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1. Rapid Screening and Quantification of PFAS Enabled by SPME-DART-MS

   https://doi.org/10.1021/jasms.3c00088  

   Emmons, Ronald V.; Fatigante, William; Olomukoro, Aghogho A.; Musselman, Brian; Gionfriddo, Emanuela (September 2023, Journal of the American Society for Mass Spectrometry)

   Per- and polyfluoroalkyl substances (PFAS), an emerging class of toxic anthropogenic chemicals persistent in the environment, are currently regulated at the low part-per-trillion level worldwide in drinking water. Quantification and screening of these compounds currently rely primarily on liquid chromatography hyphenated to mass spectrometry (LC-MS). The growing need for quicker and more robust analysis in routine monitoring has been, in many ways, spearheaded by the advent of direct ambient mass spectrometry (AMS) technologies. Direct analysis in real time (DART), a plasma-based ambient ionization technique that permits rapid automated analysis, effectively ionizes a broad range of compounds, including PFAS. This work evaluates the performance of DART-MS for the screening and quantification of PFAS of different chemical classes, employing a central composite design (CCD) to better understand the interactions of DART parameters on their ionization. Furthermore, in-source fragmentation of the model PFAS was investigated based on the DART parameters evaluated. Preconcentration of PFAS from water samples was achieved by solid phase microextraction (SPME), and extracts were analyzed using the optimized DART-MS conditions, which allowed obtaining linear dynamic ranges (LDRs) within 10 and 5000 ng/L and LOQs of 10, 25, and 50 ng/L for all analytes. Instrumental analysis was achieved in less than 20 s per sample. 

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2. Quantitative analysis of cannabinoids by zone heat-assisted DART-MS with in-situ flash derivatization

   https://doi.org/10.1016/j.forc.2025.100641  

   Dong, Wen; Yuan, Junxiaohan; Yang, Xin; Zhang, Ning; Zhang, Mengliang (January 2025, Forensic Chemistry)

   Accurate quantitation of cannabinoids, particularly Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD), is essential for regulatory compliance, forensic investigations, and cannabis product development. Traditional methods, such as liquid chromatography (LC) and gas chromatography (GC) coupled with mass spectrometry, provide reliable results but are time-consuming and resource-intensive. This study introduces a rapid and high-throughput analytical method using zone heat-assisted direct analysis in real time mass spectrometry (DART-MS) combined with in-situ flash derivatization. The method employs trimethylphenylammonium hydroxide (TMPAH) for efficient derivatization, allowing for the differentiation of THC, CBD, and their acidic precursors, Δ9-tetrahydrocannabinolic acid (THCA) and cannabidiolic acid (CBDA). A custom heated transfer zone was implemented to enhance derivatization efficiency and reduce carryover effects. The method was optimized for reagent concentration and gas stream temperature, achieving high specificity by minimizing interference from isomeric cannabinoids. Validation studies demonstrate good accuracy (relative error within ±15.9 %) and precision (relative standard deviation ≤15 %), with limits of quantitation of 7.5 µg/mL for THC/CBD and 0.5 µg/mL for THCA/CBDA. Comparative analysis of cannabis samples showed a strong correlation with reference LC/MS results, highlighting the reliability of the proposed method. DART-MS offers a significant time advantage, requiring only 10 s per analysis, making it a promising tool for high-throughput screening of cannabis samples in forensic laboratories. 

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3. Analysis of oil-based ignitable liquid residues by GC–MS and DART–MS

   https://doi.org/10.1016/j.forc.2025.100701  

   Dong, Wen; Chong, Ngee Sing; Thanni, Qudus Ayodeji; de_Boves_Harrington, Peter; Zhang, Mengliang (September 2025, Forensic Chemistry)

