Anal Bioanal Chem (2011) 400:30653071 DOI 10.

1007/s00216-011-5013-4

ORIGINAL PAPER

Are these liquids explosive? Forensic analysis of confiscated indoor fireworks

Kepa Castro & Silvia Fdez-Ortiz de Vallejuelo & Izaskun Astondoa & Flix M. Goi & Juan Manuel Madariaga

Received: 11 January 2011 / Revised: 23 March 2011 / Accepted: 12 April 2011 / Published online: 1 May 2011 # Springer-Verlag 2011

Abstract Complete forensic analysis of several confiscated liquids and gels putatively used as firework components was achieved by combining Raman, FTIR spectroscopy, and scanning electron microscopy combined with energydispersive spectroscopy (SEMEDS). The chemical composition of the liquids was consistent with their use as indoor fireworks. Alcohols (methanol and isopropyl alcohol) were used to solubilise compounds producing coloured flames. Boric acid, recently introduced in the list of Substances of Very High Concern (SVHC) for the REACH Regulation of the European Union, was found in one of the samples. Keywords Raman . SEMEDS . FTIR . Fireworks . Forensic

Introduction Indoor fireworks are regarded as low explosives and are widely used in music concerts, theatre and street performK. Castro (*) : S. Fdez-Ortiz de Vallejuelo : J. M. Madariaga Faculty of Science and Technology, Department of Analytical Chemistry, University of the Basque Country, P.O. Box 644, 48080 Bilbao, Spain e-mail: kepa.castro@ehu.es I. Astondoa Astondoa Piroteknia, 48143 Areatza - Villaro, Bizkaia, Spain F. M. Goi Unidad de Biofsica (CSIC-UPV/EHU) and Department of Biochemistry and Molecular Biology, Faculty of Science and Technology, University of the Basque Country, P.O. Box 644, 48080 Bilbao, Spain

ances, local and popular festivals, during sports events (Olympic Games, Super Bowl, European football league), etc. However, low explosives have been also used during riots, in street demonstrations, inside football stadiums, etc., by violent extreme groups and hooligans. Every year tons of indoor pyrotechnics are confiscated by police and local authorities in almost every country. Much effort has been devoted to the detection of explosives, especially those regarded as high explosives, for example trinitrotoluene (TNT), octogen (HMX), cyclonite/hexogen (RDX), and pentaerythritol tetranitrate (PETN). The development of rapid and direct analytical procedures for detection of explosives is of increasing importance for security and counter-terrorism issues [17]. Several stand-off detection procedures have been developed for detection of explosives and precursors also [810]. In addition to this, several applications using portable systems have also been tested in an attempt to provide easy and rapid methods for implementation in airports, customs, and seaport offices [11]. From a forensic standpoint, very interesting analytical methods have been described for establishing criminal evidence [12, 13], and it is now possible to determine explosive residues even after explosions [14, 15]. From the literature it is evident that vibrational spectroscopic techniques (Raman and FTIR) have been widely proposed for the study of explosives to the detriment of other techniques, for example X-ray fluorescence, X-ray diffraction, chromatography, etc. However, despite much effort devoted to the detection of high explosives [17], it seems that low explosives and pyrotechnics artefacts have been scientifically ignored. As mentioned above, these substances have been widely used in street riots and can cause severe injuries or even aerial disasters. Consequently, in order to support accusatory evidence, the appropriate forensic studies are required.

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Although solid and powder substances are easily detected during inspections and searching, liquids and gels are very easy to camouflage, and special efforts must be made to develop methods to find forensic evidence [16]. According to the literature, Raman spectroscopy is a very valuable tool for explosive detection [11, 17, 18]. The main advantages of Raman spectroscopy are its non-invasiveness and non-destructiveness, very critical characteristics when irreplaceable forensic evidence has to be analysed. Unfortunately, molecular analysis of liquids is not a trivial task This is the reason it is always interesting to combine Raman analysis with other techniques, for example FTIR, scanning electron microscopy energy-dispersive spectroscopy (SEMEDS), etc. [19], because not all the compounds that are usually present in this kind of explosive are Ramanactive compounds, thus, a complementary technique must be used. The basic composition of indoor liquid pyrotechnics is usually a flammable solvent mixed with a compound that, after ignition, produces coloured light, smoke, or sparks. The compound mixed with the solvent can be organic or inorganic or both. In addition, particularly when gels are used, the mixture also contains a thickener. Usually, a piece of cotton or fabric is impregnated with the liquid and ignited. This means that to completely characterise the composition of these indoor liquid fireworks, a multianalytical approach is needed. This approach should include molecular speciation and elemental analysis of organic and inorganic compounds. In this work, some confiscated liquids were analysed by use of a combination of Raman spectroscopy and scanning electron microscopy (SEM) coupled to an energydispersive X-ray analyser (EDS). In all cases, the Raman results were complemented with FTIR analysis in order to test whether the combination of results obtained by these three analytical techniques can solve the challenge of analysis of liquids potentially used in the manufacture of low explosives. In one case flame atomic absorption spectroscopy (FAAS) had to be used to determine the presence of lithium. The reliability of the results was very important because severe consequences could arise.

