Standardized Method for Measuring Collection Efficiency from Wipe-sampling of Trace Explosives

One of the limiting steps to detecting traces of explosives at screening venues is effective collection of the sample. Wipe-sampling is the most common ...

National Institute of Standards and Technology

An adjustable Wollaston-like prism is characterized for use in shearing- and differential schlieren-interferometry with laser and white-light illumination. We demonstrate that a polycarbonate prism under mechanical loading behaves identically to Wollaston's classical birefringent beam splitter. A linear relationship is found between the pure bending moment applied to the polycarbonate prism and the resulting light-beam-divergence angle. The utility of this prism in shearing-interferometry is shown by using it in place of the knife-edge in small and large schlieren optical systems. It is inexpensive to fabricate, and it yields adjustable beam-divergence angles over a range of at least 0-24 arc min.

Differential schlieren-interferometry with a simple adjustable Wollaston-like prism.

We present a methodology for fabricating polymer microspheres using inkjet printing of a biodegradable polymer containing either high explosives or high explosive simulant. Poly(DL-lactide/glycolide) 85:15 (PLGA) microsphere production is based on an oil/water emulsion solvent extraction process. The inkjet printing process allows for precise control of the microsphere diameter and the chemical composition. The microspheres can be used as calibrants or verification standards for explosives trace detection instruments. Gas chromatography/mass spectrometry analysis demonstrated that the composition of the microspheres was consistent with predicted concentrations based on the amount of analyte incorporated into the polymer solution and the inkjet operating parameters. We have demonstrated that the microspheres can be fabricated with a mass fraction of 70% of an analyte compound.

Fabrication of polymer microsphere particle standards containing trace explosives using an oil/water emulsion solvent extraction piezoelectric printing process.

Swipe-based explosive trace detectors rely on thermal desorption to vaporize explosive particles collected on a swipe. The vaporized material is carried by air flows from the desorption unit to the inlet of the chemical analyzer, typically an ion mobility spectrometer. We have observed that the amount of explosives detected from a swipe varies with the physical location of explosives collected on the swipe. There are two issues that may contribute to this effect: inhomogeneous or insufficient heating of the swipe during desorption and low velocity air flows that inefficiently transport desorbed vapor during the instruments analysis time. To better characterize this effect, we have simulated the air movements within a generic desorption unit using commercially available computational fluid dynamics software. Simulations are three dimensional, symmetric and solved under steady, laminar flow conditions. The calculated velocity field correlates directly with experimental detector response to the high explosive RDX. Results suggest that the limiting factor in this model thermal desorption unit is the flow-field around the swipe and flow rate into the detector, rather than heat transfer to the swipe itself. Buoyancy effects due to heating dominate the flow-field and produce a vertical bulk fluid motion within the domain that opposes much of the flow drawn into the analyzer.

Thermal desorption and vapor transport characteristics in an explosive trace detector.

In this work we evaluate the influence of thermal desorber temperature on the analytical response of a swipe-based thermal desorption ion mobility spectrometer (IMS) for detection of trace explosives. IMS response for several common high explosives ranging from 0.1 ng to 100 ng was measured over a thermal desorber temperature range from 60 °C to 280 °C. Most of the explosives examined demonstrated a well-defined maximum IMS signal response at a temperature slightly below the melting point. Optimal temperatures, giving the highest IMS peak intensity, were 80 °C for trinitrotoluene (TNT), 100 °C for pentaerythritol tetranitrate (PETN), 160 °C for cyclotrimethylenetrinitramine (RDX) and 200 °C for cyclotetramethylenetetranitramine (HMX). By modifying the desorber temperature, we were able to increase cumulative IMS signal by a factor of 5 for TNT and HMX, and by a factor of 10 for RDX and PETN. Similar signal enhancements were observed for the same compounds formulated as plastic-bonded explosives (Composition 4 (C-4), Detasheet, and Semtex). In addition, mixtures of the explosives exhibited similar enhancements in analyte peak intensities. The increases in sensitivity were obtained at the expense of increased analysis times of up to 20 seconds. A slow sample heating rate as well as slower vapor-phase analyte introduction rate caused by low-temperature desorption enhanced the analytical sensitivity of individual explosives, plastic-bonded explosives, and explosives mixtures by IMS. Several possible mechanisms that can affect IMS signal response were investigated such as thermal degradation of the analytes, ionization efficiency, competitive ionization from background, and aerosol emission.

Optimized thermal desorption for improved sensitivity in trace explosives detection by ion mobility spectrometry.

