: we applied 100
randomly-chosen slopes from the list of measured corrections and
calculated the mean of the corrected values. The standard deviation of the
100 iterations were added in quadrature to the analytical uncertainty to
account for the error in the correction. Data for which the amount effect
correction has been applied has a third position 'r'. A third position 'R'
flag was added where the sample peak height differs from the standard peak
height by more than 2.5 nA, where the correction was significant. This
correction is imperfect, but does reduce a positive bias in the data
suggested by intercomparisons with other research groups. If further evidence
suggests a better way to handle this effect, we may revisit the correction
for this time period. Evidence suggests that the amount effect comes from the
combustion process, though investigations continue. In late-2020, the
obstruction in the system was resolved and we now reliably control for peak
size across sample types; therefore the amount effect is now within
measurement noise.
Pacific Ocean Cruise (POC, travelling between the US west coast
and New Zealand or Australia) flask-air samples were collected in
about 5 degree latitude intervals. For South China Sea (SCS), samples
were collected at about 3 degree latitude intervals.
Sampling intervals are approximately weekly for fixed sites
and average one sample every 3 weeks per latitude zone for POC and
about one sample every week per latitude for SCS.
Historically, samples have been collected using two general methods:
flushing and then pressurizing glass flasks with a pump, or opening a
stopcock on an evacuated glass flask; since 28 April 2003, only the
former method is used. During each sampling event, a pair of flasks
is filled.
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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/.
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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 (optional); 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]_[optional 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 https://gml.noaa.gov/ccgg/obspack/labinfo.html).
5. [optional measurement group]
Identifies the group within the NOAA GML or the Institute of Arctic and Alpine
Research (INSTAAR) at the University of Colorado Boulder that made the
measurement.
It is possible to have multiple different 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)
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
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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 (technically UTF-8 encoded) file is derived directly from the
netCDF file. The text file is also self-describing and can be viewed using
any ASCII or UTF-8 capable 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. Note that some non-ASCII characters (accents,
international character sets) may be present in various names and contact
information. These may require a UTF-8 capable text editor to view properly.
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7.4 DATA - CONTENT
See individual files for description of the provided variables and other
dataset metadata.
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7.5 QC FLAGS
Reject flags (1st flag character)
A known problem in analysis (poor precision of measured standard air)
a analysis problem (specifics unknown)
! Hand-flagged by INSTAAR researcher: analytical problem.
E specific analysis problem due to extraction manifold problem
B specific analysis problem due to transfer pump
n known sampling problem -- taken from NOAA CH4 data base
+ bad pair, high member
- bad pair, low member
. good flask
Data measured after 2006 may have these flags:
H mean of trap (cylinder of known isotopic value run as sample) in same
run as sample was more than 0.3 permil above the long-term
mean
L mean trap value in same run as sample was more than 0.3 permil
below the long term mean
P small peak (less than 2 nA) - too low for accurate analysis
Y peak too large (greater than 18 nA) - swamps collectors
D too much drift; more than 0.3 permil drift in the reference gas
(this limit was previously set at 0.25 permil)
Data measured before 2006 may have these flags:
D a second aliquot taken more than 20 days after the first
2 a 'D' flag applied over another hard flag (e.g., D+n=2 or D+A=2)
M a third or greater aliquot taken more than 20 days after the first
3 a 'M' flag applied over another hard flag (e.g., T+n=2 or T+A=2)
Data measured 2020 and after may have this flag
Z standard and sample peaks are more than 1 nA different
------------------------------------------------------------------------------
Non-background flags (2nd flag character)
X outlier by more than 3-sigma from a smooth curve fit to CH4C13 data
x outlier flag taken from CH4 data (ie, outlier in CH4 concentration)
Z hand-flagged by NOAA (not INSTAAR) researchers
. good flask
-----------------------------------------------------------------------------
Retain flags (3rd flag character)
S flask analyzed singly, without its mate
. good flask
I intercomparison sample
i intercomparison sample flag overwriting previous (now lost) flag
o No surveillance cylinder data associated with this sample
T trap samples had unusually high variance (0.2 permil)
Data measured 2018-2020 may have these third position flags
r Correction for 'amount effect' applied to these data
R Correction for 'amount effect' is significant, because peak
height of sample differs from standard by more than 2.5 nA
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7.6 COLLECTION METHODS
A single-character code is used to identify the sample collection method.