The samples were analysed directly by Raman spectroscopy as liquids. The solvent was then evaporated inside an oven at low temperature. The dry residue obtained was analysed by Raman spectroscopy and FTIR. In two cases, the residue was treated with water, filtered, and finally analysed by flame atomic absorption spectroscopy (FAAS). Instrumental set-up Raman analysis was performed with a Renishaw InVia Raman spectrometer connected to a Leica DMLM microscope. Spectra were acquired with the Leica 50 N Plan (0.75 aperture) objective. The spatial resolution for the 50 objectives is approximately 2 m. For focusing and searching for points of interest, the microscope includes a Prior Scientific motorised stage (XYZ) with a joystick. The system has two lasers, 514 nm (ionargon laser) and 785 nm (diode laser). The 514-nm laser has a nominal power at the source of 50 mW, with a maximum power at the sample of 20 mW. For the 785-nm laser, the power at the source is 350 mW, and the maximum power at the sample is 150 mW. In all measurements, laser power was reduced by use of neutral density filters in order to avoid sample photo-decomposition and possible explosion. Each spectrum was acquired for at least 10 s, and 10 scans were accumulated at 10% of the maximum laser power in the spectral window from 100 cm1 (due to the notch filter) to 2500 cm1. This is the spectral window in which almost all signals of organic and inorganic compound can be found. The Raman spectra obtained were compared with those in several databases [20, 21] and with our own collection of spectra. The samples (all liquids and gels) were deposited on a microscope slide and analysed directly with the Raman microscope. The liquid was then evaporated and the residue analysed as a powder. For FTIR analysis, a Jasco Nexus 6300 spectrometer was used in transmittance mode, collecting 128 scans per spectrum at a spectral resolution of 4 cm1. Pellets were prepared under 10 tons pressure by mixing approximately 0.5 mg dry sample (the residue) with 150 mg spectroscopic-grade KBr. The FTIR spectra obtained were compared with those in several databases [22] and in our own collection of spectra. A scanning electron microscope (EVO 40; Carl Zeiss NTS, Germany) coupled to energy-dispersive X-ray spectroscopy equipment (Max; Oxford Instruments, Abingdon, Oxfordshire, UK) was used for electron image acquisition and elemental composition determination (single-point and mapping) of the samples. The SEM images were obtained at high vacuum using an acceleration voltage of 20 kV and a working distance between 6 and 13 mm, and they were taken at different magnifications (up to 10,000) by use of the secondary electron detector. Elemental analysis was carried out using an 8.5 mm working distance, a 35 take-

Experimental Samples Several samples of confiscated liquids/gels putatively used as indoor (theatre) fireworks were sent to the laboratory in order to determine their chemical composition and identify potential firework materials used in their manufacture. Among the materials, five different samples were selected as representative of the whole and labelled liquid 1 to liquid 5.

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off angle, and an acceleration voltage of 20 kV. An integration time of 50 s was used to improve the signalto-noise ratio. Apart from the single EDS analysis of the targeted crystals, EDS distribution maps of the elements and EDS false colour images were obtained for better interpretation of the data. The samples (residue after liquid evaporation) were deposited on the surface of an aluminium pin for SEM analysis. Power samples were glued to the surface by using a special carbon adhesive tape for SEM analysis. Because the samples may contain carbon compounds, to avoid interference they were not covered with graphite.

