Sediment direct introduction and analysis of paraffinic alkanes by thermodesorption-GC–MS.

Chemometric optimisations of microwave-assisted and thermal desorptions.

Sediment dilution with sand reduces matrix effects from TD for accurate quantification.

Solventless, automated TD-GC–MS is suitable for alkanes direct analysis from sediments.

Direct sample introduction thermal desorption (TD) coupled to GC–MS was investigated for the analysis of paraffinic hydrocarbons (HCs) from polluted sediments. TD-GC–MS is sometimes used for analysing paraffinic HCs from atmospheric particles but rarely for their direct desorption from sediments. So, the new TD methodology, applied to sediments, required development, optimization and validation. A definitive screening experimental design was performed to discriminate the critical factors on TD efficiency, from model sediments containing various organic matter (OM) amounts. Low molecular weight HCs had extraction behaviours markedly different from high molecular ones (HMW-HCs), but a compromise was found using very few sediment amount (5 mg), high temperature rate (55 °C min−1) and final temperature (350 °C). Linear HCs (n-C10 to n-C40) could be quantified using the matrix-matched calibration method, with very low detection limits (3.8–13.4 ng). The amount of the overall paraffinic alkanes was also determined as a sum of unresolved components between predefined equivalent carbon ranges. The developed solventless methodology was compared to an optimized solvent microwave assisted extraction (MAE). Matrix effects could be higher for TD compared to MAE but it depended on sediment matrix. When matrix effect was strong, particularly on HMW-HCs signal depletion, a dilution with pure non-porous sand was favourable for accurate quantification. The sum of resolved and unresolved HCs gave comparable results between MAE and TD extractions, with an exception of alkanes greater than C30 which were less quantitatively extracted via TD. However, TD-GC–MS was more sensitive than MAE-GC–MS. So TD-GC–MS is useful for analyzing sediments containing a great range of paraffinic HCs (C9-C34) and it has the advantages of being fully automated, with few sample preparation and operator intervention, using very low amounts of solvent, and generating few wastes.

Paraffinic alkanes

Thermodesorption GC-MS

Sediments

Experimental designs

Matrix effects

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© 2024 The Authors. Published by Elsevier B.V.