The codes are:
P - Sample collected using a portable, battery
powered pumping unit. Two flasks are
connected in series, flushed with air, and then
pressurized to 1.2 - 1.5 times ambient pressure.
D - Similar to P but the air passes through a
condenser cooled to about 5 deg C to partially
dry the sample.
G - Similar to D but with a gold-plated condenser.
T - Evacuated flask filled by opening an O-ring sealed
stopcock.
S - Flasks filled at NOAA GML observatories by sampling
air from the in situ CO2 measurement air intake system.
N - Before 1981, flasks filled using a hand-held
aspirator bulb. After 1981, flasks filled using a
pump different from those used in method P, D, or G.
F - Five liter evacuated flasks filled by opening a
ground glass, greased stopcock
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7.7 DATA - MONTHLY AVERAGES
The monthly data files in https://gml.noaa.gov/aftp/data/trace_gases/ch4c13/flask/surface/
use the following naming scheme (see Section 7.2):
[parameter]_[site]_[project]_[lab ID number]_[measurement group]_month.txt
(ex) CH4_pocn30_surface-flask_1_ccgg_month.txt contains CH4 ccgg monthly
mean values for all surface flask samples collected on the Pacific
Ocean Cruise sampling platform and grouped at 30N +/- 2.5 degrees.
(ex) CO2_brw_surface-flask_1_ccgg_month.txt contains CO2 ccgg monthly
mean values for all surface flask samples collected at Barrow, Alaska.
Monthly means are produced for each site by first averaging all
valid measurement results in the event file with a unique sample
date and time. Values are then extracted at weekly intervals from
a smooth curve (Thoning et al., 1989) fitted to the averaged data
and these weekly values are averaged for each month to give the
monthly means recorded in the files. Flagged data are excluded from the
curve fitting process. Some sites are excluded from the monthly
mean directory because sparse data or a short record does not allow a
reasonable curve fit. Also, if there are 3 or more consecutive months
without data, monthly means are not calculated for these months.
The data files contain multiple lines of header information
followed by one line for each available month.
Fields are defined as follows:
Field 1: [SITE CODE] The three-character sampling location code (see above).
Field 2: [YEAR] The sample collection year and month.
Field 3: [MONTH]
Field 4: [MEAN VALUE] Computed monthly mean value
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8. DATA RETRIEVAL
All (ASCII text and netCDF) files are located in
"https://gml.noaa.gov/aftp/data/trace_gases/ch4c13/flask/surface/".
To transfer all files in a directory, it is more efficient to
download the tar or zipped files. Individual or zipped files can
be downloaded using your web browser by clicking the hyperlinked file
or right clicking hyperlink and using browser menu to 'save as' or similar.
Files can also be accessed by anonymous ftp at aftp.cmdl.noaa.gov.
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9. REFERENCES
Conway, T.J., Tans, P.P., Waterman, L.S., Thoning, K.W., Kitzis, D.R.,
Masarie, K.A., and Zhang, N. 1994. Evidence for interannual variability
of the carbon cycle from the NOAA/CMDL global air sampling network, JGR 99, 22831-22855.
Miller, J. B., Mack, K. A., Dissly, R., White, J. W. C., Dlugokencky, E.
J. and Tans, P. P. 2002. Development of analytical methods and
measurements of 13C/12C in atmospheric CH4 from the NOAA/CMDL global air
sampling network. J. Geophys. Res. 107, doi: 10.1029/2001JD000630.
Thoning, K.W., Tans, P.P., and Komhyr, W.D. 1989, Atmospheric carbon
dioxide at Mauna Loa Observatory 2. Analysis of the NOAA GMCC Data,
1974-1985, J. Geophys. Res., 94, 8549-8565.
Umezawa, T., Brenninkmeijer, C., Rockmann, T., van der Veen, C., Tyler,
S. C., Fujita, R., Morimoto, S., Aoki, S., Sowers, T., Schmitt, J., and
Bock, M. (2018). Interlaboratory comparison of d13C and dD measurements
of atmospheric CH4 for combined use of data sets from different laboratories.
Atmospheric Measurement Techniques.
Vaughn, B., Ferretti, D., Miller, J. and White, J. 2004. Stable isotope
measurements of atmospheric CO2 and CH4. Handbook of Stable Isotope Analytical
Techniques, vol 1, ch. 14, Elsevier, 1248 p.
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