Anal Bioanal Chem (2009) 395:421428 DOI 10.

1007/s00216-009-2882-x

ORIGINAL PAPER

Urea nitrate, an exceptionally easy-to-make improvised explosive: studies towards trace characterization
Tsippy Tamiri & Rinat Rozin & Nitay Lemberger & Joseph Almog

Received: 19 April 2009 / Revised: 20 May 2009 / Accepted: 28 May 2009 / Published online: 4 July 2009 # Springer-Verlag 2009

Abstract Urea nitrate is a powerful improvised explosive, frequently used by terrorists in the Israeli arena. It was also used in the first World Trade Center bombing in New York in February 1993. It is difficult to identify urea nitrate in post-explosion debris, since only a very small fraction survives the blast. Also, in the presence of water, it readily decomposes to its original components, urea and nitric acid. It is suspected that post-blast debris of urea nitrate can be confused with ammonium nitrate, the main solid product of urea nitrate thermal decomposition. In a comprehensive study towards identification of urea nitrate in post-blast traces, a spectrophotometric technique for quantitative determination of urea nitrate was developed, and conditions were found for extraction and separation of un-exploded traces of urea nitrate with minimal decomposition. Nevertheless, out of 28 samples collected from a series of three controlled firings of urea nitrate charges, only one gave the typical adduct ion by liquid chromatography/mass spectrometry analysis. We found that urea nitrate can be extracted from solid mixtures to organic solvents by using Crown ethers as host compounds. The adducts thus formed are solid, crystalline compounds that can be characterized by microanalysis and spectroscopic techniques.

Keywords Forensics . Improvised explosives . Post-blast . Urea nitrate . LC/MS . Crown ethers

Introduction The detection of concealed explosives and their identification has become an important component in combating terror. In forensic investigations, it is equally important to be able to identify also explosive traces from post-blast debris. Unequivocal identification in post-blast residue is required by investigators (was there an explosive, or was the explosion an accident caused by a mixture of, e.g., fuel gases and air), intelligence (identification of new trends, source detection, association between cases), and the legal system (suspects' indictment). The analysis of explosive material from debris is considered a difficult task since the small amount of original material which survives the blast is spread over a large area and is contaminated with large amounts of irrelevant materials which greatly interfere with the analytical procedure. Sometimes, thermal decomposition products play an important role in the identification of post-blast debris, such as in the case of black powder explosions [1]. Urea nitrate (uronium nitrate, UN) is a powerful improvised explosive [2]. Even nonprofessionals can easily prepare large amounts of this material from urea and nitric acid in back-yard facilities. UN has been used in improvised mines, which destroyed three Israeli Merkava tanks, and in suicide bomber belts, which caused the loss of well over 100 lives in Israel during the years 20012004. In the USA, UN was used as the main charge in the first bombing of the World Trade Center in February1993 [3]. Subsequently, it became essential to be able to identify UN not only as a suspicious white powder but also in postexplosion debris.

T. Tamiri Division of Identification and Forensic Science (DIFS), Israel Police National HQ, Jerusalem 91906, Israel R. Rozin : N. Lemberger : J. Almog (*) Casali Institute of Applied Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel e-mail: almog@vms.huji.ac.il

