Measuring aliphatic hydrocarbons in sediments by direct thermal desorption-gas chromatography-mass spectrometry: Matrix effects and quantification challenges.

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.

Direct thermal desorption-gas chromatography-tandem mass spectrometry versus microwave assisted extraction and GC-MS for the simultaneous analysis of polyaromatic hydrocarbons (PAHs, PCBs) from sediments.

Polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) are regulated contaminants usually investigated in sediments. Conventional approaches often use GC-MS to analyse them with a preliminary extraction step which can be solvent- and time-consuming. Here two extraction methodologies were optimized using experimental designs, and compared: microwave assisted extraction (MAE) and thermal desorption (TD); the latter was rarely used for sediments analyses. Several factors that may influence extraction recoveries were studied including matrix parameters (mass, organic matter (OM) content) and processing parameters. A definitive screening design DSD was performed to screen the 6 most influencing factors and model the extraction recoveries using TD. Whatever the OM content, a minimum sediment mass (5 mg) was better for an optimal extraction, with a minimum temperature rate (15 °C min-1), a maximum final temperature (350 °C) associated with a minimum hold time (5 min), and a maximum vent flow (150 mL min-1) between the TD unit and the cryogenic trap. Thereafter matrix effects were evaluated using standard addition, and quality assurance and control were implemented for comparing MAE and TD. TD-GC-MS/MS sensitivity was higher than MAE-GC-MS with detection limits in the range 5-1160 pg and 20-125 pg for PAHs and PCBs, respectively. When considering the appropriate strategy for quantification, TD was also reliable for sediments analysis. Although MAE was less sensitive to matrix effects, TD could significantly improve the analytical process, due to direct coupling with GC-MS/MS and complete automation. Moreover, TD offered possible higher spatial resolution than MAE, particularly for sediment cores analysis, due to the 1000-times lower sample size. At last, TD-GC-MS/MS appeared as a greener analytical procedure.