Trace level detection and identification of nitro‐based explosives by surface‐enhanced Raman spectroscopy

Methods for rapid identification of explosives and their associated compounds at trace level quantities are needed for security screening applications. In this paper, we apply the surface‐enhanced Raman spectroscopy (SERS) to detect and identify traces (as low as tens of pg) of pentaerythritol tetranitrate (PETN), ethylene glycol dinitrate (EGDN), cyclotrimethylene‐trinitramine (RDX) and trinitrotoluene (TNT) using commercially available substrates (Klarite®, Renishaw diagnostics). High quality spectra were achieved within 10 s with a compact Raman spectrometer. Principal component analysis (PCA) of the data was performed to understand what factors affected the spectral variation across the samples. It was found that 76% of the spectral variation was explained by the first three PCs. Score plots for these components showed that the energetic materials can be clearly classified on the basis of SERS spectra also at trace level quantity. Our measurements further demonstrate the potential for using SERS as fast, in situ analytical tool for safety devices, with a sensitivity which competes and, in some cases, overcomes other techniques. Copyright © 2013 John Wiley & Sons, Ltd.     

太赫兹技术在爆炸物检测中的应用

研究了太赫兹成像技术在爆炸物探测中的应用,分析了太赫兹透射型时域光谱系统的实验装置,介绍了太赫兹时域光谱的测量步骤。确定了四种爆炸物样品(TNT,RDX,DNT,HMX)在太赫兹波段的吸收谱。结果表明,这四种爆炸物样品在0~2.5THz的频率范围内均存在特征吸收峰,这为太赫兹技术检测爆炸物提供了一种有效的途径。     

Identification of standard explosive traces by infrared laser spectroscopy: PCA on LPAS data

Infrared spectroscopy based methods are promising in the design of an integrated optical system for the real time detection and identification of explosive species to support homeland security. Infrared laser photoacoustic spectroscopy (LPAS) analysis of explosive compounds (DNT; TNT; RDX; HMX; TATP; PETN; TETRYL) and TOLUENE was reported. Standard commercial samples of the explosive species were analyzed in solid phase by a home made PAS apparatus equipped with a stabilized 10 W continuous wave CO₂ laser source. A very small amount (less than 100 ??g) of the sample was sufficient to produce a clear signal in a 3 cc volume PA cell. The spectral data were treated by a principal component analysis (PCA) based algorithm. In a three principal components representation of the results, every explosive species resulted to be very well distinguishable from each other, as well as from toluene and other solvents. The reported experimental activity was performed in the Molecular Spectroscopy Laboratory of ENEA Research Centre in Frascati in the frame of ISOTREX European Project.     

Application of mid-infrared cavity-ringdown spectroscopy to trace explosives vapor detection using a broadly tunable (6–8 μm) optical parametric oscillator

A novel instrument, based on cavity-ringdown spectroscopy (CRDS), has been developed for trace gas detection. The new instrument utilizes a widely tunable optical parametric oscillator (OPO), which incorporates a zinc–germanium–phosphide (ZGP) crystal that is pumped at 2.8 μm by a 25-Hz Er,Cr:YSGG laser. The resultant mid-IR beam profile is nearly Gaussian, with energies exceeding 200 μJ/pulse between 6 and 8 μm, corresponding to a quantum conversion efficiency of approximately 35%. Vapor-phase mid-infrared spectra of common explosives (TNT, TATP, RDX, PETN and Tetryl) were acquired using the CRDS technique. Parts-per-billion concentration levels were readily detected with no sample preconcentration. A collection/flash-heating sequence was implemented in order to enhance detection limits for ambient air sampling. Detection limits as low as 75 ppt for TNT are expected, with similar concentration levels for the other explosives. Received: 1 April 2002 / Revised version: 13 June 2002 / Published online: 12 September 2002 RID="*" ID="*"Corresponding author. Fax: +1-408/524-0551, E-mail: mtodd@picarro.com     

