Optimizing Headspace Analysis to Assess the Suitability of Fused Deposition Modeling Materials Used in Cultural Heritage

Volatile emissions from conservation materials can pose risks to cultural heritage objects, especially in enclosed environments. The Oddy test, though widely used, is limited by long testing times, low chemical specificity, and subjective interpretation. This study applies trap‐enrichment solid‐phase microextraction coupled with gas chromatography–mass spectrometry (SPME‐GC–MS) to analyze volatile emissions from nine fused deposition modeling (FDM) polylactic acid materials previously assessed by the Oddy test. The aim was to chemically characterize emitted compounds and relate them to observed corrosion, supported by Raman spectroscopy of corrosion products. Method optimization using three representative materials identified 1 g as an optimal sample mass for sensitivity and reproducibility. Sampling temperature was critical: higher temperatures enhanced analyte release but were kept below 80°C to prevent thermal degradation. Results show that SPME‐GC–MS offers significantly greater chemical resolution than the Oddy test, enabling identification of specific volatiles associated with corrosion. Correlation with Raman data strengthened links between emissions and corrosion products.