The feasibility of a low temperature plasma (LTP) probe as a way to prepare polymer bevel cross sections for secondary ion mass spectrometry (SIMS) applications was investigated. Poly(lactic acid) and poly(methyl methacrylate) films were etched using He LTP, and the resulting crater walls were depth profiled using time-of-flight secondary ion mass spectrometry (ToF-SIMS) to examine changes in chemistry over the depth of the film. ToF-SIMS results showed that while exposure to even 1 s of plasma resulted in integration of atmospheric nitrogen and contaminants to the newly exposed surface, the actual chemical modification to the polymer backbone was found to be chemistry-dependent. For PLA, sample modification was confined to the top 15 nm of the PLA surface regardless of plasma exposure dose, while measurable change was not seen for PMMA. The confinement of chemical modification to 15 nm or less of the top surface suggests that LTP can be used as a simple method to prepare cross sections or bevels of polymer thin films for subsequent analysis by surface-sensitive molecular depth profiling techniques such as SIMS, X-ray photoelectron spectroscopy (XPS), and other spatially resolved mass spectrometric techniques.

Ambient low temperature plasma etching of polymer films for secondary ion mass spectrometry molecular depth profiling.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) was used to determine the effect of ambient probe incidence angle on the amount and direction of analyte molecules transported from the sample surface for desorption electrospray ionization (DESI). Incidence angle was critical to both the lateral dispersion and vertical take-off angles of analyte molecules desorbed from the surface; as the incidence angle was increased from 30° to 45° to 60° (relative to the sample surface), the lateral dispersion angle decreased from 79° to 71° to 62°, respectively, while the vertical take-off angle decreased dramatically from 12° to 6° to 4°, respectively. As for the amount of material transported, the ToF-SIMS normalized secondary ion intensity of the molecular ion (peak counts per total spectrum counts) showed a significant decrease in the signal when the incidence angle was made steeper, decreasing from 8.1 × 10(-3) to 4.2 × 10(-3) to 7.5 × 10(-4), respectively. The ambient mass spectrometer interfaced with DESI also showed a similar analyte response, where the intensity of the molecular ion decreased from 1.6 × 10(7) counts to 3.3 × 10(6) counts to 5.4 × 10(5) counts, respectively. Overall, a steeper incidence angle was characterized by smaller amount of material desorption and tighter dispersion in both lateral and vertical directions. The study showed how ToF-SIMS can be used as a unique tool for characterizing the transport of desorbed analyte molecules in ambient ionization mass spectrometry, potentially offering new interface designs for optimal analyte collection.

Visualizing mass transport in desorption electrospray ionization using time-of-flight secondary ion mass spectrometry.

The use of silver nanoparticles (AgNPs) in textiles for enhanced anti-microbial properties has led to concern about their release and impact on both human and environmental health. Here a novel method for in situ visualization of AgNP release from silver-impregnated wound dressings is introduced. By combining an environmental scanning electron microscope, a gaseous analytical detector and a peltier cooling stage, this technique provides near-instantaneous nanoscale characterization of interactions between individual water droplets and AgNPs. We show that dressings with different silver application methods have very distinct AgNP release dynamics. Specifically, water condensation on dressings with AgNP deposited directly on the fiber surface resulted in substantial and rapid AgNP release. By comparison, AgNP release from wound dressing with nanoparticles grown, not deposited, from the fiber surface was either much slower or negligible. Our methodology complements standard bulk techniques for studying of silver release from fabrics by providing dynamic nanoscale information about mechanisms governing AgNP release from individual fibers. Thus coupling these nano and macro-scale methods can provide insight into how the wound dressing fabrication could be engineered to optimize AgNP release for different applications.

Dynamics of silver nanoparticle release from wound dressings revealed via in situ nanoscale imaging.

This paper describes a method for combining direct chemical analysis of latent fingerprints with subsequent biometric analysis within a single sample. The method described here uses ion mobility spectrometry (IMS) as a chemical detection method for explosives and narcotics trace contamination. A collection swab coated with a high-temperature adhesive has been developed to lift latent fingerprints from various surfaces. The swab is then directly inserted into an IMS instrument for a quick chemical analysis. After the IMS analysis, the lifted print remains intact for subsequent biometric scanning and analysis using matching algorithms. Several samples of explosive-laden fingerprints were successfully lifted and the explosives detected with IMS. Following explosive detection, the lifted fingerprints remained of sufficient quality for positive match scores using a prepared gallery consisting of 60 fingerprints. Based on our results (n = 1200), there was no significant decrease in the quality of the lifted print post IMS analysis. In fact, for a small subset of lifted prints, the quality was improved after IMS analysis. The described method can be readily applied to domestic criminal investigations, transportation security, terrorist and bombing threats, and military in-theatre settings.

