Atmospheric Solids Analysis Probe Research Articles

Demonstration of an End-To-End Workflow Using Atmospheric Solids Analysis Probe-Mass Spectrometry (ASAP-MS) With Real-Time Sample Recognition Software for the Identification of Falsified and Substandard Pharmaceutical Tablets.

Counterfeit pharmaceuticals are a subclass of falsified and substandard medicines. They are illicit products, purporting to be genuine medicines, that are made and sold by criminal organisations. They represent a significant risk to patient safety, as well as a financial and reputational threat to the companies who make the genuine medicines. It is essential to have analytical methods to determine if suspect samples seized by law enforcement agencies are counterfeit, with mass spectrometry (MS) being a commonly used technique in forensic cases. Speed-to-answer is vital to enable law enforcement agencies to progress investigations, as well as for pharmaceutical companies so that they can notify health authorities of the circulation of counterfeit medicines. In this work, an atmospheric solids analysis probe (ASAP)-MS was assessed as a fast and simple-to-use approach to analyse tablets on a commercially available instrument. Complementing the analytics with real-time sample recognition software demonstrated that the classification of tablets as authentic or counterfeit could be achieved quickly (< 2 min) and without the need for MS interpretation skills. Authentication of five tablets (two authentic pharmaceuticals, one placebo and two counterfeits containing the correct active pharmaceutical ingredient [API] but at lower quantities than in the genuine medicine and with different excipient contents) of unknown origin was achieved with 100% success. This creates the opportunity to deploy the end-to-end workflow as a tool for non-scientists, such as law enforcement officers and border control staff, for use in-territory to obtain fast answers and make data-led decisions to control the illegal trading of medicines.

Performance Comparison of Ambient Ionization Techniques Using a Single Quadrupole Mass Spectrometer for the Analysis of Amino Acids, Drugs, and Explosives.

The utilization of ambient ionization (AI) techniques for mass spectrometry (MS) has significantly grown due to their ability to facilitate rapid and direct sample analysis with minimal sample preparation. This study investigates the performance of various AI techniques, including atmospheric solids analysis probe (ASAP), thermal desorption corona discharge (TDCD), direct analysis in real time (DART), and paper spray coupled to a Waters QDa mass spectrometer. The focus is on evaluating the linearity, repeatability, and limit of detection (LOD) of these techniques across a range of analytes, including amino acids, drugs, and explosives. The results show that each AI technique exhibits distinct advantages and limitations. ASAP and DART cover high concentration ranges, which may make them suitable for semiquantitative analysis. TDCD demonstrates exceptional linearity and repeatability for most analytes, while paper spray offers surprising LODs despite its complex setup (between 80 and 400 pg for most analytes). The comparison with electrospray ionization (ESI) as a standard method shows that ambient ionization techniques can achieve competitive LODs for various compounds such as PETN (80 pg ESI vs 100 pg ASAP), TNT (9 pg ESI vs 4 pg ASAP), and RDX (4 pg ESI vs 10 pg ASAP). This study underscores the importance of selecting the appropriate ambient ionization technique based on the specific analytical requirements. This comprehensive evaluation contributes valuable insights into the selection and optimization of AI techniques for diverse analytical applications.

Rapid and accurate detection of cinnamon oil adulteration in perilla leaf oil using atmospheric solids analysis probe-mass spectrometry

Perilla leaf oil (PLO) is a global premium vegetable oil with abundant nutrients and substantial economic value, rendering it susceptible to potential adulteration by unscrupulous entrepreneurs. The addition of cinnamon oil (CO) is one of the main adulteration avenues for illegal PLOs. In this study, new and real-time ambient mass spectrometric methods were developed to detect CO adulteration in PLO. First, atmospheric solids analysis probe tandem mass spectrometry combined with principal component analysis and principal component analysis-linear discriminant analysis was employed to differentiate between authentic and adulterated PLO. Then, a spectral library was established for the instantaneous matching of cinnamaldehyde in the samples. Finally, the results were verified using the SRM mode of ASAP-MS/MS. Within 3 min, the three methods successfully identified CO adulteration in PLO at concentrations as low as 5% v/v with 100% accuracy. The proposed strategy was successfully applied to the fraud detection of CO in PLO.