Nuclear quadrupole resonance of explosives: Simultaneous detection of RDX and PETN in semtex

We have used nuclear quadrupole resonance (NQR) for the detection of¹⁴N in explosives and introduce a new method for the simultaneous detection of the explosives cyclotrimethylene trinitramine (RDX) and pentaerythritol tetranitrate (PETN). We have developed an interleaved pulse sequence, which provides efficient excitation of both RDX and PETN, to drive a solenoid coil that is doubly resonant at 3.41 and 0.89 MHz (suitable resonant frequencies of RDX and PETN, respectively). The excitation of RDX and PETN is carried out alternately within the pulse sequence via frequency hops in the spectrometer; no electronic switching is required to alternately returne the doubly resonant probe to the resonant frequency of each material. The signals from RDX and PETN, which are separated by about 2.52 MHz, are brought into the same audio window by mixing with a suitable intermediate frequency. We have tested the doubly resonant probe and interleaved pulse sequence on plastic formulations of RDX and PETN, on their own (PE-4 and Detasheet respectively) and as a mixture in Semtex.     

Development and evaluation of magnetic resonance technologies, particularly NMR, for detection of explosives

Beginning in 1972 nuclear magnetic resonance (NMR) technologies for detecting explosives and illegal contraband were developed and evaluated at the Southwest Research Institute. Fullscale systems on the basis of hydrogen transient NMR were developed and evaluated in laboratory and field tests with generally favorable results but with some limitations. These included (1) an experimental, mobile system for detecting buried, nonmetallic land mines; (2) an instrument for inspection of letters and small parcels for small quantities of explosives or illegal drugs; (3) a system for inspection of checked airline baggage and air cargo for concealed explosives and illegal drugs; and (4) a system for rapid inspection of quantities of mail for illegal drugs.¹H NMR offers high sensitivity and detects high-energy explosives such as RDX, TNT, and PETN, as well as nitroglycerine and ammonium-nitrate-based explosives and illegal drugs. Challenges in both physics and engineering were successfully addressed to achieve the goals of rapid inspection with low false-alarm and high detection probability. Electron paramagnetic resonance was found suitable for detecting black powder in laboratory tests as was nuclear quadrupole resonance for a few high-energy explosives. Low-field¹H NMR was also explored in the laboratory to make it practical for explosives detection and found to have potential, but numerous implementation problems must be overcome.     

Raman spectroscopy and security applications: the detection of explosives and precursors on clothing

This study describes the application of confocal Raman microscopy to the detection and identification of explosives and their precursors in situ on undyed natural and synthetic fibres and coloured textile specimens. Raman spectra were obtained from explosives particles trapped between the fibres of the specimens. The explosives pentaerythritol tetranitrate (PETN), trinitrotoluene (TNT), and ammonium nitrate as well as the explosives precursors hexamethylenetetraamine (HMTA) and pentaerythritol were used in this study. Raman spectra were collected from explosives particles with maximum dimensions in the range 5–10 µm. Despite the presence of spectral bands arising from the natural and synthetic polymers and dyed textiles, the explosive substances could be identified by their characteristic Raman bands. Furthermore, Raman spectra were obtained from explosives particles trapped between highly fluorescent clothing fibres. Raman spectra of the explosive and explosive precursor substances on dyed and undyed clothing substrates were readily obtained in situ within 90 s without sample preparation and with no alteration of the evidential material. Copyright © 2009 John Wiley & Sons, Ltd.     

Spectrochemical properties of some explosives in the vapor state

The FTIR spectra of 1,3,5-trinitro-1,3,5-triazacyclohexane (RDX) and pentaerythritol tetranitrate (PETN) in the vapor phase over wide frequency (3500–500 cm^?1) and temperature ranges (293–383 K) is experimentally studied and the assignment of the observed vibrational bands is performed. To clarify the nature of the physicochemical processes that occur during the heating and evaporation of RDX and PETN and to detect and identify their characteristic components, the mass spectra and sub-THz spectra of these explosives are studied. To obtain spectroscopic information, special experimental techniques for recording of IR, sub-THz, and mass spectra of vapors of explosives and for preparation of high-purity RDX and PETN samples (with a main substance content of >99.7%) are developed based on modern methods of synthesis and purification.     

