The measurements I would like to report are [cid:image001.png at 01D4C387.33A59D40] . Here is the complete definition of how we have calculated [cid:image002.png at 01D4C387.33A59D40] .
The isotopic composition can be expressed in delta values, in units of per mil (?). The small delta (?) is the isotopic ratio R (heavy C / light C) of a sample relative to the isotope ratio of a standard substance (Equation 2, Stuiver & Polach (1977)).
[?(_^14)C= [((_^14)C sample?C sample)/((_^14)C std?C std) -1] ?1000] (2)
Here, 14C sample is the 14C content of sample, C sample is the carbon content of sample, 14C std is the 14C content of standard and C standard is the carbon content of standard. ?14C is used to calculate ?14C.
14C can also be expressed as capital delta ?14C (Equation 3, (Stuiver and Polach, 1977)). The ?14C is normalized to a ?13C value of -25 ?, this is done to account for fractionation. Fractionation effects discriminate against 14C twice as much as for 13C (Stuiver and Polach, 1977). Normalising 14C measurements to a common ?13C should, therefore, remove reservoir specific differences caused by fractionation,
[?(_^14)C= ?(_^14)C-2?(?(_^13)C+25)?(1+(?(_^14)C)/1000)] (3)
where ?14C is 14C signature [?] and ?13C is 13C signature [?].
[cid:image005.png at 01D4C387.33A59D40] (4)
[cid:image006.png at 01D4C387.33A59D40] (5)
Here, 13CO2 i is the abundance 13CO2 from sector i [mol mol-1][cid:image007.png at 01D4C387.33A59D40] 13CO2 i is 13CO2 signature sector i [?], CO2 i = abundance CO2 from sector i [mol mol-1], 13R ref is the ratio of reference standard [(mol mol-1)/ (mol mol-1)] and CO2 is the total abundance CO2 enhancement [mol mol-1] from Equation 1.
[cid:image008.png at 01D4C387.33A59D40] (6)
[cid:image009.png at 01D4C387.33A59D40] (7)
Where, 14CO2 i is the abundance 14CO2 from sector i [mol mol-1][cid:image010.png at 01D4C387.33A59D40] 14CO2 i is the 14CO2 signature sector i [?], 12CO2 i is the abundance CO2 from sector i [mol mol-1], 14R ref is the ratio of reference standard [(mol mol-1)/ (mol mol-1)], 12CO2 is the total abundance CO2 enhancement [mol mol-1] from Equation 1 and[cid:image011.png at 01D4C387.33A59D40] 13CO2 is the 13CO2 signature [?] from Equation 5.
From: "Lowry, Roy K." <rkl at bodc.ac.uk>
Date: Wednesday, 13 February 2019 at 10:06
To: Katherine Pugsley <katherine.pugsley at bristol.ac.uk>, Jonathan Gregory <j.m.gregory at reading.ac.uk>, "cf-metadata at cgd.ucar.edu" <cf-metadata at cgd.ucar.edu>
Cc: Bob Key <key at princeton.edu>
Subject: Re: [CF-metadata] New standard name for 14CO2
Hello again,
Bob Key contacted me off-list to point out that d14C and D14C are different, but didn't tell me how. Reading around (
http://www.c14dating.com/agecalc.html) I find that D14C is d14c with the 13C correction applied using the equation D14C=d14C - 2(dC13 + 25)(1 + d14C/1000) per mille where d14C is what I'd described in the draft definition. Bob also made it clear that the carbon dating community regard d14C and D14C as significantly different measurements, with d14C consigned to history.
So, Katherine's measurements are D14C. I just need to be sure that the fractionation correction she has applied is as given above - Katherine?