Raman analysis of the residue after solvent evaporation (Fig. 3) revealed the presence of ammonium sulfate (bands at 451, 512, 530, 615, 624, and 975 cm1), also determined in the direct Raman analysis, and ammonium dihydrogen phosphate (Raman bands at 178, 338, 399, 477, 540, 924, 1436, and 1660 cm1) [23, 24], confirming the data obtained by SEMEDS. The mixture found in this sample is rather strange as compared with the other samples analysed in this work. Apparently, this mixture would not have any use in pyrotechnics [2527]. No organic solvent was found (the salts were dissolved in water), and none of the components are known to produce either explosions or coloured flames. Liquid 2 This sample was labelled green fire. Direct Raman analysis of this sample (Fig. 4) revealed the presence of the organic solvent methanol (Raman bands at 1033, 1109, 1159, 1450, 2835, and 2943 cm1) [28, 29], and no other band could be seen in the spectra. After solvent evaporation, SEMEDS analysis of the powder (SEM image of flaky crystals) revealed high correlation in the distribution maps of the elements boron and oxygen. No other element was present in noticeable amounts. Raman analysis of the residue (Fig. 5) showed the presence of boric acid (Raman bands at 132, 185, 210, 500, 555, 880, 1167, and 1383 cm1). This result was confirmed by FTIR analysis (Fig. 5); the spectrum contained bands arising from boric acid (3217, 2514, 2360, 2261, 1645, 1462, 1228, 1194, 1116, 1026, 925, 883, 793, 675, 649, and 547 cm1). Boric acid can be used as a colorant to make green flames. For example, when dissolved in methanol it is popularly used among fire jugglers and fire spinners to create a deep green flame [30]. Liquid 3 This sample was labelled red fire. Direct Raman analysis of this sample showed only the characteristic bands of methanol (Raman bands at 1033, 1109, 1159, 1450, 2835, and 2943 cm1) [28, 29]. The sample solvent was evaporated, but Raman analysis of the powder could not be achieved because of its high deliquescence. In order to obtain more information, the power was heated, mounted quickly on an SEM sample pin holder and introduced in the SEM vacuum chamber. Surprisingly, SEMEDS analysis showed only the presence of chlorine. No other element or metal was detected by the EDS analyser. The hygroscopic properties of the precipitated solid and the absence of any other element except chlorine in the EDS analysis, made us suspect the presence of a lithium

Results and discussion Liquid 1 This sample arrived at the laboratory without any label. Direct Raman analysis of this sample furnished bands arising from ammonium sulfate only (Raman bands at 451, 612, and 974 cm1). After solvent evaporation, SEMEDS analysis of the residue was conducted. According to the EDS distribution maps of the detected elements (Figs. 1 and 2), a high correlation between sulfur, oxygen, and nitrogen was seen. This result was consistent with the presence of ammonium sulfate, already determined in the direct Raman analysis. In contrast, bromine appeared in areas where none of the cited elements appeared. In fact, it seemed that sodium and potassium were correlated with bromine. Besides, there was also phosphorus, with negative correlation with bromine and sulfur. Thus, the mixture could also contain sodium/ potassium bromide, some kind of sulfate, and phosphate.

Fig. 1 False colour EDS image of the residue from liquid 1. The red colour corresponds to the energies of bromine, blue to those of sulfur, and green to those of phosphorus

3068 Fig. 2 EDS element map distribution in liquid 1

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Fig. 3 Raman spectra of ammonium sulfate (top) and ammonium dihydrogen phosphate (bottom) found in liquid 1

Are these liquids explosive? Fig. 4 Raman spectra of the alcohols found in the sample liquid 2: methanol (top) and isopropyl alcohol (bottom)

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salt. Because lithium is too light to be detected by EDS analysis, flame atomic absorption analysis (FAAS) was carried out to determine if it was present in the sample. As expected, FAAS revealed the presence of lithium. Lithium chloride is used in pyrotechnics to produce a red colour [30] and it is soluble in methanol (2141 g LiCl/100 g H2O at 25 C) [31] and highly deliquescent. Liquid 4 This sample was labelled fire gel. The Raman spectrum of the liquid contained bands due to the presence of hydroxypropylcellulose (Raman bands at 208, 474, 853, 928, 1086, 1126, 1152, 1204, 1260, 1365, 1405, 1457, 2728, 2879, 2932, and 2971 cm1), a well known thickener. Bands due to an organic solvent were also present (375, 428, 488, 634, 819, 938, 953, 1134, 1166, 1339, 1450, 2717, 2880, 2919, 2941, and 2974 cm1). The Raman bands were consistent with the presence of isopropyl
Fig. 5 Raman ( bottom ) and infrared (top) spectra in transmittance mode of the boric acid found in liquid 2