Detection of explosives on human nail using confocal Raman microscopy

Trace amounts of explosives were detected on human nail using confocal Raman microscopy. Contamination of the nail can result from the manual handling, packaging or transportation of explosive substances. Raman spectra were obtained from pentaerythritol tetranitrate (PETN), trinitrotoluene (TNT), ammonium nitrate and hexamethylenetetramine (HMTA) particles on the surface of the nail with dimensions in the range 5–10 µm. An added difficulty in an analytical procedure is the presence of a nail varnish coating that has been applied, which traps the particulate matter between the coating and nail. Using confocal Raman microscopy, interference‐free spectra could be acquired from particles of explosives visually masked by the nail varnish. Spectra of the explosives could be readily obtained in situ within 90 s without alteration of the evidential material. Acquisition of a Raman point map of a PETN particle under the nail varnish coating is also reported. Copyright © 2008 John Wiley & Sons, Ltd.     

Generation of coherent tunable deep UV radiation for detection and absorption studies of explosives RDX and TNT

We report a technique for the efficient generation of tunable coherent deep UV radiation and its application in studies of RDX and TNT at the ppm level on the basis of their absorption characteristics. The obtained experimental absorption data are compared with conventional spectrophotometric data. The UV radiation in the range 200–260 nm has been generated by the type-I noncollinear third harmonic of the dye laser radiation (600–700 nm) and also by sum frequency mixing (SFM) of Nd:YAG output (1064 nm) with the second harmonic of the dye laser in β-barium borate (BBO) crystal. The maximum conversion efficiency of the generated signal is estimated to be 57.5% at λ = 218.9 nm wavelength. Apart from measurements of the absorbance of RDX and TNT at different concentrations in their respective solutions, the minimum detection concentrations have also been ascertained. The estimated minimum detectable concentration of RDX is 8.47·10⁻⁹ M, whereas that for TNT is 35.7·10⁻⁹ M. The data were obtained using only ∼100 μJ/pulse of laser energy. Published in Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 516–521, July–August, 2007.     

Detection and analysis of cyclotrimethylenetrinitramine (RDX) in environmental samples by surface‐enhanced Raman spectroscopy

Techniques for rapid and sensitive detection of energetics such as cyclotrimethylenetrinitramine (RDX) are needed both for environmental and security screening applications. Here we report the use of surface‐enhanced Raman scattering (SERS) spectroscopy to detect traces of RDX with good sensitivity and reproducibility. Using gold (Au) nanoparticles (∼90–100 nm in diameter) as SERS substrates, RDX was detectable at concentrations as low as 0.15 mg/l in a contaminated groundwater sample. This detection limit is about two orders of magnitude lower than those reported previously using SERS techniques. A surface enhancement factor of ∼6 × 10⁴ was obtained. This research further demonstrates the potential for using SERS as a rapid, in situ field screening tool for energetics detection when coupled with a portable Raman spectrometer. Copyright © 2010 John Wiley & Sons, Ltd.     

Electroconductivity profiles in dense high explosives

A method for measuring the electroconductivity profiles behind the detonation front in dense solid high explosives with a resolution of 0.1 mm was developed. The method has a measurement range more than an order of magnitude wider than the available methods. During the detonation of pressed PETN, RDX, and HMX, an electroconductivity peak with an amplitude of several Ω^?1 cm^?1 and a width of 40 to 70 ns was observed. The peak width is in agreement with the available data on the width of the chemical reaction zone. The peak is accompanied by a tail with an electroconductivity several times lower.     