Following Bob's intervention I feel the Standard Name and definition should be for D14C, not d14C such as:
enrichment_with_respect_to_radiocarbon_absolute_reference_standard_of_ 14C_in_carbon_dioxide_in_air_expressed_as_D14C
Isotopic enrichment of 14C (d14C or delta14C), is a parameterisation of the 14C/12C isotopic ratio in the sample with respect to the isotopic ratio in a standard, in this case the radiocarbon absolute reference standard. It is computed using the formula (((14C/12C) sample / (14C/12C) standard) - 1) * 1000. D14C or Delta14C is d14C corrected for isotopic fractionation using the 13C/12C ratio. D14C = d14C - 2(dC13 + 25)(1 + d14C/1000). If the sample is enriched in 14C then the value is positive.
I know Jonathan won't be comfortable with this, but carbon chemistry is a discipline where precise measurement semantics is very important.
Cheers, Roy.
Radiocarbon Date calculation - c14dating.com<
http://www.c14dating.com/agecalc.html>
Figure 1: Decay curve for C14 showing the activity at one half-life (t/2). The terms "%Modern", or "pmC" and D14C are shown related in this diagram along with the Radiocarbon age in years BP (Before 1950 AD).
www.c14dating.com
I have now retired but will continue to be active through an Emeritus Fellowship using this e-mail address.
________________________________
From: Katherine Pugsley <katherine.pugsley at bristol.ac.uk>
Sent: 13 February 2019 08:35
To: Lowry, Roy K.; Jonathan Gregory; cf-metadata at cgd.ucar.edu
Subject: Re: [CF-metadata] New standard name for 14CO2
Hi Roy, Jonathan,
The normalisation mathematically corrects for the effects of isotopic fractionation, such that the processes which naturally fractionate during exchange have no impact on atmospheric Delta14C and thus, only disequilibrium terms need to be considered. For example, photosynthetic uptake of CO2.
Thanks,
Katherine
On 12/02/2019, 10:58, "CF-metadata on behalf of Lowry, Roy K." <cf-metadata-bounces at cgd.ucar.edu on behalf of rkl at bodc.ac.uk> wrote:
Dear Jonathan,
Whilst I initially favoured relegating the standard to the long name, after a bit of thought and reading around I changed my mind. Whilst multiple standards may not be in use today, a number have been favoured at different times over the past 50 years. See for example
https://www.researchgate.net/publication/222399840_Future_needs_and_requirements_for_AMS_14C_standards_and_reference_materials
Consequently, I feel inclusion of the name of the standard in the Standard name is prudent.
I think I understand what the 13C normalisation is about, but I'll leave it to Katherine to explain in case I haven't got it exactly right.
Cheers, Roy.
-----Original Message-----
From: CF-metadata <cf-metadata-bounces at cgd.ucar.edu> On Behalf Of Jonathan Gregory
Sent: 12 February 2019 10:13
To: cf-metadata at cgd.ucar.edu
Subject: Re: [CF-metadata] New standard name for 14CO2
Dear Katherine and Roy
Thanks for the information. I think enrichment is fine. Unlike Roy, I would favour not mentioning the standard (and likewise I would not mention pee dee belemnite in d13O) unless there is more than one standard routinely in use, so that we need to distinguish. Are there any others in this case?
I am curious to know what this means:
> The sample ratio is normalised to ? 25 per mil delta13C (to correct for isotopic fractionation).
(although I understand Roy's remark that it doesn't affect the definition).
Best wishes
Jonathan
----- Forwarded message from "Lowry, Roy K." <rkl at bodc.ac.uk> -----
> Date: Mon, 11 Feb 2019 16:05:13 +0000
> From: "Lowry, Roy K." <rkl at bodc.ac.uk>
> To: Katherine Pugsley <katherine.pugsley at bristol.ac.uk>, Alison Pamment -
> UKRI STFC <alison.pamment at stfc.ac.uk>, "cf-metadata at cgd.ucar.edu"
> <cf-metadata at cgd.ucar.edu>
> Subject: Re: [CF-metadata] New standard name for 14CO2
>
> Thanks Katherine,
>
> That looks a complete set of information to me. I think we're all happy using 'enrichment'. Next issue to resolve is whether two items of information - the standard used and the delta13C normalisation - are built into the Standard Name or consigned to the Long Name. I would argue that the normalisation is an experimental detail and policy has been not to include these in Standard Names. However, to me the standard used is a fundamental attribute of what has been measured so I would go for its inclusion giving us:
>
>
> enrichment_with_respect_to_radiocarbon_absolute_reference_standard_of_
> 14C_in_carbon_dioxide_in_air
>
> Her'e a straw man for a definition
>
> Isotopic enrichment of 14C, sometimes called Delta14C or delta14C, is a parameterisation of the 14C/12C isotopic ratio in the sample with respect to the isotopic ratio in a standard, in this case the radiocarbon absolute reference standard. It is computed using the formula (((14C/12C) sample / (14C/12C) standard) - 1) * 1000. If the sample is enriched in 14C then the value is positive.