Identification of MDA in seized ecstasy-like samples using atmospheric solids analysis probe mass spectrometry and machine learning

In this study, a total of 64 samples of ecstasy tablets seized during operations conducted within the State of Rio Grande do Sul – Brazil in 2021–2022 were analyzed. The instrumental analysis was performed using the Radian ASAP MS instrument with a single quadrupole mass spectrometer and an Atmospheric Solids Analysis Probe (ASAP) interface. Data preprocessing was conducted using MATLAB to improve data quality for subsequent chemometric analyses. Classification models seeking to identify samples containing MDA (3,4-methylenedioxyamphetamine) were developed using Linear Discriminant Analysis (LDA) with variable selection through the genetic algorithm (GA), stepwise (SW), and successive projections algorithm (SPA). Additionally, Partial Least Squares Discriminant Analysis (PLS-DA) models were explored. The GA-LDA model achieved an accuracy of approximately 95% for both training and testing sets, demonstrating its effectiveness in distinguishing between sample classes. It selected only five variables during model building. The SW-LDA model displayed exceptional performance in the training set, achieving 100% for all metrics. However, its accuracy for the testing set was slightly lower at 84.7%, suggesting potential overfitting due to the inclusion of numerous variables. The SPA-LDA model, while not the best performer in the testing set, selected variables that were more easily attributed to specific ions/fragments, aiding in the interpretation of results. Interpretation of selected variables revealed key m/z values associated with different compounds found in the samples, such as MDMA, cocaine, and amphetamine-related fragments. Notably, the SPA method selected six variables that played a crucial role in distinguishing between sample groups. These findings contribute to the advancement of forensic drug analysis and quality control processes.

"Screening of Phytochemicals, Antibacterial and Antioxidant Activities Determination for the Plant “Allium Sativum” and Identification of Allicin (from Fresh Garlic) using ASAP (Atmospheric Solids Analysis Probe) Technique with a Compact Mass Spectrometer"

"Screening of Phytochemicals, Antibacterial and Antioxidant Activities Determination for the Plant “Allium Sativum” and Identification of Allicin (from Fresh Garlic) using ASAP (Atmospheric Solids Analysis Probe) Technique with a Compact Mass Spectrometer"

University teaching of mass spectrometry as a key practical technique within the context of a fully integrated, spiral curriculum

RationaleMass spectrometry (MS) is introduced to high school students in the UK in many pre‐university course syllabi. As such, we have identified the use of MS as a key technique that should be taught practically to undergraduates from the outset of their studies. This mini‐review describes how we introduce and develop students' use of MS throughout our three‐year undergraduate spiral curriculum practical programme, using atmospheric pressure chemical ionization MS (APCI‐MS).MethodsWe have used an Advion ExpressionL spectrometer, fitted with an atmospheric solids analysis probe or a Plate Express TLC sampler for sample introduction.ResultsWe have successfully demonstrated the use of APCI‐MS in a range of practicals and experiments covering organic and organometallic chemistries, with large cohorts of students gaining hands‐on instrumental experience in authentic research settings.ConclusionsAPCI‐MS has proven to be an easy‐to‐use and valuable addition to our undergraduate practical course. The robustness of the spectrometer enables routine use by large cohorts of students with minimal supervision, and routine maintenance can be carried out by non‐specialist technicians. Students can readily process and interpret results for a series of routine analyses, as well as demonstrate uses in problem‐solving exercises.

Assessment of a Single Quadrupole Mass Spectrometer Combined with an Atmospheric Solids Analysis Probe for the On-Site Identification of Amnesty Bin Drugs.

The surging number of people who abuse drugs has a great impact on healthcare and law enforcement systems. Amnesty bin drug analysis helps monitor the "street drug market" and tailor the harm reduction advice. Therefore, rapid and accurate drug analysis methods are crucial for on-site work. An analytical method for the rapid identification of five commonly detected drugs ((3,4-methylenedioxymethamphetamine (MDMA), cocaine, ketamine, 4-bromo-2,5-dimethoxyphenethylamine, and chloromethcathinone)) at various summer festivals in the U.K. was developed and validated employing a single quadrupole mass spectrometer combined with an atmospheric pressure solids analysis probe (ASAP-MS). The results were confirmed on a benchtop gas chromatography-mass spectrometry instrument and included all samples that challenged the conventional spectroscopic techniques routinely employed on-site. Although the selectivity/specificity step of the validation assessment of the MS system proved a challenge, it still produced 93% (N = 279) and 92.5% (N = 87) correct results when tested on- and off-site, respectively. A few "partly correct" results showed some discrepancies between the results, with the MS-only unit missing some low intensity active ingredients (N-ethylpentylone, MDMA) and cutting agents (caffeine, paracetamol, and benzocaine) or detecting some when not present. The incorrect results were mainly based on library coverage. The study proved that the ASAP-MS instrument can successfully complement the spectroscopic techniques used for qualitative drug analysis on- and off-site. Although the validation testing highlighted some areas for improvement concerning selectivity/specificity for structurally similar compounds, this method has the potential to be used in trend monitoring and harm reduction.