Towards optoelectronic detection of explosives

Detection of explosives is an important challenge for contemporary science and technology of security systems. We present an application of NOx sensors equipped with concentrator in searching of explosives. The sensors using CRDS with blue — violet diode lasers (410 nm) as well as with QCL lasers (5.26 μm and 4.53 μm) are described. The detection method is based either on reaction of the sensors to the nitrogen oxides emitted by explosives or to NOx produced during thermal decomposition of explosive vapours. For TNT, PETN, RDX, and HMX the detection limit better than 1 ng has been achieved.     

爆炸性物质太赫兹时间分辨光谱测量

利用自由空间电光取样方法,研究了四种炸药在太赫兹(THz)频段的光学特性。通过太赫兹时间分辨光谱测量,作者得到了四种炸药DNT(2,4-二硝基甲苯)、钝化的RDX(黑索今)、HMX(奥克托金)和TNT(2,4,6-三硝基甲苯)的透射光谱,进而计算得出它们在0.2～2.5 THz频段的吸收系数和折射率。作者发现,2,4-DNT在1.08 THz,HMX在1.82 THz存在显著的吸收尖峰,RDX在此频段存在多个吸收峰,TNT的吸收谱线相对其他三种样品比较平缓,这种共振吸收一般认为是由分子间相互作用或声子共振模式引起的。四种炸药对太赫兹波独特的吸收性质说明,太赫兹时间分辨光谱测量技术在炸药特征识别及安全检测领域具有潜在应用价值。作者对致癌物质偶氮苯进行了太赫兹光谱研究,发现了国产偶氮苯和进口偶氮苯在太赫兹波段均存在特征吸收峰,可用于物质鉴别。     

表面增强拉曼光谱检测爆炸物研究进展

近年来,恐怖袭击、刑事犯罪等爆炸事件频发,对社会的公共安全构成了严峻挑战。炸药是各种爆炸物的核心成分,因此对炸药的分析检测与识别是公共安全领域研究的热点之一。表面增强拉曼光谱可以对爆炸物分子实现指纹谱性、超痕量、实时高效的探测和识别,在安全检测和法庭科学等公共安全领域展现了极具诱惑力的应用前景。最近几年,国际上针对表面增强拉曼光谱检测爆炸物的研究十分活跃,取得了丰富的成果,文章综述了爆炸物表面增强拉曼基底,包括表面修饰改性和复合功能结构基底;有机和无机爆炸物的检测;以及爆炸物光谱识别的研究进展。分析了需要面对的问题,并总结展望了未来的发展趋势。相信随着纳米科学与技术、表面科学、仪器科学以及深度学习等新兴科技的快速发展,表面增强拉曼光谱一定能在爆炸物检测和识别方面取得更大进展。     

Surface‐enhanced Raman spectroscopy for trace‐level detection of explosives

The detection of explosives and their associated compounds for security screening is an active area of research and a wide variety of detection methods are involved in this very challenging area. Surface‐enhanced Raman scattering (SERS) spectroscopy is one of the most sensitive tools for the detection of molecules adsorbed on nano‐scale roughened metal surface. Moreover, SERS combines high sensitivity with the observation of vibrational spectra of species, giving complete information on the molecular structure of material under study. In this paper, SERS was applied to the detection of very small quantities of explosives adsorbed on industrially made substrates. The spectra were acquired with a compact Raman spectrometer. Usually, a high signal‐to‐noise (S/N) spectrum, suitable for identification of explosive molecules down to few hundreds of picograms, was achieved within 30 s. Our measurements suggest that it is possible to exploit SERS using a practical detection instrument for routine analysis. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis of indium–silver bimetallic nanocomposites for surface-enhanced Raman scattering

We report on the synthesis of indium–silver bimetallic nanocomposites by chemical reduction method under atmospheric condition and their activity for surface-enhanced Raman scattering (SERS). It is found that the indium–silver bimetallic nanocomposites have better SERS activity with larger enhancement factors (EF) than pure silver nanoparticles with similar size. The SERS EF can reach 10⁷ for 4-mercaptobenzoic acid and 10⁹ for crystal violet and rhodamine 6G adsorbed on the nanocomposites and the detection limits can be at least down to 10^?7 and 10^?10 M, respectively. The results demonstrate that the indium–silver bimetallic nanocomposites are promising as SERS substrate for a myriad of chemical and biological sensing applications.     