>
> Cheers, Roy.
>
>
>
> I have now retired but will continue to be active through an Emeritus Fellowship using this e-mail address.
>
> ________________________________
> From: Katherine Pugsley <katherine.pugsley at bristol.ac.uk>
> Sent: 11 February 2019 14:33
> To: Alison Pamment - UKRI STFC; Lowry, Roy K.;
> cf-metadata at cgd.ucar.edu
> Subject: Re: [CF-metadata] New standard name for 14CO2
>
>
> Hi All,
>
>
>
> Thank you, Roy, Jonathon and Alison, for your feedback on this new standard name.
>
>
>
> Some more information on how the measurements are made and calculated.
>
>
>
> Measurements are made using Accelerator Mass Spectrometry.
>
> Roy is correct Delta14C is calculated similar to delta13C.
>
> Delta14C = (((14C/12C) sample / (14C/12C) standard) - 1) * 1000 per mil in accordance to Stuiver and Polach (1977).
>
> The standard this is calculated in relation to is the radiocarbon absolute reference standard, Oxalic Acid I. The sample ratio is normalised to ? 25 per mil delta13C (to correct for isotopic fractionation).
>
>
>
> Either of the names Roy suggests
> (enrichment_of_14C_in_carbon_dioxide_in_air or
> delta14C_in_carbon_dioxide_in_air
>
> ) could work.
>
>
>
> Thanks,
>
>
>
> Katherine
>
>
>
> From: CF-metadata <cf-metadata-bounces at cgd.ucar.edu> on behalf of
> Alison Pamment - UKRI STFC <alison.pamment at stfc.ac.uk>
> Date: Monday, 11 February 2019 at 12:59
> To: "rkl at bodc.ac.uk" <rkl at bodc.ac.uk>, "cf-metadata at cgd.ucar.edu"
> <cf-metadata at cgd.ucar.edu>
> Subject: Re: [CF-metadata] New standard name for 14CO2
>
>
>
> Hi Roy,
>
>
>
> Okay, thank you for spotting that!
>
>
>
> Best wishes,
>
> Alison
>
>
>
> ------
>
> Alison Pamment Tel: +44 1235 778065
>
> NCAS/Centre for Environmental Data Archival Email: alison.pamment at stfc.ac.uk
>
> STFC Rutherford Appleton Laboratory
>
> R25, 2.22
>
> Harwell Oxford, Didcot, OX11 0QX, U.K.
>
>
>
> From: Lowry, Roy K. <rkl at bodc.ac.uk>
> Sent: 11 February 2019 12:55
> To: Pamment, Alison (STFC,RAL,RALSP) <alison.pamment at stfc.ac.uk>;
> cf-metadata at cgd.ucar.edu
> Subject: Re: [CF-metadata] New standard name for 14CO2
>
>
>
> Hi Alison,
>
>
>
> One slight misunderstanding. 'per mil' means parts per thousand not parts per million so the units should be written as '1e-3' rather than '1e-6'.
>
>
>
> Cheers, Roy.
>
>
>
> I have now retired but will continue to be active through an Emeritus Fellowship using this e-mail address.
>
>
>
> ________________________________
>
> From: CF-metadata
> <cf-metadata-bounces at cgd.ucar.edu<mailto:cf-metadata-bounces at cgd.ucar.