Method for combined biometric and chemical analysis of human fingerprints.

The persistent hydrogen termination present in nanoporous silicon (nPS) is unique compared to other forms of nanoscale silicon (Si) which typically readily form a silicon dioxide passivation layer. The hydrogen terminated surface combined with the extremely high surface area of nPS yields a material capable of powerful exothermic reactions when combined with strong oxidizers. Here, a galvanic etching mechanism is used to produce nPS both in bulk Si wafers as well as in patterned regions of Si wafers with microfabricated ignition wires. An explosive composite is generated by filling the pores with sodium perchlorate (NaClO4). Using high-speed video including Schlieren photography, a shock wave is observed to propagate through air at 1127 ± 116 m/s. Additionally, a fireball is observed above the region of nPS combustion which persists for nearly 3× as long when reacted in air compared to N2, indicating that highly reactive species are generated that can further combust with excess oxygen. Finally, reaction products from either nPS-NaClO4 composites or nPS alone combusted with only high pressure O2 (400 psig) gas as an oxidizer are captured in a calorimeter bomb. The products in both cases are similar and verified by transmission electron microscopy (TEM) to include nano- to micrometer scale SiOx particles. This work highlights the complex oxidation mechanism of nPS composites and demonstrates the ability to use a solid state reaction to create a secondary gas phase combustion.

Nanoporous Silicon Combustion: Observation of Shock Wave and Flame Synthesis of Nanoparticle Silica.

Sample collection for Ion Mobility Spectrometry (IMS) analysis is typically completed by swiping a collection wipe over a suspect surface to collect trace residues. The work presented here addresses the need for a method to measure the collection efficiency performance of surface wipe materials as a function of the number of times a wipe is used to interrogate a surface. The primary purpose of this study is to investigate the effect of wipe reuse, i.e., the number of times a wipe is swiped across a surface, on the overall particle collection and IMS response. Two types of collection wipes (Teflon coated fiberglass and Nomex) were examined by swiping multiple times, ranging from 0 to 1000, over representative surfaces that are common to security screening environments. Particle collection efficiencies were determined by fluorescence microscopy and particle counting techniques, and were shown to improve dramatically with increased number of swiping cycles. Ion mobility spectrometry was used to evaluate the chemical response of known masses of explosives (deposited after reusing wipes) as a function of the wipe reuse number. Results show that chemical response can be negatively affected, and greatly depends upon the conditions of the surface in which the wipe is interrogating. For most parameters tested, the PCE increased after the wipe was reused several times. Swiping a dusty cardboard surface multiple times also caused an increase in particle collection efficiency but a decrease in IMS response. Scanning electron microscopy images revealed significant surface degradation of the wipes on dusty cardboard at the micrometer spatial scale level for Teflon coated wipes. Additionally, several samples were evaluated by including a seven second thermal desorption cycle at 235°C into each swipe sampling interval in order to represent the IMS heating cycle. Results were similar to studies conducted without this heating cycle, suggesting that the primary mechanism for wipe deterioration is mechanical rather than thermal.

The effect of reusing wipes for particle collection.

Unlike current chemical trace detection technology, dogs actively sniff to acquire an odor sample. Flow visualization experiments with an anatomically-similar 3D printed dog's nose revealed the external aerodynamics during canine sniffing, where ventral-laterally expired air jets entrain odorant-laden air toward the nose, thereby extending the "aerodynamic reach" for inspiration of otherwise inaccessible odors. Chemical sampling and detection experiments quantified two modes of operation with the artificial nose-active sniffing and continuous inspiration-and demonstrated an increase in odorant detection by a factor of up to 18 for active sniffing. A 16-fold improvement in detection was demonstrated with a commercially-available explosives detector by applying this bio-inspired design principle and making the device "sniff" like a dog. These lessons learned from the dog may benefit the next-generation of vapor samplers for explosives, narcotics, pathogens, or even cancer, and could inform future bio-inspired designs for optimized sampling of odor plumes.

Matthew E. Staymates

Materials Measurement Science Division

National Institute of Standards and Technology

Standardized Method for Measuring Collection Efficiency from Wipe-sampling of Trace Explosives

Matthew E. Staymates

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Materials Measurement Science Division

National Institute of Standards and Technology

Standardized Method for Measuring Collection Efficiency from Wipe-sampling of Trace Explosives

Materials Measurement Science Division