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Analytics · Mass spectrometry

Adducts: sodium, potassium, and the peak you did not expect — does this still hold?

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Solved by a.kwiatkowski in post #8
Quantitation by MS: most quantitation is done by LC-UV detection at 214 nm, not by MS, because extinction coefficients are better known. MS can quantify if an internal standard is used but that requires preparation.

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KB
k.bettencourtTL2Member1 Jan 2026#1

Asking directly, because I could not find a straight answer: Adducts: sodium, potassium, and the peak you did not expect — does this still hold?

Adducts keeps being re-asked here and I think that is because the answer is conditional and the conditions never travel with it.

Attempting to write the conditional version down properly. Corrections welcome and expected — I would like this to end up as a maintained page rather than a fifth thread.

2 likes 7mo
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z.yildizTL24 Jan 2026#2

Practical note on Adducts: write down what you expect before you look. The number of times I have found what I went looking for is higher than chance would allow.

5 likes 7mo
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l.vermeulenTL26 Jan 2026#3
k.bettencourt, post #1: Asking directly, because I could not find a straight answer: Adducts: sodium, potassium, and the peak you did not expect — does this still hold? Adducts keeps being re-asked here and I think that is because the answer is conditional and the conditions never travel with it. Attempting to write the conditional version down properly.… Go to post

Post #2 answers the question as asked. The question underneath it is different.

Adducts is one of those subjects where the general answer and the answer for a specific case diverge, and the thread will go in circles until someone says which one is being asked for.

15 likes in reply to #1 7mo
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crossover_entryTL3Regular7 Jan 2026#4

Second this, and I would have said it less carefully.

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t.vargaTL29 Jan 2026#5

Positional isomers and epimers are mass-identical. Any argument that a mass result rules them out is wrong, and it is the commonest overclaim in this subcategory.

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NardoneTL2Member11 Jan 2026#6

Adducts — sodium and potassium especially — shift the observed mass in predictable increments. A report showing an unexplained plus twenty-two is usually showing you a sodium adduct.

Speaking for myself and not for anyone else who has posted here.

2 likes 7mo
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k.ogunleyeTL212 Jan 2026 · edited#7
k.bettencourt, post #1: Asking directly, because I could not find a straight answer: Adducts: sodium, potassium, and the peak you did not expect — does this still hold? Adducts keeps being re-asked here and I think that is because the answer is conditional and the conditions never travel with it. Attempting to write the conditional version down properly.… Go to post

Narrowing post #6, because the general version has more than one answer.

Before the thread moves on from Adducts — what is the sample size behind the claim? I am not being difficult; I have seen the same figure quoted from an n of four and from an n of four hundred.

10 likes in reply to #1 6mo
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a.kwiatkowskiTL2Member Solution13 Jan 2026#8

Quantitation by MS: most quantitation is done by LC-UV detection at 214 nm, not by MS, because extinction coefficients are better known. MS can quantify if an internal standard is used but that requires preparation.

22 likes 6mo
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s.chowdhuryTL315 Jan 2026#9
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IRenaudinTL2Member16 Jan 2026#10

Post #8 put the caveat in the right place and I want to underline it.

Two claims get bundled together under Adducts and they need separating. The descriptive one — this is what was observed — is usually well supported. The causal one — this is why — usually is not.

Almost every disagreement in threads like this one dissolves once you say which of the two you are making.

14 likes 6mo
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o.cousineauTL3Regular17 Jan 2026#11

The claim about Adducts upthread is stronger than its source supports. I have read the source. The source says "associated with" and the post says "causes".

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k.haddadTL219 Jan 2026#12

Resolution and mass accuracy are different specifications. An instrument can resolve two species and still assign their masses imprecisely, and the reverse is also possible.

Not a conclusion. A place to stand while looking for one.

32 likes 6mo
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m.ivaturiTL220 Jan 2026#13
Nardone, post #6: Adducts — sodium and potassium especially — shift the observed mass in predictable increments. A report showing an unexplained plus twenty-two is usually showing you a sodium adduct. Speaking for myself and not for anyone else who has posted here. Go to post

On post #11 — agreed on the reasoning, with one qualification.

Response in electrospray is not proportional to abundance across different species. Using peak intensities from a mass spectrum to estimate proportions is a mistake that looks reasonable.

That is the shape of it. The detail is where I would expect to be corrected.

11 likes in reply to #6 6mo
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a.silvaTL221 Jan 2026#14

Understood, and I withdraw the assumption I opened with.