Optical spectroscopy to study confined and semi-closed explosions of homogeneous and composite charges

Confined and semi-closed explosions of new class of energetic composites as well as TNT and RDX charges were investigated using optical spectroscopy. These composites are considered as thermobarics when used in layered charges or enhanced blast explosives when pressed. Two methods to estimate fireball temperature histories of both homogeneous and metallized explosives from the spectroscopic data are also presented, compared and analyzed. Fireball temperature results of the charges detonated in a small explosion chamber under air and argon atmospheres, and detonated in a semi-closed bunker are presented and compared with theoretical ones calculated by a thermochemical code. Important conclusions about the fireball temperatures and the physical and chemical phenomena occurring after the detonation of homogeneous explosives and composite formulations are deduced.     

Quantification of DNT isomers by capillary liquid chromatography using at‐line SERS detection or multivariate analysis of SERS spectra of DNT isomer mixtures

With the global surge of terrorism and the increased use of bombs in terrorist attacks, national defence and security departments now demand techniques for quick and reliable analysis, in particular, for detection of toxic and explosive substances. One approach is to separate different analytes and matrix material before detection. In this work microliquid chromatography was used to separate two dinitrotoluene (DNT) isomers prior to detection via online UV–Vis spectroscopy. For identification, retention times were compared with reference samples and quantification was done by integration of UV–Vis absorption. Because UV detection is not particularly selective, Raman microscopic analysis was coupled to the liquid chromatography using a flow‐through microdispenser. Because DNT is difficult to detect with conventional Raman spectroscopy, the sensitivity was increased via surface‐enhanced Raman scattering (SERS) using silver‐quantum dots. Different analytical approaches to identify and quantify mixtures of two DNT isomers were evaluated. Good quantitative results were obtained using UV detection after microchromatographic separation (Limit of Detection: 0.11 and 0.06 for 2,4‐DNT and 2,6‐DNT). Coupling with SERS allowed for more confident differentiation between the highly structurally similar DNT isomers because of the additional spectral information provided by SERS. The application of a partial least squares algorithm also allowed direct SERS detection of DNT mixtures (root mean square error of prediction: 0.82 and 0.79 mg·L^–1 for 2,4‐DNT and 2,6‐DNT), circumventing the time‐consuming separation step completely. Copyright © 2012 John Wiley & Sons, Ltd.     

基于银胶纳米颗粒的痕量三硝基甲苯的表面增强拉曼光谱的实验研究

近年来对作为典型的硝基苯环类炸药的三硝基甲苯(TNT)的痕量检测受到越来越多的关注。将银胶纳米颗粒作为表面增强拉曼散射(SERS)基底,研究了10-6 mol.L-1的TNT的表面增强拉曼光谱的优化实验条件,重点研究了氯化钠溶液(NaCl)的含量以及碱性水解对TNT的表面增强拉曼光谱的影响。实验发现SERS样品中如果没有加入NaCl溶液,将观察不到TNT的SERS谱。加入的NaCl的含量必须在某一个范围之内才能观察到TNT的SERS谱,而且在这个范围之内,随着NaCl含量的增加,TNT的1 392cm-1处的拉曼峰出现先增大后减小的现象。对NaCl在TNT的SERS中的作用给予了理论解释。研究还发现TNT分子经过碱性水解后,与银纳米颗粒之间的吸附作用增强,其SERS谱的强度明显优于未经碱性水解的SERS结果。