Atmospheric solids analysis probe mass spectrometry: An easy bolt-on for the synthetic undergraduate teaching laboratory.

High costs and student numbers can often hinder implementation of mass spectrometry (MS) in the undergraduate teaching laboratory, often with technicians running samples on students' behalf, and the implementation of MS only in discrete or isolated experiments. This study explores the use of atmospheric solids analysis probe MS (ASAP-MS) as a relatively low-cost, benchtop instrument, and its potential for application as a 'bolt-on' to existing undergraduate organic chemistry experiments. Thirteen products synthesised in undergraduate laboratory experiments were analysed by ASAP-MS, along with their starting materials. Analysis was carried out with a Waters RADIAN ASAP mass spectrometer, at four different cone voltages simultaneously to provide fragmentation information. Out of the 13 undergraduate experiments, ASAP-MS was shown to be complementary in 11 of these, either through simple analysis of the precursor ion or by a more complex analysis of the fragments. ASAP-MS provided spectra that both complement and enhance intended learning outcomes in existing organic chemistry experiments, showing its versatility as a bolt-on technique. Moving forward, ASAP-MS will be integrated into the University of Surrey's undergraduate teaching laboratory.

Comparison of direct analysis in real-time mass spectrometry, atmospheric solids analysis probe-mass spectrometry, and ion mobility spectrometry for ensuring food safety by rapid screening of poppy seeds.

The opium poppy (Papaver somniferum) is a global commercial crop that has been historically valued for both medicinal and culinary purposes. Naturally occurring opium alkaloids including morphine, codeine, thebaine, noscapine, and papaverine are found primarily in the latex produced by the plant. If the plant is allowed to fully mature, poppy seeds that do not contain the opium alkaloids will form within the pods and may be used in the food industry. It is possible for the seeds to become contaminated with alkaloids by the latex during harvesting, posing a potential health risk for consumers. In the USA, there have been more than 600 reported adverse events including 19 fatalities that may be linked to the consumption of a contaminated poppy-containing product such as home-brewed poppy seed tea. Unwashed poppy seeds and pods may be purchased over the Internet and shipped worldwide. The Forensic Chemistry Center, US Food and Drug Administration (FDA) has evaluated several mass spectrometers (MS) capable of rapid screening to be used for high-throughput analysis of samples such as poppy seeds. These include a direct analysis in real-time (DART) ambient ionization source coupled to a single-quadrupole MS, an atmospheric solids analysis probe (ASAP) ionization source coupled to the same MS, and ion mobility spectrometers (IMS). These instruments have been used to analyze 17 poppy seed samples for the presence of alkaloids, and the results were compared to data obtained using liquid chromatography with mass spectral detection (LC-MS/MS). Results from the 17 poppy seed samples indicate that the DART-MS, ASAP-MS, and IMS devices detect many of the same alkaloids confirmed during the LC-MS/MS analyses, although both the false-positive and false-negative rates are higher, possibly due to the non-homogeneity of the samples and the lack of chromatographic separation.

OpenASAP: An affordable 3D printed atmospheric solids analysis probe (ASAP) mass spectrometry system for direct analysis of solid and liquid samples

Atmospheric Solids Analysis Probe (ASAP) mass spectrometry is a versatile technique allowing direct sampling of solid and liquid samples, but its adoption is limited due to the high cost of commercial ASAP systems. To address this, we present OpenASAP, an open-source ASAP system for mass spectrometers that can be fabricated for $20 or less using 3D-printing. Our design is readily adaptable to instruments from different manufacturers and can be produced with a variety of additive manufacturing techniques on consumer-grade 3D-printers. The probe allows for rapid sampling of solid and liquid samples without sample preparation, making it useful for high throughput screening, investigating spatial localization and function of analytes in biological samples, and incorporating mass spectrometry in instructional settings. We demonstrate its effectiveness by obtaining mass spectra of three natural product standards at levels as low as 10 ng/ml in liquid samples, and detecting these metabolites in microbial cultures that are difficult to analyze due to complex sample matrices or analyte properties. Furthermore, we demonstrate direct sampling of thin layer chromatography (TLC) spots of these cultures.