> edu>> on behalf of Alison Pamment - UKRI STFC
> <alison.pamment at stfc.ac.uk<mailto:alison.pamment at stfc.ac.uk>>
> Sent: 11 February 2019 12:49
> To: cf-metadata at cgd.ucar.edu<mailto:cf-metadata at cgd.ucar.edu>
> Subject: Re: [CF-metadata] New standard name for 14CO2
>
>
>
> Dear Katherine, All,
>
> Katherine and I had briefly discussed this name before it was proposed to the mailing list - the suggestion of using mole_fraction was originally mine. Evidently I had misunderstood the quantity in question, and it's clear from the discussion so far that it wouldn't be appropriate to use mole_fraction in this case. Thank you to Roy and Jonathan for clarifying this (and my apologies to Katherine for misleading advice - I've not come across this quantity before).
>
> It does seem that we will need to introduce some new terminology into standard names. Of Roy's two suggestions I prefer enrichment_of_14C_in_carbon_dioxide_in_air. From Roy's explanation, it looks like the quantity is in effect a ratio of ratios. While I appreciate that this may be referred to as a 'delta' in the chemistry community, 'delta' is often used as a mathematical symbol for calculating a difference or change, so I feel that it's best avoided in the standard name.
>
> Regarding the units of 'per mil', the canonical unit in the standard name table would be written as '1e-6'.
>
> Whichever terminology we choose, certainly we do need a clear definition - in particular if the quantity is being calculated with reference to a particular standard we should include that in the information. Katherine, please could you give us some more details about exactly how this quantity is being measured/calculated in your data?
>
> Best wishes,
> Alison
>
> ------
> Alison Pamment Tel: +44 1235 778065
> NCAS/Centre for Environmental Data Archival Email: alison.pamment at stfc.ac.uk<mailto:alison.pamment at stfc.ac.uk>
> STFC Rutherford Appleton Laboratory
> R25, 2.22
> Harwell Oxford, Didcot, OX11 0QX, U.K.
>
>
> -----Original Message-----
> From: CF-metadata
> <cf-metadata-bounces at cgd.ucar.edu<mailto:cf-metadata-bounces at cgd.ucar.
> edu>> On Behalf Of Jonathan Gregory
> Sent: 11 February 2019 04:57
> To: cf-metadata at cgd.ucar.edu<mailto:cf-metadata at cgd.ucar.edu>
> Subject: Re: [CF-metadata] New standard name for 14CO2
>
> Dear all
>
> I agree with Roy that delta-14C is not a mole fraction, but a way of expressing the deviation of an isotopic ratio in a sample from a standard isotopic ratio.
> The definition Roy gives for delta-13C is shown in several websites. I think we need the precise definition of the quantity being proposed, because there appear to be variou quantities with big and small delta and D, and maybe they are all different, and would need distinct standard names. I think Roy is right that we have not given standard names to such quantities before.
>
> Best wishes
>
> Jonathan
>
> ----- Forwarded message from "Lowry, Roy K."
> <rkl at bodc.ac.uk<mailto:rkl at bodc.ac.uk>> -----
>
> > Date: Fri, 8 Feb 2019 12:55:31 +0000
> > From: "Lowry, Roy K." <rkl at bodc.ac.uk<mailto:rkl at bodc.ac.uk>>
> > To: Katherine Pugsley <katherine.pugsley at bristol.ac.uk<mailto:katherine.pugsley at bristol.ac.uk>>,
> > "cf-metadata at cgd.ucar.edu<mailto:cf-metadata at cgd.ucar.edu>"
> > <cf-metadata at cgd.ucar.edu<mailto:cf-metadata at cgd.ucar.edu>>
> > Subject: Re: [CF-metadata] New standard name for 14CO2
> >
> > I think that delta-14CO2 is not the same thing as the mole fraction. Rather, it is an expression of isotopic enrichment/depletion with respect to a standard. Whilst I have no experience of atmospheric 14C, I have come across delta notation a lot with other isotopes in geology and oceanography such as 13C and 18O. There, delta is an expression of the ratio of the target isotope to another isotope in the sample relative to some standard - ((sample 13C/12C ratio / standard 13C/12C ratio) - 1) * 1000 to give a result scaled to per mil. I presume that delta-14C is no different.