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Unlike most common explosives, urea nitrate is a salt. It is composed of uronium cation and nitrate anion. Crystallographic measurements show that the proton is attached to the carbonylic oxygen rather than to the amidic nitrogen [4, 5] giving rise to a structure of uronium nitrate (1) (Fig. 1). Diagnostic tests for un-exploded UN include the Griess color test (after reduction to nitrite) [6], X-ray diffraction (XRD) [5], infrared (IR) spectroscopy [7], ion chromatography (IC) [8], and capillary electrophoresis (CE) [9]. A specific color test for detecting minute amounts of the uronium ion was suggested lately by this group [10]. It is much harder to identify UN in post-blast traces. Identification of urea and nitrate components in the residues, by IC or CE, does not necessarily imply the presence of urea nitrate! For instance, many inorganic fertilizers contain mixtures of urea and potassium nitrate [11]. It is, therefore, required to unequivocally identify the intact salt molecule or at least some typical specific decomposition products. In powder exhibits, this can be accomplished by spectroscopic methods such as XRD or IR spectroscopy. Nevertheless, XRD and IR might not always be suitable for the analysis of post-blast samples where trace amounts of amorphous residues are dealt with, accompanied by large amounts of impurities. In a recent report, we described a method for the recovery and detection of urea nitrate in traces [12]. The residues are extracted with hot acetone, and the extract chromatographed on chromosorb G-HP. The eluent is analyzed by liquid chromatography/mass spectrometry (LC/MS) using atmospheric pressure chemical ionization (APCI). By applying this technique, we were able to identify urea nitrate in an actual exhibit. We noticed, however, that UN can be formed also during the analytical procedure by certain combinations of urea, nitrate ions, and a source of protons, and hence, the presence of the characteristic adduct ion does not necessarily allude to authentic urea nitrate [12, 13]. The main nuisance was found to be a mixture of urea and ammonium nitrate [12]. Another major source of ambiguity is the fact that the main solid product of UN thermal decomposition is ammonium nitrate [14, 15]; hence, the presence of ammonium and nitrate ions in the debris does not necessarily indicate authentic ammonium nitrate! Urea nitrate is quite sensitive to environmental conditions. In presence of water, it readily decomposes to urea and nitric acid [16], and in contact with carbonates, it forms urea and nitrate salts.
Fig. 1 The ionic structure of urea nitrate (1)

Our study involved two consecutive parts: a series of controlled firing experiments with UN charges followed by further examination of analytical techniques for post-blast residues of UN. This part included also a study of the reaction between UN and certain host compounds to form crystalline, well characterized adducts. To examine how much UN remains intact after contact with different neighboring materials such as soil and structure components and also after clean-up on various stationary phases and elution with different solvent systems, we required a technique for quantitative determination of UN. We found that the diagnostic UN color reagent p-dimethylaminocinnamaldehyde (p-DMAC, UN-1) [10] can also be used for quantitative spectrophotometric determination of UN. To imitate real post-blast conditions, with UN charges of the size that can be carried in a handbag or on the body of suicide bombers, three UN charges (0.5, 2, and 5 kg) were fired under controlled conditions. The debris were collected and analyzed by color tests as well as the above described analytical techniques. Upon reaction with 18-crown-6 ether, UN forms a solid crystalline adduct [17], which can be fully characterized. Also, ammonium nitrate forms a crystalline adduct under similar conditions. We noticed that the same reaction can be applied to extract UN from a solid mixture into a non-polar solvent (acetone or dichloromethane (DCM)) containing crown ethers (18-crown-6 or its dibenzo derivative). Under such conditions, the nuisance combination ammonium nitrate/urea does not form urea nitrate!

Experimental Materials Ammonium nitrate, 18-crown-6, and dibenzo-18-crown-6 ethers were obtained from Sigma-Aldrich Chemie GmbH (Steinheim, Germany); urea was obtained from Riedel-de Haan (Seelze, Germany); 4-dimethylaminocinnamaldehyde was from ACRS organics (New Jersey, USA). Urea nitrate was synthesized from urea and nitric acid, according to literature procedures [10, 13]. All solvents were obtained from Bio Lab (Jerusalem, Israel). Urea:18-crown-6 adduct was prepared according to literature procedure [17]. Instrumentation IR spectroscopy was carried out on Nicolet 460 ESP Protg using KBr pellets. Attenuated total reflectance Fourier transform infrared (ATR FTIR)an Alpha model spectrometer, equipped with a single reflection diamond ATR sampling module, manufactured by Bruker (Ettlingen, Germany), was used to record the FTIR spectra. X-ray diffraction measure-