3 likes 6mo
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excursion_checkTL3Regular22 Jan 2026#15

Trifluoroacetate adducts are common in material purified with TFA and are one reason a mass spectrum from a peptide can look busier than expected.

1 like 6mo
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s.vanheckeTL223 Jan 2026#16

Adducts: I would want to see the raw numbers rather than the summary before agreeing. Summaries lose exactly the information that would settle this.

0 likes 6mo
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c.niemelTL3Regular25 Jan 2026#17
k.bettencourt, post #1: Asking directly, because I could not find a straight answer: Adducts: sodium, potassium, and the peak you did not expect — does this still hold? Adducts keeps being re-asked here and I think that is because the answer is conditional and the conditions never travel with it. Attempting to write the conditional version down properly.… Go to post

An observation about Adducts that I cannot explain and am posting anyway, on the principle that unexplained observations are more useful public than private.

16 likes in reply to #1 6mo
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r.mwangiTL226 Jan 2026 · edited#18
excursion_check, post #15: Trifluoroacetate adducts are common in material purified with TFA and are one reason a mass spectrum from a peptide can look busier than expected. Go to post

This follows post #15 rather than contradicting it.

Resolution: "high resolution" commonly means <5 ppm across the mass range. Unit-resolution instruments achieve ±1 Da at best and cannot distinguish two species differing by less than 1 Da in total mass.

Written quickly, so the reasoning may be tighter than the wording.

6 likes in reply to #15 6mo
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l.chevalierTL327 Jan 2026#19
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m.adebayoTL228 Jan 2026#20

Electrospray ionisation produces multiply charged ions. For a 4 kDa peptide you expect mostly 2+, 3+, and 4+ charge states. Reading an electrospray spectrum means recognizing the envelope, not looking for one peak.

0 likes 6mo
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e.kimaniTL229 Jan 2026#21

Taking post #20 at face value and following it one step further.

The version of Adducts that circulates here is a simplification of a simplification. It is not wrong, but it has lost the conditions under which it holds, and those conditions are where the interesting cases live.

27 likes 6mo
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s.silvaTL230 Jan 2026#22

Post #18 and I disagree about the size of the effect, not about the direction.

I have no financial interest in anything named in this thread and I want to say so before I comment on Adducts, because it is the sort of subject where it matters.

0 likes 6mo
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e.ferrariTL231 Jan 2026#23
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p.amankwahTL21 Feb 2026#24

Two people in this thread mean different things by Adducts and are disagreeing about the definition while believing they are disagreeing about the facts. Worth pausing to define it.

8 likes 6mo
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i.rasmussenTL22 Feb 2026#25

This follows post #24 rather than contradicting it.

Quantitation by MS: most quantitation is done by LC-UV detection at 214 nm, not by MS, because extinction coefficients are better known. MS can quantify if an internal standard is used but that requires preparation.

None of the above is medical advice and I am not qualified to give any.

20 likes 6mo
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VThorvaldsenTL3Regular3 Feb 2026#26

Agreed on Adducts, with one qualification that I think matters. The reasoning holds for the case as described. Change the starting assumption and it does not, and the starting assumption is the part nobody states.

0 likes 6mo
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s.achebeTL24 Feb 2026#27
k.haddad, post #12: Resolution and mass accuracy are different specifications. An instrument can resolve two species and still assign their masses imprecisely, and the reverse is also possible. Not a conclusion. A place to stand while looking for one. Go to post

Taking Adducts seriously for a moment rather than deflecting: the honest position is that the community has observations and no controlled comparison, and those two things support very different sentences.

0 likes in reply to #12 6mo
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KnowltonTL3Regular5 Feb 2026#28

Coming back to post #26, because the follow-up matters more than the original answer.

Resolution: "high resolution" commonly means <5 ppm across the mass range. Unit-resolution instruments achieve ±1 Da at best and cannot distinguish two species differing by less than 1 Da in total mass.

If the premise is wrong, everything after it is decoration.

5 likes 6mo
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KLindqvistTL4 Moderator6 Feb 2026#29

Adducts is well covered in the tag pages, and the older discussions are better than the recent ones because they were argued out properly. Worth twenty minutes before adding to this one.

14 likes 6mo
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c.tullochTL27 Feb 2026 · edited#30

The reason Adducts keeps being re-asked is that the answer is conditional and people quote it without the condition. It is not that the answer is unknown.

28 likes 6mo