Fast and reliable characterization of egg triacylglycerol profiles using atmospheric solids analysis probe tandem mass spectrometry (ASAP-MS/MS) combined with chemometric tools

In this study, the potential of atmospheric solid analysis probe tandem mass spectrometry (ASAP-MS/MS) was assessed as a green and rapid method combined with gas chromatography with flame ionization detection (GC-FID) and chemometrics to determine the triacylglycerol (TAG) profile of eggs from various housing systems, including indoor, cage-free, free-range, organic, and enriched systems. The most abundant ions were identified using the product ion and neutral loss scan. The fatty acid composition, mainly unsaturated, palmitic, and stearic acids of eggs was influenced by the housing systems. The optimal conditions of ASAP-MS for cone voltage, desolvation gas temperature, and desolvation gas flow were determined to be 40 V, 600 °C, and 1100 L h−1, respectively. The main TAGs (50:2, 50:1, 52:4, 52:3, 52:2, 52:1, 54:4, 54:3, 54:2, 54:1) were observed in the mass range m/z 830–890. Notable differences were observed for TAGs 54:1 and 52:4, which were found in significantly higher levels on WE and CE. The proposed methodology enables rapid and efficient TAG profiling of egg yolks, providing a solid foundation for future research in this field.

Assessment of atmospheric solids analysis probe as a tool for the rapid determination of drug purity.

The ability to determine the purity (% controlled compound) of drug-of-abuse samples is necessary for public health and law enforcement. Here, we describe the assessment of atmospheric solids analysis probe (ASAP) for the rapid determination of drug purity for a set of formulated pharmaceuticals, chosen due to their availability, uncontrolled status and consistency. Paracetamol and loratadine were used as models of high and low purity compounds being ~90% and ~10% active ingredient, respectively. Individual tablets were ground up and diluted in an internal standard solution. The resulting samples were analysed by ASAP coupled to a Waters QDa mass spectrometer followed by confirmatory testing by liquid chromatography-tandem mass spectrometry (LC-MS/MS). The inclusion of a non-matched internal standard (quinine) improved linearity and repeatability of drug analysis by ASAP-MS. Levels of drug purity using formulated pharmaceutical tablets were found to be highly comparable with results produced by the 'gold standard' LC-MS/MS technique. Rapid determination of drug purity is therefore possible with ASAP-MS for highly concentrated samples with minimal sample preparation. It may be possible to use this deployable system to determine drug purity outside of a laboratory setting.

Supramolecular solvent extraction and ambient mass spectrometry for the determination of organic contaminants in food packaging material

A rapid method based on a fast sample treatment with supramolecular solvents (SUPRASs) and ambient mass spectrometry (AMS) analysis was developed for the screening and quantification of organic contaminants in food packaging materials (FCMs). The suitability of SUPRASs made up of medium chain alcohols in ethanol:water mixtures was investigated, given their low toxicity, proven capacity for multi-residue analysis (since they provide a wide variety of interactions and multiple binding sites) and restricted access properties for simultaneous sample extraction and clean-up. Two families of emerging organic pollutants, bisphenols and organophosphate flame retardants, were targeted as representative compounds. The methodology was applied to 40 FCMs. Target compounds were quantitated using ASAP (atmospheric solids analysis probe)-low resolution MS and a broad-spectrum screening of contaminants was performed through spectral library search using direct injection probe (DIP) and high resolution MS (HRMS). The results showed the ubiquity of bisphenols and of some flame retardants, as well as the presence of other additives and unknown compounds in about half of the analyzed samples, which highlight the complex composition of FCMs and the possible associated health risks.

Impact of Ambient Vapors on Spectra of 4-Nitroaniline Recorded under Atmospheric Solids Analysis Probe (ASAP) Mass Spectrometric Conditions.