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ments were carried out on Bruker SMART APEX CCD X-ray diffractometer (Bruker Axe GHBH, Karlsruhe, Germany). UVvis spectra were recorded on a Varian Cary 100 Bio spectrophotometer. 1H and 13C NMR spectra were recorded on a 400 MHz Bruker DRX 400 and on a 500 MHz Bruker Ultrashield Plus instrument. API mass spectrometer An LCQDUO mass spectrometer (Thermo-Finnigan, San Jose, CA, USA) with ESI and APCI interfaces, coupled with a Thermo-Separation liquid chromatograph (P4000) was used. Analysis of UN was carried out according to [12]. Adducts of UN and crown ethers were analyzed by APCI in the positive mode with heated capillary and vaporizer temperatures of 90 and 300 C, respectively. The collision gas was helium. The separation of UN:18-crown-6 adduct was performed on Gemini C-18 column (1502 mm i.d., 5 m particle size) purchased from Phenomenex. Mobile phase was water with 0.1% formic acid/methanol (isocratic 50/50) at a flow rate 0.3 mL/min. Injection volume was 10 L. Instrument control and data processing were performed using Xcalibur software (version 1.1).

Scheme 1 Explosive charge setup

Quantitative determination of UN For the calibration curve, urea nitrate (100 mg) is dissolved in EtOH (100 mL). Aliquots in the range of 0.11.0 mL are transferred to a 10-mL flask; EtOH (3 mL) is added, followed by p-DMAC solution (0.4%, 2.85 mL). The solution is shaken for a few seconds and diluted to 10 mL with EtOH. Three minutes after the addition of p-DMAC, the flask is immersed in an ice bath for 2 h. The absorption is read at 514 nm. Concentrations of 0.051 mg/mL UN were successfully determined (9%) in four consecutive blind tests. Firing of UN charges Charge configuration Urea nitrate used for the firing experiments was obtained from an Israeli governmental laboratory and confirmed by IR and UN-1 color test. Three devices containing UN as the main charge (0.5, 2, and 5 kg), RDX as the booster (ca 10% of UN weight) and pentaerythritol tetranitrate detonation cord were contained in empty fire extinguishers as shown in Scheme 1. Witness materials The charges were surrounded by witness materials representative of those which will be found at real bomb scenes. Aluminum plates 5050 cm, cement blocks, cloth, and

plywood boards were arranged in a setup shown in Scheme 2. Soil samples from the bomb seat were collected before and after the firings. Collection of chemical evidence Chemical evidence was collected by clean personnel, wearing disposable oversuits, boots, and gloves. The debris (soil, aluminum plates, cement blocks, cloth, and plywood boards) were collected, sealed in polyethylene bags, and transported to the laboratory. Soil, powdered cement blocks, and cloth were transferred into glass beakers and extracted with hot acetone. Aluminum plates and plywood boards were swabbed with acetone-soaked cotton wool, which was further extracted in boiling acetone. All solutions were evaporated and the residues analyzed. Preparation of UN:18-crown-6 adduct (2) UN (1) (147.7 mg, 1.2 mmol) and 18-crown-6 ether (414.7 mg, 1.6 mmol) were dissolved in hot methanol (0.5 mL) followed by addition of chloroform (1 mL) and diethyl ether (3 mL) [17]. The precipitate was washed with diethyl ether and air-dried. Colorless crystals were obtained, m.p. 8890 C; ATR FTIR 3,353, 2,895, 2,353, 1,703, 1,651, 1,569, 1,351, 1,318, 1,325, 1,096, 955, 890, 570 cm1; 1H NMR (acetone-d6, 400 MHz) 3.60 (s, 24 H), 7.70 (br s, 4 H); 13C (NMR) (acetone-d6, 125 MHz) 70.03 (18-crown-6 C), 162.09 (UN C); Anal.