   Fatty acid-based ignitable liquids (ILs), such as biodiesels and bio-based lighter fluids, represent a growing class of accelerants with limited forensic characterization. In this study, we applied gas chromatography–mass spectrometry (GC–MS) and direct analysis in real time mass spectrometry (DART–MS) to analyze plant oil-derived IL residues on wood and fabric substrates. ILs were prepared from ten different plant oils, subjected to burning, and extracted from fire debris using the ASTM E1412 activated charcoal method. GC–MS analysis resolved characteristic fatty acid methyl esters (FAMEs) and identified diagnostic fragment ions (m/z 55, 67, 74, 79). The fragmentation patterns of unsaturated and saturated FAMEs were systematically examined and compared against experimental data and reference spectra from online databases, demonstrating strong agreement and validating the reliability of these ion ratios as qualitative indicators of FAME saturation. DART–MS enabled rapid confirmation of major unsaturated FAMEs through the detection of protonated molecular ions, offering complementary identification without chromatographic separation. Chemometric analysis using principal component analysis (PCA) and analysis of variance-PCA revealed that FAME profiles were strongly dependent on the IL sources and remained reliable across replicate preparations and synthesis conditions, while substrate and combustion effects were mitigated using targeted ion extraction. These findings demonstrate the practical casework relevance of combining GC–MS and DART–MS for the detection and classification of fatty acid–based ILs in fire debris, providing robust chemical evidence to support arson investigations and to guide the inclusion of these emerging accelerants in forensic ignitable-liquid classification schemes. 

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4. New insights into atmospherically relevant reaction systems using direct analysis in real-time mass spectrometry (DART-MS)

   https://doi.org/10.5194/amt-10-1373-2017  

   Zhao, Yue; Fairhurst, Michelle C.; Wingen, Lisa M.; Perraud, Véronique; Ezell, Michael J.; Finlayson-Pitts, Barbara J. (January 2017, Atmospheric Measurement Techniques)

   The application of direct analysis in real-time mass spectrometry (DART-MS), which is finding increasing use in atmospheric chemistry, to two different laboratory model systems for airborne particles is investigated: (1) submicron C₃–C₇ dicarboxylic acid (diacid) particles reacted with gas-phase trimethylamine (TMA) or butylamine (BA) and (2) secondary organic aerosol (SOA) particles from the ozonolysis of α-cedrene. The diacid particles exhibit a clear odd–even pattern in their chemical reactivity toward TMA and BA, with the odd-carbon diacid particles being substantially more reactive than even ones. The ratio of base to diacid in reacted particles, determined using known diacid–base mixtures, was compared to that measured by high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), which vaporizes the whole particle. Results show that DART-MS probes  ∼  30 nm of the surface layer, consistent with other studies on different systems. For α-cedrene SOA particles, it is shown that varying the temperature of the particle stream as it enters the DART-MS ionization region can distinguish between specific components with the same molecular mass but different vapor pressures. These results demonstrate the utility of DART-MS for (1) examining reactivity of heterogeneous model systems for atmospheric particles and (2) probing components of SOA particles based on volatility. 

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5. Recovery and detection of ignitable liquid residues from the substrates by solid phase microextraction – direct analysis in real time mass spectrometry

   https://doi.org/10.1016/j.forc.2024.100611  

   Perna, Shruthi; Chong, Ngee-Sing; Zhang, Mengliang (December 2024, Forensic Chemistry)

   In this study, direct analysis in real time mass spectrometry (DART-MS) was coupled to the solid phase microextraction (SPME) to extract and analyze the ignitable liquid residues (ILR) present in the sample matrices. The SPME extraction parameters, such as extraction temperature and extraction time, were optimized using a two factor central composite design. The SPME-DART-MS setup was utilized to analyze the substrates and fire debris matrices spiked with gasoline. The results indicate that the less volatile marker compounds from gasoline were recovered from the substrates and fire debris, and their profiles matched well with the gasoline liquid samples analyzed directly by DART-MS. As expected, the effective extraction of marker compounds in gasoline required a relatively high temperature, i.e., 150 ℃. In the presence of a matrix, a higher extraction temperature and longer extraction time could benefit the extraction efficiency. The desorption of ILR on SPME fiber was performed by inserting the fiber into the DART-MS helium gas stream at 300 ℃ for 1 min with no carry-over residues being observed between successive samples. The chemical information attained with this method is typically not observed in the current GC/MS-based practice. The SPME-DART-MS was also extended to reanalyze less volatile components of ILR on substrates after the ASTM E1412 activated charcoal method, which indicates its possible application subsequent to the traditional GC/MS ILR analysis. The SPME-DART-MS has shown promise in ILR detection as an important complementary tool. 

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