alcohol (Fig. 4). Further FTIR analysis confirmed the presence of hydroxypropylcellulose (2968, 2922, 2859, 2149, 1639, 1452, 1415, 1383, 1333, 1271, 1155, 953, 840, 714, 614, and 431 cm1) in the collected spectra. After evaporation of the solvent from the sample, Raman analysis of the residue again revealed the bands due to the presence of hydroxypropylcellulose, whereas SEMEDS analysis revealed the presence of a film composed of carbon and oxygen, in complete correlation of their distribution maps. No other chemical element was present in the residue. Liquid 5 This sample was labelled red gel. Direct Raman analysis of the liquid revealed the presence of the characteristic bands of methanol (at 1033, 1109, 1159, 1450, 2835, and 2943 cm1) [28, 29]. Unfortunately, Raman analysis after solvent evaporation did not reveal any band, because of

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fluorescence phenomena. SEMEDS analysis of the residue revealed the presence of high quantities of chlorine, oxygen, and silicon. As for liquid 3, no metallic component responsible for the supposed red colour was detected. In order to determine whether lithium was present, simple extraction with water in an ultrasonic bath was carried out, and, after filtering, the solution was analysed by FAAS. As in the case of liquid 3, lithium was present. The large amount of chlorine determined by EDS analysis suggested that lithium chloride was used to produce the red colour when this gel is burnt. Finally, FTIR analysis of the sample after solvent evaporation revealed broad bands located at 3434, 1638, 1109, 800, 572, and 472 cm1. According to the literature, [32] the spectrum obtained was very close to that of silica gel, another well known thickener.

Concluding remarks With this combination of analytical techniques it was possible to analyse several liquid samples of confiscated materials probably used to manufacture indoor fireworks. In general, Raman spectroscopy enabled identification of the solvents directly, without any sample preparation, and, after solvent evaporation, complete molecular characterization of the residue. Only for the silica gel in liquid 5 did FTIR analysis provide information Raman could not provide. That is, in almost all cases, the FTIR information was redundant, and the combination of Raman spectroscopy and SEMEDS turned out to be of great efficiency. Unfortunately, lithium is too light to be identified by EDS analysis, and had to be identified by FAAS. Some authors claim that X-ray diffraction (XRD) is a superior technique to Raman and FTIR for identification of crystalline materials. However, XRD has several difficulties in the analysis of liquids, whereas Raman can achieves this without any problem. Raman spectroscopy provides as good results as XRD does in many cases. Besides, Raman spectroscopy can be used to analyse non-crystalline organic compounds. Finally, Raman spectroscopy can be used nondestructively, something very important when forensic samples are analysed. Overall, Raman spectroscopy is a more universal technique; this is the reason this technique was selected as the most important in the methodology described. It is apparent the composition of four of the five samples was consistent with their use in indoor pyrotechnics. In contrast, the liquid 1 was rather strange and its chemical composition would not produce any explosion, flame, or colour. Special attention must be focused on some of the compounds found during the analysis of the samples. For

example, the use of methanol as the main solvent came as a surprise. Methanol is highly poisonous for human beings, causing acidosis and blindness [33]. Its use is governed by special regulation in many countries. Moreover, boric acid, a compound detected in liquid 2, is also rather toxic [34]. Recently, the group of chemicals known as borates (including boric acid) were reclassified as Reprotoxic Category 2 by the European Union. This classification suggests that the compounds, in high doses, are harmful to the reproductive functions of humans. This also means that sale to the general public of products with boric acid at concentrations above 5.5% is banned. Borates are now on the list of Substances of Very High Concern (SVHC) for the REACH Regulation which was set up to protect the population from exposure to harmful substances. REACH introduces a process in which those substances that are considered to pose an unacceptably high risk to human health and the environment may be removed from the market unless there is a justifiable need for them to remain. Boric acid was added to the Candidate List in June 2010. Entry onto the Candidate List places some legal obligations on suppliers of those substances. Whether or not boric acid will make it to the end of the REACH process and become completely restricted is still uncertain. However, EU Law states that this reclassification of borates must take place in each member state by December 2010. It is also well known that non-allowed substances are occasionally used in pyrotechnic artefacts [35]. Thus, control of this kind of artefact should be recommended.
Acknowledgements Technical and human support provided by SGIker (UPV/EHU, MICINN, GV/EJ, ERDF, and ESF) in the Raman and SEMEDS analysis is gratefully acknowledged. Part of this work was supported by the Environmental Analytical Chemistry project (ref. IT-245-07 from the Basque Government).

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