424 Scheme 2 Site plan for UN firings

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Calcd for C13H29N3O10: C, 40.31; H, 7.55; N, 10.85. Found: C, 40.29; H, 7.70; N, 11.03; (LC/MS) (+ APCI) m/z 325.1 [M+urea+H]+ (shown in Fig. 3). A few crystals of the adduct (2) were placed on a spot-test plate, and one drop of UN-1 reagent was added. After a few seconds, the typical red-orange color, characteristic of UN, developed. Preparation of ammonium nitrate:18-crown-6 adduct (3) Ammonium nitrate:18-crown-6 adduct was prepared by two procedures: (1) according to literature [18], m.p. 187.3 188.5 C and (2) following the procedure for UN:18-crown6 adduct. Both provided the same product, (3). According to the second procedure, ammonium nitrate (96.5 mg, 1.2 mmol) and 18-crown-6 (414.7 mg, 1.6 mmol) were dissolved in hot methanol (0.5 mL) followed by addition of chloroform (1 mL) and diethyl ether (2 mL). After 24 h, the precipitate was filtered and washed with diethyl ether. Colorless crystals, m.p. 187.0188.3 C; 1H NMR (acetone-d6, 400 MHz) 3.62 (s, 24 H), 6.91 (s, 1 H), 7.04 (s, 1 H), 7.17 (s, 1 H); LC/MS (+ APCI) m/z 282.3 corresponds to [M + NH4]+ (identical with the compound described earlier [18]). Preparation of UN:dibenzo-18-crown-6 adduct (4) A solution of dibenzo-18-crown-6 (40.8 mg, 0.11 mmol) in chloroform (1 mL) was added to UN (10.7 mg, 0.09 mmol) solution in methanol (0.3 mL) followed by addition of diethyl ether (1 mL). After 2 days, the precipitate was filtered and washed with cold chloroform followed by

acetone. Crystallization from acetonitrile afforded colorless crystals, m.p.143147 C; 1H NMR (acetone-d6, 400 MHz) 3.96 (m, 8 H), 4.15 (m, 8 H), 6.91 (m, 4 H), 6.96 (m, 4 H), 7.1 (br s, 4 H); IR (KBr) 742, 932, 998, 1,132, 1,232, 1,257, 1,383, 1,454, 1,510, 1,596, 1,696 cm1; Anal. Calcd for C21H29N3O10: C, 52.17; H, 6.05; N, 8.69. Found: C, 52.55; H, 5.91; N, 8.23; LC/MS (+ APCI) m/z 421.0 [M + urea + H]+, 780.8 [2M + urea + H]+. Extractions with 18-crown-6 ether under laboratory conditions A mixture of substrate (urea nitrate; urea; NH4NO3; urea + NH4NO3; urea + KNO3; 0.05 g of each), 18-crown-6 ether (1 g) and solvent (50 mL) was shaken at room temperature. The solvent was decanted and evaporated. Color test (UN-1) and liquid chromatography/mass spectrometry analysis were carried out on the residue. UN-1 color test After evaporation, one drop of UN-1 reagent (0.4% ethanolic solution) was added to the solid residue (The appearance of an orange/red color after a few seconds, which turns intense red after 1 min, is considered a positive test for UN). Ammonium nitrateurea color test Crystals of urea and ammonium nitrate were crushed together (without solvent), and a few drops of ethanolic UN-1 were dripped on the mixture. After 30 min, a strong orange color appeared which gradually turned into dark red.

