ABSTRACT
RATIONALE: The increased frequency in the number of international terror threats has led to a corresponding increase in demand for fast, sensitive and reliable screening methods suitable for the detection of airborne explosive vapors. We demonstrate herein a workflow suitable for the determination of nitrogen-based explosives at the picogram level in just minutes. METHODS: A method is described that combines Thermal Desorption (TD) sample introduction with Differential Mobility Analysis (DMA) Tandem Mass Spectrometry (MS/MS), enabling a sensitive and accurate workflow suitable for the rapid detection of trace nitroaromatic, nitroester and nitramine explosive vapors. The methods are bridged using a novel low-flow, field-free Atmospheric Pressure Photoionization (APPI) source, intended specifically for the analysis of gas-phase analytes and airborne particles. RESULTS: Limits of detection within or below the picogram range were determined for the analysis of a range of explosives standards including 2,6-DNT, TNT, TATB, Tetryl, RDX, EGDN, PETN, HMX, and NG. Practical application of the TD-APPI-DMA-MS/MS workflow was demonstrated for the detection of real trace explosive vapors produced from the volatilization of solid explosive samples stored within a sealed cardboard box. A single complete analysis was performed in less than 2 min. CONCLUSIONS: The highly sensitive and accurate detection of a variety of common nitrogen-based explosive vapors has been demonstrated, at levels suitable for practical, high-throughput security screening applications.
ABSTRACT
A comparison study is presented in which the relative performance of a new orthogonal geometry field-free atmospheric pressure photoionization (FF-APPI) source was evaluated against both electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) for the analysis of a small panel of clinically relevant steroids, spiked within various complex biological matrices. Critical performance factors like sensitivity and susceptibility to matrix effects were assessed using a simple, isocratic, high-throughput LC-MS workflow. FF-APPI was found to provide the best performance in terms of both sensitivity and detection limit for all of the steroids included in the survey. Order-of-magnitude sensitivity advantages were realized for some low polarity analytes including both estradiol and estrone. A robust linear regression, post extraction addition method was used to evaluate the relative impact of matrix effects upon each ionization method using protein precipitated human serum, plasma and Surine (simulated urine) as standard clinical matrices. Under conditions optimized for sensitivity, both the field-free APPI and APCI sources were found to provide similarly high resistance to matrix suppression effects, while ESI performance was impacted the most dramatically. For the prototype FF-APPI source, a strong relationship was established between optimizable source parameters and the degree of ion suppression observed. Through careful optimization of vaporization temperature and nebulizer gas pressure it was possible to significantly reduce or even eliminate the impact of matrix effects, even for high-throughput LC-MS methods.
Subject(s)
Steroids/analysis , Atmospheric Pressure , Chromatography, Liquid , Humans , Mass Spectrometry , Photochemical ProcessesABSTRACT
RATIONALE: Atmospheric pressure photoionization (APPI) is considered a candidate ionization method suitable for a broad range of liquid chromatography/mass spectrometry (LC/MS) applications. Questions remain, however, regarding the ultimate potential of the technique. We propose that sensitivity and thus detection limits may be restricted by geometric source design, limiting widespread acceptance of the technique. METHODS: The relative performance of two geometrically distinct APPI source configurations was evaluated through comprehensive performance comparison upon a single MS platform. To facilitate a fair comparison, a prototype orthogonal geometry, field-free APPI source was developed and tested against two currently commercially available open-geometry APPI sources. The prototype device was engineered based upon the geometry and functionality of first-generation, co-axial field-free APPI sources. RESULTS: Initial characterization experiments were performed by flow injection analysis using a range of analyte standards exhibiting a variety of chemical properties. A standard panel of 16 polycyclic aromatic hydrocarbons (PAHs) identified as priority pollutants by the EPA was also analyzed, demonstrating relative performance using an LC/MS workflow. The prototype field-free APPI source demonstrated the potential for order-of-magnitude performance enhancement over open-geometry sources that lack a confined field-free reaction region. CONCLUSIONS: An APPI source configuration that includes an extended field-free reaction region was demonstrated to have the potential to provide enhanced sensitivity relative to commercially available open-geometry source designs. Improved performance will no doubt lead to increased acceptance and widespread application of the technique.
ABSTRACT
This technical note describes in detail the fabrication, operation and characterization of a pneumatically driven dopant introduction device, with a solvent reservoir capacity of 300 mL. Dopant flow rates and stability for this device are governed by the simple regulation of gas pressure rather than the progression of a stepper motor and syringe diameter, as is the case for typical infusion pumps. The device has the potential to provide days or even weeks of continuous, uninterrupted dopant flow at rates commonly adopted for atmospheric pressure photoionization (APPI) experiments without the need to replenish the dopant supply. Although not a refined instrumental design, this device was developed as an alternative cost-effective means of introducing stable dopant flow to an APPI source. The device was designed such that all components would be commercially available and easily procurable from common scientific part vendors. Figures and suggested part numbers are provided to allow those interested to fabricate similar devices to suit their individual experimental needs. Device characterization was performed while monitoring such factors as flow rate calibration, overall flow stability and reproducibility. In addition, a standard mixture of three polycyclic aromatic hydrocarbons was employed as a model sample for a typical reversed-phase liquid chromatography/atmospheric pressure photoionization mass spectrometry (LC/APPI-MS) application in order to demonstrate device performance.