Thermally desorbed 4-nitroaniline (4-NA), upon atmospheric pressure chemical ionization (APCI), generates gaseous ions for its protonated species. The APCI mass spectrum recorded under mild in-source ion-activating conditions from 4-NA showed a peak at m/z 139, whereas that acquired under high ion-activating conditions showed two additional peaks at m/z 122 (•OH loss) and 92 (•NO loss). The spectrum changed instantaneously when acetonitrile vapor was introduced to the source. In the new spectrum, both m/z 122 and 92 peaks were absent, while a new peak appeared at m/z 93. Ion-mobility separation carried out with the m/z 139 ion revealed that the initial ion represented the thermodynamically favored nitro-protonated tautomer. The ion population changed to an ensemble dominated by the less-favored amino-protomer when acetonitrile vapor was introduced to the ion source. The amino-protomer, upon collisional activation, loses •NO2 to generate an m/z 93 ion, which was confirmed to be the 4-dehydroanilinium ion. Ion mobility provided a practical way to monitor the changes secured by acetonitrile vapor because the two protomers showed different arrival times. Under spray-ionization conditions, the formation of the thermodynamically less favored protomer has been attributed to kinetic trapping. Our study demonstrated that the less favored amino-protomer could be generated by introducing acetonitrile vapor under nonspray conditions. Apparently, under APCI conditions, protonated water vapor attaches to the nitro group to generate a proton-bound heterodimer, which upon activation dissociates to yield the nitro-protomer. In contrast, protonated acetonitrile makes a tighter complex preferentially with the amino group, which upon activation breaks to the amino-protomer.

First report on quality and purity assessment of sweet almond oil in Brazilian body oils by gas chromatography and mass spectrometry.

Sweet almond oil is a raw material with high-added value used in different products. Then, the aim of this study is to evaluate the quality and purity of 10 body oils based on sweet almond oils currently available in the Brazilian market. Fatty acid composition and triacylglycerol (TAG) profile were determined by gas chromatography with flame ionization detector (GC-FID) and atmospheric solids analysis probe mass spectrometry (ASAP-MS), respectively. The authenticity of samples was assessed using an analytical curve equation. Soybean oil was chosen as the adulterant because it is the cheapest vegetable oil commercialized in Brazil. Hierarchical clustering analysis (HCA) in conjunction with ASAP-MS classified product samples according to the type of vegetable oil (soybean and sweet almond oils). The addition of soybean oil (8.79% to 99.70%) was confirmed in samples. However, only two samples stated in their label the presence of soybean oil as an ingredient. These findings highlight the need for better oversight by regulatory bodies to ensure that consumers acquire high quality and authentic products based on equally high quality and purity of sweet almond oils.

Rapid Single Particle Atmospheric Solids Analysis Probe-Mass Spectrometry for Multimodal Analysis of Microplastics.

Despite mass spectrometry (MS) being proven powerful for the characterization of synthetic polymers, its potential for the analysis of single particle microplastics (MPs) is yet to be fully disclosed. To date, MPs are regarded as ubiquitous contaminants, but the limited availability of techniques that enable full characterizations of MPs results in a lack of systematic data regarding their occurrence. In this study, an atmospheric solid analysis probe (ASAP) coupled to a compact quadrupole MS is proposed for the chemical analysis of single particle microplastics, while maintaining full compatibility with complementary staining and image analysis approaches. A two-stage ASAP probe temperature program was optimized for the removal of additives and surface contaminants followed by the actual polymer characterization. The method showed specific mass spectra for a wide range of single particle MPs, including polyolefins, polyaromatics, polyacrylates, (bio)polyesters, polyamides, polycarbonates, and polyacrylonitriles. The single particle size detection limits for polystyrene MPs were found to be 30 and 5 μm in full scan and selected ion recording mode, respectively. Moreover, results are presented of a multimodal microplastic analysis approach in which filtered particles are first characterized by staining and fluorescence microscopy, followed by simple probe picking of individual particles for subsequent analysis by ASAP-MS. The method provides a full characterization of MP contamination, including particle number, particle size, particle shape, and chemical identity. The applicability of the developed multimodal method was successfully demonstrated by the analysis of MPs in bioplastic bottled water.

Secret Recipe Revealed: Chemical Evaluation of Raw Colouring Mixtures from Early 19th Century Moravia.

An archaeological excavation in Prostějov (Czech Republic) revealed a workshop of a local potter with colourless, pink, and blue powders presumably used to produce faience/surface decoration. A comprehensive analytical study, which combined elemental and molecular analysis techniques, was performed to shed light on the chemical composition of these unique findings. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM EDX), inductively coupled-plasma mass spectrometry (ICP MS), flow injection analysis (FIA) with electrospray ionisation mass spectrometry (ESI MS), laser desorption ionisation mass spectrometry (LDI MS), and Raman spectroscopy were applied to reveal the elemental composition of the powders and identify the colouring agents in the pink and blue powders. The colouring agents in the pink powder were probably iron and the agent in the blue powder is Prussian blue. On top of that, it was also possible to determine the organic additives in these powders through pyrolysis gas chromatography with mass spectrometric detection (Py GC/MS), atmospheric solids analysis probe ion mobility mass spectrometry (ASAP IM MS), and LDI MS. The organic constituents were identified as plant resin, beeswax, and fats. These results point to the preparation of faience/pigment mixtures as oil paint.