Urea nitrate, an exceptionally easy-to-make improvised explosive: studies towards trace characterization Fig. 2 The smoothed mass chromatogram of the ion at m/z 184.7, (a), full scan (b), and MS/MS at the negative mode of the adduct ion at 184.8 (c) from an extract of a metal witness plate, 1 m from the UN (0.5 kg) charge

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426 Fig. 3 LC/APCI/MS full scan in the positive mode of compound 2

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Results and discussion Quantitative determination of urea nitrate Urea nitrate could be determined in ethanolic solutions at concentrations in the range 0.050.15 mg/mL. Solutions of higher concentrations were diluted to the appropriate range. The equation of the straight line, corresponding to the calibration curve (maximum absorbance at 514 nm vs. UN concentration) is y 37:037x 1:0724; R2 0:9958 1

the UN-1 color test (only after acidification with acetic acid), indicating the presence of urea, which was subsequently confirmed by LC/MS. Samples from each one of the scenes also responded positively to the Nessler color test for ammonium ions. The presence of nitrate ions was indicated by LC/MS in samples collected from all three scenes, with stronger signals from the 0.5 kg charge. All blank soil samples were negative for uronium, urea, ammonium, and nitrate. Adducts of urea nitrate with crown ethers Characterization of UN:18-crown-6 (2)

The effect of potential interferences has not been tested in this series. Chemical residue analysis The exhibits collected before and after the UN firings were extracted with hot acetone and evaporated as in the method described earlier [12]. The residues were analyzed by LC/MS. Urea nitrate was identified in one sample out of 28: on the metal witness plate placed 1 m from the 0.5 kg charge. The smoothed mass chromatogram of the ion at m/z 184.7, full scan, and MS/MS of the adduct ion at m/z 184.8 [UN + NO3] is shown in Fig. 2. The extracts were tested for the presence of uronium cation using the color test UN-1 [10]. In addition, some samples were extracted with hot distilled water, filtered, evaporated to dryness, and tested for urea and biuret by LC/MS and for the presence of uronium or ammonium ions using the color tests UN-1 and Nessler [19], respectively. Some of the samples reacted positively to

There is a small but noticeable difference between the 1H NMR spectrum, in acetone-d6 of UN:18-crown-6 adduct, and that of the superimposed spectra of the two precursors, UN ( 7.9 broad singlet for four amidic hydrogens) and the free 18crown-6 ether ( 3.58 singlet for 24 hydrogens of the crown). The singlet referring to the adduct's amidic hydrogens is located in a higher magnetic field (7.70 ppm) than the singlet of free UN (7.9 ppm). In the 13C NMR spectra of the three compounds, no difference could be noticed; an exact superimposed spectrum is obtained. This observation may indicate a loose bond between the crown ether and UN. In addition, the adduct UN:18-crown-6 (2) reacts with UN-1 reagent in the same manner as free UN, to produce the typical orange-red color. This observation supports the assumption of a loose bond between UN and the crown ether. Compound 2 was analyzed by LC/MS using APCI in the positive mode. The full-scan mass spectrum is shown in Fig. 3. The ion at m/z 325 corresponds to uronium adduct with the crown ether. Possible explanation for the ions at m/z

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Fig. 4 a ORTEP drawing of UN:18-crown-6 adduct (2). The thermal ellipsoids are scaled to 50% probability. b Side view (Dreiding model) of the crystal structure of 2 (notice that the uronium ion is quite far from the crown ether plain and is not embedded in it)
+ +

Other crown ethers tested for trapping UN were dicyclohexano-18-crown-6, benzo-15-crown-5, and tertbutylbenzo-12-crown-4 ethers. All three failed to produce adduct compounds with UN. Experiments continued with 18-crown-6 ether as a host molecule for extracting UN from solid samples, as it can easily trap UN, and the adduct is readily soluble in organic solvents (e.g., acetone and dichloromethane). Seven experiments were carried out with potentially interfering guest molecules in solid mixtures (Table 1). Since the realization that urea nitrate is the most widely used illegal explosive in our arena, it became essential to develop analytical techniques for the unambiguous identification of UN traces in post-explosion scenes. Gozin et al. reported lately the development of a novel chemosensor for detecting urea nitrate [20]; another detection technique, based on voltammetry, was recently suggested by Cagan et al. [21], but the question of identification in post-blast debris has not gained much attention. In a recent article, we reported a set of conditions which enable the extraction; separation, and cleanup of UN samples, followed by LC/MS analysis of two typical adduct ions [12]. This technique gave satisfactory results under laboratory conditions, working with known samples of crystalline UN. In one case, it enabled us to identify traces of intact UN in debris collected from a terrorist attack. The main nuisance for LC/MS analysis was found to be the rather common combination of ammonium nitrate and urea, which gives rise to the same adduct ions, probably from the following equilibrium: NH2 2 CO NH4 NO3 , NH2 2 COH NO3 2

