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Internal or external standards for quantification volatiles

Discussions about GC and other "gas phase" separation techniques.

3 posts Page 1 of 1
Hi,
I’m currently conducting a study on the (semi-)quantification of acetic acid (AA) concentration in a blueboard box containing q cellulose acetate object. The goal is to compare the acetic acid concentration in the box with and without passive adsorbers, in order to evaluate whether these adsorbers effectively reduce the AA content.
I plan to use headspace solid-phase microextraction (HS-SPME) to sample the acetic acid in the box. However, as you know, a standard method is required to achieve quantification—or at least semi-quantification—of AA. The challenge is that I probably won’t be able to use the standard internal calibration approach, since I need to measure the concentration inside the box (which is quite large) and cannot introduce a standard solution into it.
Would it be possible to sample the AA inside the box and then, immediately after sampling, expose the same SPME fiber to a vial containing the internal standard for a specific amount of time before running the analysis and have results comparable to a traditional internal standard procedure?

Regarding the external standard approach, I was wondering if the following simplified procedure could be acceptable, even without creating a full calibration curve at different standard concentrations:
1. Sample the AA in the box.
2. Analyze the fiber that was used in the box.
3. Using the same fiber (right after analysis), expose it to a standard solution (I’d appreciate suggestions on the most appropriate compound to use) for a defined period, then run the analysis again.
4. Compare the integrated area of the AA peak with that of the standard peak to obtain preliminary information on the AA amount.
5. Repeat the same procedure with the adsorbers placed inside the box, and compare the results obtained in step 4 with and without adsorbers.

All measurements would, of course, be performed in replicate.
I’d like to know whether this procedure is fundamentally flawed, or if you have any suggestions for improving it to achieve at least a reliable semi-quantification.
If I read this correctly, you want to know the concentration of AA in the gas phase inside the box?

Or is it really that you want to know how much AA is in the box material?

These are different problems for certain.
Hi,
This is an interesting study and quite a brain teaser.
I have been working with HS-SPME for some time and I am still not sure if it is a proper technique for quantification.
I prefer to work by comparison between samples and I believe it is what you should do.
Simply compare the signal obtained for AA in the box w/ and wo/ adsorbant.

I do see another issue however.
By experience, I know carboxylic acids (CAs) can be (very) strongly retained on some fibers (CAR/PDMS in my case).
When I approached Supelco about this problem, here is the answer I received:
"The problem of incomplete cleaning of SPME fibers, particularly with polar compounds like carboxylic acids, is recognized. These compounds can adhere to the fiber and may not be fully removed by standard cleaning protocols or heating alone. This can lead to carryover effects, where residual compounds from previous samples contaminate subsequent analyses."
Besides the fact that a special column is needed to analyze CAs.

Maybe you could check the free Scanview software from Agilent where you can find a lot of application notes.

Good luck
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