In this work, a new analytical approach is proposed for monitoring biogenic volatile organic compounds (BVOCs) by combining headspace bar adsorptive microextraction (HS-BAμE) with gas chromatography–mass spectrometry (GC-MS). The HS-BAμE methodology was developed, optimized, validated and applied for the analysis of BVOCs emitted from two tree species (Eucalyptus globulus Labill. and Pinus pinaster Aiton) and compared with headspace solid phase microextraction (HS-SPME), commonly accepted as a reference technique. To achieve optimum experimental conditions, numerous assays were carried out by both methodologies, studying the release of the five major monoterpenoids (α-pinene, β-pinene, myrcene, limonene and 1,8-cineole) from the leaves of the tree species, whereas the maximum selectivity and efficiency were obtained using an activated carbon and PDMS/DVB fiber as sorbent phases for HS-BAμE and HS-SPME, respectively. Under optimized experimental conditions, both methodologies showed similar profiling and proportional responses, although the latter present a higher sensitivity in the analytical configuration used. For the five monoterpenoids studied, acceptable detection limits (LODs = 5.0 μg L−1) and suitable linear dynamic ranges (20.0–100.0 mg L−1; r2 ≥ 0.9959) were achieved, and intra- and inter-day studies proved that both methodologies exhibited good results (RSD and %RE ≤ 19.9%), which indicates a good fit for the assessment of BVOCs by the HS-BAμE/GC-MS methodology. Assays performed on sampled leaves by both optimized and validated methodologies showed high levels of the five major BVOCs released from E. globulus Labill. (10.2 ± 1.3 to 7828.0 ± 40.0 μg g−1) and P. pinaster Aiton (9.2 ± 1.4 to 3503.8 ± 396.3 μg g−1), which might act as potential fuel during forest fire’s propagation, particularly under extreme atmospheric conditions. This is the first time that BAμE technology was applied in the HS sampling mode, and, in addition to other advantages, it has proven to be an effective and promising analytical alternative for monitoring VOCs, given its great simplicity, easy handling and low cost.

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