265, 282, 283, and 589 are [M + H] , [M + NH4] , [M + H3O]+, [2M + urea + H]+, respectively. LC/MS analysis showed no indication of the presence of intact adduct UN:18-crown-6 (2) neither in the positive nor in the negative mode. The crystal structure of the complex 2 is shown in Fig. 4. The complex UN:dibenzo-18-crown-6 (4) produces strong orange-red color upon reaction with UN-1 color reagent, also suggesting a loose bond between UN and the crown ether.
Table 1 Extractions of UN and potential interferences with 18-crown-6 ether solution Substrate Solvent

In order to lessen the possibility that the combination ammonium nitrateurea would be mistakenly identified as urea nitrate, we searched for conditions that would allow only authentic UN to pass the analytical protocol and prohibit the equilibrium mentioned above. The extraction of solid UN into nonpolar solvents by forming typical adducts with crown ethers might serve this goal. While UN does not dissolve in, e.g., dichloromethane, the addition of crown ethers to the solvent greatly increased its solubility by
Reaction with UN-1 Presence of [crown + uronium]+ adduct ion (LC/MS) + +a +a + +a

Urea nitrate Urea NH4NO3 Urea + NH4NO3 Urea + KNO3 Urea nitrate Urea + NH4NO3

Acetone Acetone Acetone Acetone Acetone DCM DCM

Since the analysis was done in APCI LC/MS at the positive mode, the analyte is protonated, and hence, the same adduct ion [crown + urea + H]+ is expected not only with uronium but also with urea

Positive (after 1 min strong orange-red color) Negative Negative Negative Negative Positive Negative

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forming 1:1 adduct compounds. The bond between UN and the crown ether is rather loose, as can be deduced from the color reaction with the UN-1 reagent, characteristic of the presence of free UN, and also from the long distance between the uronium ion and the crown ether's plain, which is deduced from its crystal structure (Fig. 4b). The mixture ammonium nitrateurea does not produce the color under similar conditions, indicating that the equilibrium, by which UN is formed (2), does not take place under nonpolar conditions. This was probably the most important finding of the study. It is hoped that the hostguest approach may be applied also to the efficient recovery of the little intact UN that is left in post-blast debris and its transfer to nonpolar solvents, thus reducing also the interference by ammonium nitrateurea. Subsequently, either the free UN or its adduct with the host compound may be characterized by LC/MS. Experiments are under way. The disappointing results that were obtained after applying the extraction and cleanup technique to traces from controlled firings of UN charges may indicate that in many cases, very little UN survives the blast or that it is difficult to extract and detect intact UN in traces [22]. Only one out of 28 samples could be positively identified as containing UN. The other samples were either negative or showed the presence of only nonspecific decomposition products, urea and ammonium and nitrate ions. It is noteworthy that, in their joint experiment a few years ago, the British Defence Evaluation and Research Agency and the Federal Bureau of Investigation reported only ammonium and nitrate ions in the debris after controlled detonation of a much larger UN charge [2]. In their recent comprehensive article on the thermal decomposition of UN, Oxley et al. have reported several solid products, urea, ammonium nitrate, biuret, cyanuric acid, and melamine [15]. While the first two, urea and ammonium nitrate, are not very indicative, the latter three compounds could serve as additional indicators for UN; however, biuret, which was chosen as an easy indicator, could not be detected in any of the post-blast extracts from the firing of UN charges. These findings strengthen the need to focus on traces of intact UN. The hostguest methodology may provide the solution.