Analysis of Thermoplastic Copolymers by Mild Thermal Degradation Coupled to Ion Mobility Mass Spectrometry.

Thermal desorption/degradation with an atmospheric solids analysis probe (ASAP) and ion mobility (IM) separation are coupled with mass spectrometry (MS) analysis and tandem mass spectrometry (MS/MS) fragmentation to characterize thermoplastic elastomers. The compounds investigated, which are used in the manufacture of a wide variety of packaging materials, are mainly composed of thermoplastic copolymers, but also contain additional chemicals ("additives"), like antioxidants and UV stabilizers, for enhancement of their properties or protection from degradation. The traditional method for analyzing such complex mixtures is vacuum pyrolysis followed by electron or chemical ionization mass spectrometry, often after gas chromatography separation. Here, an alternative, faster approach, involving mild degradation at atmospheric pressure (ASAP) and subsequent characterization of the desorbates and pyrolyzates by IM-MS, and if needed, MS/MS is presented. Such multidimensional dispersion considerably simplifies the resulting spectra, permitting the conclusive separation, characterization, and classification of the multicomponent materials examined.

New insights into the Van Krevelen diagram: Automated molecular formula determination from HRMS for a large chemical profiling of lichen extracts.

In recent years, LC-MS has become the golden standard for metabolomic studies. Indeed, LC is relatively easy to couple with the soft electrospray ionization. As a consequence, many tools have been developed for the structural annotation of tandem mass spectra. However, it is sometimes difficult to do data-dependent acquisition (DDA), especially when developing new methods that stray from the classical LC-MS workflow. An old tool from petroleomics that has recently gained popularity in metabolomics, the Van Krevelen diagram, is adapted for an overview of the molecular diversity profile in lichens through high-resolution mass spectrometry (HRMS). A new method is benchmarked against the state-of-the-art classification tool ClassyFire using a database containing most known lichen metabolites (n ≈2,000). Four lichens known for their contrasted chemical composition were selected, and extractions with apolar, aprotic polar, and protic polar solvents were performed to cover a wide range of polarities. Extracts were analyzed with direct infusion electrospray ionization mass spectrometry (DI-ESI-MS) and atmospheric solids analysis probe mass spectrometry (ASAP-MS) techniques to be compared with the chemical composition described in the literature. The most common lichen metabolites were efficiently classified, with more than 90% of the molecules in some classes being matched with ClassyFire. Results from this method are consistent with the various extraction protocols in the present case study. This approach is a rapid and efficient tool to gain structural insight regarding lichen metabolites analyzed by HRMS without relying on DDA by LC-MS/MS analysis. It may notably be of use during the development phase of novel MS-based metabolomic approaches.

ASAP-MS and DART-MS as ancillary tools for direct analysis of the lichen metabolome.

Lichens contain unique metabolites that most often need to be characterized from a limited amount of material. While thin layer chromatography is still the preferred analysis method for most lichenologists, liquid chromatography gives a deeper insight in the lichen metabolome, but an extractive step is needed before any analysis. Therefore, ambient ionization mass spectrometry (MS) analysis of lichen samples using Atmospheric Solid Analysis Probe (ASAP) and Direct Acquisition in Real Time (DART) techniques is evaluated. We looked for a faster method to screen the metabolome by disrupting the classical workflow of analysis. Four lichens selected for their metabolic diversity were analyzed with MS; namely Evernia prunastri, Lichina pygmaea, Parmelia saxatilis, and Roccella fuciformis. ASAP and DART analyses were compared against the reference electrospray ionization with a bioinformatic process including Van Krevelen diagrams as well as the multivariate comparison of the ionization methods in positive and negative modes. Metabolite profiles obtained from DART and ASAP analyses of lichen samples are consistent with classical analyses of lichen extracts. Through an easy and rapid experiment and without any extraction solvent, a large and informative profile of lichen metabolites is obtained when using complementary ionization modes of these high resolution mass spectrometry methods. ASAP-MS and DART-MS are two ancillary methods that provide a comprehensive evaluation of the lichen metabolome.