> >
> > I am unaware (i.e. I couldn't find) a precedent for delta values in CF Standard Names. The issue of describing these things has been addressed at length in the BODC parameter descriptions with almost 400 measurement descriptions. A typical example is:
> >
> > Enrichment with respect to Vienna Pee Dee Belemnite (VPDB) of
> > carbon-13 in carbonate in the sediment
> >
> > This particular example includes information on the specific standard used. Many do not because the information is often unavailable for older data.
> >
> > A straw man alternative to Kate's proposal could be
> >
> > enrichment_of_14C_in_carbon_dioxide_in_air
> >
> > If information on the standard is available then that could be added as an 'enrichment_with_respect_to_whatever' clause or the information could be confined to the long name. The better solution depends upon the use case (e.g. does it require inclusion of data where standard is unknown).
> >
> > Another approach could be to adopt community vocabulary such as:
> >
> > delta14C_in_carbon_dioxide_in_air
> >
> > Others may have alternative suggestions.
> >
> > I went for 'enrichment of x' in the BODC dictionary because it provides a better fit to a normalised semantic model for mapping purposes. One only has to include one 'enrichment' rather than a long list of 'deltas' in the semantic element.
> >
> > Cheers, Roy.
> >
> >
> > I have now retired but will continue to be active through an Emeritus Fellowship using this e-mail address.
> >
> > ________________________________
> > From: CF-metadata
> > <cf-metadata-bounces at cgd.ucar.edu<mailto:cf-metadata-bounces at cgd.uca
> > r.edu>> on behalf of Katherine Pugsley
> > <katherine.pugsley at bristol.ac.uk<mailto:katherine.pugsley at bristol.ac
> > .uk>>
> > Sent: 08 February 2019 10:46
> > To: cf-metadata at cgd.ucar.edu<mailto:cf-metadata at cgd.ucar.edu>
> > Subject: [CF-metadata] New standard name for 14CO2
> >
> >
> > Dear All,
> >
> > I'd like to request an addition to the standard name list for atmospheric 14CO2 measurements. Here are the details of the proposed standard name.
> >
> > Proposal for a new standard variable name
> >
> > Name: mole_fraction_of_14C_dioxide_in_air
> >
> > Canonical Units: 1
> >
> > Description: Atmospheric 14CO2 measurements are reported in ?14C notation with units of per mil, the deviation from the absolute radiocarbon reference standard. ?14C is used to calculate fossil fuel CO2 content. The long name will contain information that the variable is ?14C.
> >
> >
> >
> > Thanks,
> >
> > Katherine
> >
> >
> >
> >
> > This email and any attachments are intended solely for the use of the named recipients. If you are not the intended recipient you must not use, disclose, copy or distribute this email or any of its attachments and should notify the sender immediately and delete this email from your system.
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>
> > _______________________________________________
> > CF-metadata mailing list
> > CF-metadata at cgd.ucar.edu<mailto:CF-metadata at cgd.ucar.edu>
> > http://mailman.cgd.ucar.edu/mailman/listinfo/cf-metadata
>
>
> ----- End forwarded message -----
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> This email and any attachments are intended solely for the use of the named recipients. If you are not the intended recipient you must not use, disclose, copy or distribute this email or any of its attachments and should notify the sender immediately and delete this email from your system.
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> Opinions, conclusions or other information in this message and attachments that are not related directly to UK Research and Innovation business are solely those of the author and do not represent the views of UK Research and Innovation.
>
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> This email and any attachments are intended solely for the use of the named recipients. If you are not the intended recipient you must not use, disclose, copy or distribute this email or any of its attachments and should notify the sender immediately and delete this email from your system.
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> Opinions, conclusions or other information in this message and attachments that are not related directly to UK Research and Innovation business are solely those of the author and do not represent the views of UK Research and Innovation.
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Received on Wed Feb 13 2019 - 03:30:56 GMT