3. Urea nitrate can be extracted into nonpolar solvents containing crown ethers by forming typical 1:1 adducts. 4. Upon reaction with UN-1 reagent, urea nitrate-crown ether adducts produce the red color typical of the presence of free urea nitrate. 5. A mixture of ammonium nitrate and urea, the main nuisance in the identification of authentic urea nitrate, does not form urea nitrate in nonpolar solvents, as indicated by the negative reaction with UN-1 reagent. This behavior might provide the way to distinguish between authentic urea nitrate and urea nitrate which is formed in the equilibrium reaction between urea and ammonium nitrate.
Acknowledgments The authors are indebted to the Bomb-Squad Laboratory of the Israel Police for designing and carrying out the firing experiments and to Mrs. Sara Abramovich-Bar and Mrs.Yael Shloosh for processing the samples from the firing tests.

References
1. Tamiri T (2000) in: Siegel JA (ed) Encyclopedia of Forensic Sciences. Academic, London 2. Phillips SA, Lowe A, Marshall M, Hubbard P, Burmeister SG, Williams DR (2000) J Forensic Sci 45(2):324332 3. http://www.usdoj.gov/oig/special/9704a/00exesum.htm 4. Worsham JE, Busing WR (1969) Acta Crystallogr A B25:572 578 5. Harkema S, Feil D (1969) Acta Crystallogr A B25:589591 6. Almog J, Kraus S, Glattstein B (1986) J Energ Mater 4:159167 7. Kohno Y, Takahashi O, Hiyoshi RI, Nakamura J, Saito K (2003) J Phys Chem A 107:64446450 8. McCord BR, Hargadon KA, Hall KA, Burmeister SG (1994) Anal Chim Acta 288(12):4356 9. Hargadon KA, McCord BR (1992) J Chromatogr 602:241247 10. Almog J, Klein A, Tamiri T, Shloosh Y, Abramovich-Bar S (2005) J Forensic Sci 50(3):582586 11. http://pubs.usgs.gov/fs/fs155-99/fs155-99.html 12. Almog J, Burda G, Shloosh Y, Abramovich-Bar S, Wolf E, Tamiri T (2007) J Forensic Sci 52(6):12841290 13. Tamiri T (2005) Rapid Commun Mass Spectrom 19:20942098 14. Kutty TRN, Murthy ARV (1972) Indian J Technol 10(8):309312 15. Oxley JC, Smith JL, Naik S, Moran J (2009) J Energetic Mat 27 (1):1739 16. Kutty TRN, Murthy ARV (1972) Indian J Technol 10(8):305308 17. Uiterwijk JWHM, van Hummel GJ, Harkema S, Aarts VMLJ, Daasvatn K, Geevers J, den Hertog JrHJ, Reinhoudt DN (1988) J Incl Phenom 6(1):79100 18. Doxsee KM, Francis PE, Weakley TJR (2000) Tetrahedron 56 (36):66836691 19. Partington JR (1944) In: A text-book of inorganic chemistry, 5th edn. Macmillan, London, p. 858 20. Engel Y, Dahan A, Rozenshine-Kemelmakher E, Gozin M (2007) J Org Chem 72(7):23182328 21. Cagan A, Lu D, Cizek K, La Belle J, Wang J (2008) Analyst 133 (5):585587 22. Riegner DE, Kazmi SH, Kaplan SEF, Fountain AWIII (2009) 237th ACS National Meeting, Salt Lake City, UT, United States, March22 26

Conclusions 1. Urea nitrate has a low survivability to detonation. Only one out of 28 samples collected from post-blast debris showed the characteristic adduct ion by LC/MS. 2. The main decomposition products that are identified in post-blast debris of UN are urea and ammonium and nitrate ions.