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Analytics · Method validation

Relative retention time as a better inter-laboratory comparator — does this still hold?

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Solved by dr_seong in post #7
I had written a reply contradicting post #5 and deleted it. Here is what survived. The most useful single question about a method: what would it fail to detect? Every method has an answer and few documents state it. Scoping that to what I have actually seen rather than what I have read.

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EA
e.almeidaTL2Member14 Jun 2024#1

Relative retention time as a better inter-laboratory comparator — does this still hold? I have a specific reason for asking rather than idle curiosity, and the context is below.

What changes if the standard account of Relative retention time is wrong? I ask because I have been treating it as settled and I noticed this week that I could not say why.

Working through the consequences rather than the evidence, since others here are better placed on the evidence.

0 likes 2.1y
RF
ro.friskTL21 Jul 2024#2

The useful distinction on Relative retention time is between what was measured and what was inferred from it. Both end up in the same sentence and only one of them has error bars.

26 likes 2.1y
WN
w.novakTL3Regular13 Jul 2024#3

Where I part company with the opening post, and it is a narrow parting.

Where a pharmacopoeial monograph exists, a method that follows it inherits a great deal of assurance. Almost nothing discussed here has one.

I would want a second opinion before relying on that.

8 likes 2y
FW
f.weissTL223 Jul 2024#4
Community wiki post. Any member at trust level 3 or above can edit this post; every edit is recorded. Last edited by r.aldana_pharmd on 27 Oct 2024.
  • 28 Sep 2024 — TL4_Halvorsen: Replaced an unsourced figure with the published one and cited it.
  • 27 Oct 2024 — r.aldana_pharmd: Removed a claim that the cited source did not support.
Editors: TL4_Halvorsen, r.aldana_pharmd

The opening post is the version of this I will quote in future. One addition.

A request rather than an answer: could whoever has the primary source for Relative retention time post it? I have seen the claim three times this month and each version had lost a qualifier.

2 likes 2y
OO
orbitrap_olaTL3Mass spectrometrist2 Aug 2024#5

Two claims get bundled together under Relative retention time 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.

0 likes 2y
NB
n.brobergTL211 Aug 2024#6
orbitrap_ola, post #5: Two claims get bundled together under Relative retention time 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. Go to post

Useful. I had the fact and not the reason, which turns out to be the important half.

0 likes in reply to #5 2y
DS
dr_seongTL3Physician Solution20 Aug 2024#7

I had written a reply contradicting post #5 and deleted it. Here is what survived.

The most useful single question about a method: what would it fail to detect? Every method has an answer and few documents state it.

Scoping that to what I have actually seen rather than what I have read.

12 likes 23mo
IA
i.almeidaTL229 Aug 2024#8

I changed my mind about Relative retention time after someone here asked me for the source and I could not produce one. That is worth saying out loud because it is the ordinary way it happens.

4 likes 23mo
BJ
b.jankowiakTL3Regular6 Sep 2024#9

Everything in post #5 holds. The case it does not cover is the one I have.

Relative retention time has been discussed here with more heat than it deserves, mostly because two definitions have been in play the whole time.

27 likes 23mo
JF
j.falkTL214 Sep 2024#10
i.almeida, post #8: I changed my mind about Relative retention time after someone here asked me for the source and I could not produce one. That is worth saying out loud because it is the ordinary way it happens. Go to post

Narrowing post #9, because the general version has more than one answer.

The limit of quantitation determines what the impurity table can honestly contain. Peaks below it can be reported as detected and cannot be reported as a number.

Second-hand, so weight it accordingly.

13 likes in reply to #8 22mo
EO
e.okaforTL222 Sep 2024#11

Reporting a result to more decimal places than the method's precision supports is a small dishonesty that appears everywhere. A method with a two per cent relative standard deviation does not support a figure quoted to a hundredth.

6 likes 22mo
LT
l.trevinoTL230 Sep 2024#12
e.almeida, post #1: Relative retention time as a better inter-laboratory comparator — does this still hold? I have a specific reason for asking rather than idle curiosity, and the context is below. What changes if the standard account of Relative retention time is wrong? I ask because I have been treating it as settled and I noticed this week that I could… Go to post

Everything in post #8 holds. The case it does not cover is the one I have.

Nobody has said the unglamorous part of Relative retention time yet, so: most of the variation is explained by things that are boring to write about and easy to check.

15 likes in reply to #1 22mo
SR
s.rasmussenTL27 Oct 2024#13
w.novak, post #3: Where I part company with the opening post, and it is a narrow parting. Where a pharmacopoeial monograph exists, a method that follows it inherits a great deal of assurance. Almost nothing discussed here has one. I would want a second opinion before relying on that. Go to post

My experience of Relative retention time contradicts the reply above. I am posting it as a data point rather than as a refutation, because one person's experience is exactly that.

0 likes in reply to #3 22mo
FW
f.wojcikTL215 Oct 2024#14

System suitability is the ongoing evidence that a validated method is still performing. Validation is done once; suitability is done every run, and it is the one that appears on a certificate.

I have no interest in any supplier named above.

1 like 21mo
J
JFitzgibbonTL2Member22 Oct 2024 · edited#15

Small correction to my own earlier position on Relative retention time. I had the units the wrong way round, which changes the conclusion by an order of magnitude and therefore changes it entirely.

9 likes 21mo
NN
n.nakamuraTL229 Oct 2024#16
f.wojcik, post #14: System suitability is the ongoing evidence that a validated method is still performing. Validation is done once; suitability is done every run, and it is the one that appears on a certificate. I have no interest in any supplier named above. Go to post

Peak purity assessment using a diode-array detector checks whether a peak is spectrally homogeneous. It is a weak test and it is better than not looking.

22 likes in reply to #14 21mo

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