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PAH Stability and GC-MS issue

Posted: Fri Jun 13, 2025 9:05 pm
by Peppels
Good evening,
I'm having some issues related to the PAH analysis on my GC-MSMS.
I'm trying to validate a method for PAH determination following the EPA3546+EPA8270D. I'm working with a Shimadzu GC2010-TQ8040, which i'm using ad a single quadrupole.
I've few questions about different issues i'm facing:
1) First of all, i've started to use this instrument in January. Everything worked almost perfectly although it had been used without paying much attention. Calibrations where very good, although nobody had ever provided to change syringe, septa or glass insert. The only issue I could complain about was the very weak stability of the calibration, which lasted just 5 or 6 days. During the last days of March I've tried using the automatic addition of the internal standard using the autosampler, anda also this function worked great. On 16th of April I've done a new calibration, whitout any problem: R^2 was higher than 0.99 for almost all the analytes (23 PAH + 3 surrogates) and internal standars areas where perfectly replicable. Well, on 28th of April, the instrument started having trouble. No replicable areas for internal standards nor for the analytes. Planned a PM done by Shimadzu technician, who cleaned everything, from the inlet to the detector, replacing the syringe too. Although this, the instrument hasn't come back to its previous performaces. Tried to do diffent calibration, but couldn't achieve the previous performances. Since the 28th of April, I've tried replacing the syringe, septa, glass inserts different times, but can't understand why areas, which were perfectly replicable (1/2% difference between injections) before that day, have a 5 to 10% difference now. Have you any idea about this?
2) Yesterday I've calibrated the instrument using RSD<20% as acceptability criterion. Today, I've tried to analyse a 10ug/L and a 25ug/L standard, to verify the calibration, and noticed that the analytes concentration rised from 10ug/L to 15ug/L, and from 25ug/L to 37ug/L for the heavier analytes of the mix (Indeno-1,2,3-c,d,fluoranthene, benzo(ghi)perylene and the 4dibenzopyrene). Consider that the solutions where prepared from a 200ppm solution for both PAH and Surrogates, stored at -8°C and left at room temperature for 20minutes to avoid poor solubility of the heavier compounds in the mix. I've spiked 50ul of both in 10mL of DCM, obtaining a 1ppm and then, from the 1ppm spiked respectively 200ul and 500ul to 10mL of DCM to obtain the 20ug/L and 50ug/L solutions. All the spikes where done using a 5190 Agilent syringe. Have you any advice about this problem?
Thank you so much in advance and thank for the amount of informations available on the forum!
Peppels

Re: PAH Stability and GC-MS issue

Posted: Sat Jun 14, 2025 9:01 pm
by Peter Apps
Has there been any deterioration in peak shapes; tailing or broadening, or any loss of resolution?

Re: PAH Stability and GC-MS issue

Posted: Sun Jun 15, 2025 10:17 pm
by Peppels
Has there been any deterioration in peak shapes; tailing or broadening, or any loss of resolution?
Thanks for the answer. No, anything. The only factor I hadn't thought about Is the enviroment temperature. Consider that till the end of april the room was quite cool, 23/25°C. Since May temperature started raising and altough we try to keep the room cool, It can go from 25°C in the early morning to 36/38°C in the middle of the day.

Re: PAH Stability and GC-MS issue

Posted: Mon Jun 16, 2025 7:40 am
by Peter Apps
That room temperature is too high if you have DCM as a solvent. You really need an air conditioner, or run all your analyses over night.

Peter

Re: PAH Stability and GC-MS issue

Posted: Mon Jun 16, 2025 8:32 am
by Peppels
That room temperature is too high if you have DCM as a solvent. You really need an air conditioner, or run all your analyses over night.

Peter
So you would address most of the problems I described in the First part to this factor?

Re: PAH Stability and GC-MS issue

Posted: Mon Jun 16, 2025 5:11 pm
by Peter Apps
Your solutions will be evaporating and the syringe will draw bubbles instead of liquid. Try a solvent with a higher boiling point as an experiment.

Peter

Re: PAH Stability and GC-MS issue

Posted: Mon Jun 16, 2025 8:51 pm
by itspip
Metal crimp caps might help, but that room temperature will be causing DCM to evaporate too quickly for anything reproducible.

Re: PAH Stability and GC-MS issue

Posted: Tue Jun 17, 2025 10:30 pm
by Peppels
We are trying to analyze our calibration standards right now, during the night, while the room is completely closed and air conditioning Is working. Hope It works.

Re: PAH Stability and GC-MS issue

Posted: Wed Jul 02, 2025 7:21 am
by Peppels
Good morning,
after some attemps, I've obtained a good calibration after stabilizing room temperature. Now I've another problem related to the stability of the check standard after some hours.
The check standard should be 25ppb, but after few hours the instrument gives a value of 31/32ppb. Internal Standards areas are perfect.
Any idea about this issue?
Thank you.