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Hyphenated and non-hyphenated chromatographic techniques for trace level

explosives in water bodies - a review

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Hyphenated and non-hyphenated

chromatographic techniques for trace level
explosives in water bodies – a review

Cristina Veresmortean & Adrian Covaci

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hyphenated chromatographic techniques for trace level explosives in water bodies – a review,
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INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY
https://doi.org/10.1080/03067319.2018.1478969

Hyphenated and non-hyphenated chromatographic techniques

for trace level explosives in water bodies – a review
Cristina Veresmorteana,b and Adrian Covacic
a
Department of Chemistry, The Graduate Center of the City University of New York, New York, NY, USA;
b
Department of Sciences, John Jay College of Criminal Justice, The City University of New York, New York,
Wilrijk, USA; cToxicological Center, University of Antwerp, Belgium

ABSTRACT ARTICLE HISTORY

Explosives are a class of xenobiotic, which pose a permanent and Received 15 January 2018
increasing concern on human and ecosystem health. These che- Accepted 8 May 2018
micals are highly toxic, some carcinogenic, and their detection in KEYWORDS
rural areas, surrounding military bases and weapon training facil- Explosives; mass
ities, became imperious. Quality of potable water particularly in spectrometry;
rural areas, where wells are the primary water sources, is of great chromatography; water
importance. More effective ways of extraction with less solvent contamination; sample
consumption, coupled with chromatographic separation and mass preparation; ultraviolet
spectrometry/ultraviolet detection techniques, are needed to detection
quantify these trace level hazardous compounds at sub-ppb levels.
The ultimate scope of measuring the concentration for these
environmental contaminants is to build effective strategies for
site protection, remediation and removal. This complex and origi-
nal review brings together a vast amount of published work on
conventional and modern explosives extraction approaches and
their means of identification and quantification by hyphenated
chromatographic techniques. With a strong focus on aqueous
sample preparation and a multitude of analysis methods pre-
sented, this paper enables the researcher to a good assessment
on past, present and future aspects. Latest progress in the high-
resolution instrumentation is also briefly discussed.

1. Information on identity, toxicity and properties of target explosives

1.1. Overview
Listed as highly energetic compounds, explosives will rapidly decompose under chemi-
cal or physical stimuli, causing fast heat evolution and generation of high pressures of
gases, e.g. NOx, H2O, CO and CO2. According to their susceptibility to detonation,
explosives are classified into three categories: primary, secondary and tertiary. Primary
explosives are highly sensitive to ignition by friction, shock, heating or spark and serve
as detonators for secondary explosives. Secondary explosives are usually mixed with
primary explosives and linked together with plasticizers, waxes or stabilizers. Organic
secondary explosives are used for military operations, their detonation resulting in wide

CONTACT Cristina Veresmortean cveresmortean@ccny.cuny.edu

© 2018 Informa UK Limited, trading as Taylor & Francis Group
2 C. VERESMORTEAN AND A. COVACI

spreading of toxic debris over waterbodies and other environmental entities. Tertiary
explosives do not self-detonate, unless a secondary explosive is present [1,2].
Belonging to the aforementioned category of organic secondary explosives and
targeted in this review paper are: (a) nitroaromatics (NACs), a subclass of compounds
holding a C-N-NO2 bond: NB (nitrobenzene), DNBs (dinitrobenzenes), TNB (trinitro-
benzene), DNTs (dinitrotoluenes), TNT (trinitrotoluene); (b) nitroamines: RDX (hexahy-
dro-1,3,5-trinitro-1,3,5-triazine or hexogen) and HMX (octahydro-1,3,5,7-tetranitro-
1,3,5,7-terazocine or octogen); (c) nitroesters: PETN (pentaerythritol tetranitrate or
penthrite). These pollutants were selected to be presented, due to their high prob-
ability to exist in waterbodies next to military establishments and based on numerous
publications, reports and statistics about their negative impact on human health and
environment [3].
TNT, RDX and HMX are being regularly investigated, as part of wastewater monitoring
process. Due to the nitro group existence with electron-withdrawing properties, these
compounds are not prone to aerobic attacks, making them persistent environmental
pollutants. DNB, DNT and TNB will appear as co-pollutants, with faster mobility in
waterbodies. As subjects of our interest, organic secondary explosives will be addressed
in this paper, with the selection rationale as follows:

(a) NB is an oxidizing agent used in explosives manufacturing. Owing a high biode-

gradability, it will not accumulate in soil or sediment, thus showing a potential to
be present in surface water and groundwater [4]. NB is also listed as a transfor-
mation product of TNT [5].
(b) DNBs, by-products of TNT, can be formed in small quantities in the manufac-
turing process and accidentally released to the environment [6]. DNB is identi-
fied as a degradation product of TNT, in cyclic voltammetry studies [7]. Three
isomers are encountered: ortho, meta and para DNB. The physical and chemical
properties of the isomers are generally similar, with the difference that 1,2
isomer is more soluble in water [8].
(c) TNB is a compound resulting from TNT’s photodegradation, being itself resistant
to further photodegradation. Biotransformation of TNB yields to dinitroaniline, a
target contaminant on Environmental Protection Agency (EPA)’s list [9].
(d) DNTs are not specific explosives targets, being detected as impurities in TNT
manufacturing or as degradation products of TNT [7]. DNTs are also used as
propellants [9]. Among six isomers 2,4 and 2,6 DNT are the most common
forms. The other forms make up only 5% of the technical grade [3].
(e) RDX and HMX are the most mobile contaminants present in groundwater [9]. The
high explosive RDX production is limited to US Army ammunition plants solely
[2]. RDX and HMX are chemical homologues having similar properties. HMX is
used as booster in Octol (a TNT-based explosive) and as oxidizer in gun propel-
lants. RDX and nitroglycerin form a plastic explosive mass [10].
(f) PETN is the strongest explosive known, less soluble in water and less persistent
in the environment, compared to RDX. PETN is used in blasting caps, detonat-
ing fuses and manufacturing of pentolite [10]. Replacing plastic-based RDX
explosives with plastic-based PETN might become a viable option for the US
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 3

Department of Defense, in the efforts to minimise contamination, especially at

military training ranges [11].

1.2. Toxicity
Many explosives are very toxic, some mutagenic or possibly carcinogenic [12]. NB is one of
the extremely toxic chemicals, detrimental to human health, and is listed as a contaminant
of concern. At higher than 30 µg/L nitrobenzene concentration, symptoms include fatigue,
weakness, dyspnoea, headache and dizziness. Potential human exposure at elevated levels
of nitrobenzene might include depressed respiration, bluish-grey skin, disturbed vision
and coma. Reproductive effects, such as a decrease in fertility, reduced testicular weights
and decreased sperm production, have been found in animal studies. The criterion for
protecting freshwater aquatic life is set at concentration level <1.1 mg/L [3]. Following
chronic exposures to DNBs, anaemia and sometimes hepatic injury, impaired vision and
yellow discoloration of the conjunctiva and sclera of the eye were observed. TNBs are
expected to cause similar toxic actions as DNB. The oral lethal values in rats are reported
to be 275 mg/kg of TNB and 59 mg/kg of DNB [13]. Toxicity of TNT was well documented
in the twentieth century, when many fatalities were reported during manufacturing
operations of explosives. EPA established a drinking water lifetime advisory guidance
level of 2 µg/L. The health advisory for cancer risk in drinking is 0.1 mg/L [3].
Information on the adverse health effects of HMX is limited. In one human study, no
adverse effects were reported in workers exposed to HMX in air. Studies in rats, mice and
rabbits indicate that HMX may be harmful to your liver and central nervous system, if it is
swallowed or gets on your skin. A single oral dose of 100 mg/kg caused death in rabbits [14].
The reproductive and developmental effects of HMX have not been well studied in humans
or animals. At present information on HMX human carcinogenicity is not available [14].
There are no studies reported of cancer in people exposed to RDX. The EPA has determined
that RDX is a possible human carcinogen based on the presence of liver tumours in mice that
were exposed to RDX in the food for 1–2 years. Lifetime levels in drinking water set by EPA are
2 µg/L. People exposed to large amounts of RDX also have alterations in blood pressure and in
some components of the blood, but these effects may be secondary to the seizures [15]. In
humans PETN may cause effects on the cardiovascular system, resulting in lowering of blood
pressure, as well as dyspnoea and convulsions. There was no evidence of carcinogenicity in
mice. There was a marginal increase in Zymbal gland tumours in rats that suggests a possible
PETN-related effect, but it did not provide unequivocal evidence of carcinogenicity. Lethal
concentrations for some freshwater crustacean species are reported in the range of 9–10 g/L,
after 24 and 48 h of exposure, respectively. Some of freshwater species were exposed for 96 h
to a lethal dose of 27 g/L [12]. In 2011, Kalderis et al. published an extensive discussion on the
toxicity of explosives on humans, plants, vertebrates, invertebrates, bacteria and algae [16].
Remediation of polluted sites containing toxic materials emerging from explosive-related
operations had been in focus for many years. Contaminated debris from explosives utilisation,
containing toxic and/or carcinogenic degradation products of TNT (1,3 DNB, NB), contributes
to soil and water pollution [17,18]. Quality of drinking water supplies (wells, springs and lakes)
shall be closely monitored to assure residents of clean and safe resources [19]. Weapon testing
during training activities has a direct impact on the flora and fauna, due to the debris fallout
4 C. VERESMORTEAN AND A. COVACI

[18]. Accounting for their toxicity it is imperative to know their environmental fate and modes
of transport through waterbodies, particularly near military establishments or military grounds
of operation [16,17]. Photodegradation is considered a major attenuation mechanism, build-
ing the foundation for remediation processes [20,21]. Open burning/open detonation and sea/
land dumping of outdated munitions (OB/OD), unexploded ordnance (UXO) are other poten-
tial sources of pollution. Continuing studies are required in order to minimise or eliminate
population exposure to such harmful chemicals [22]. Photodegradation is being considered a
new trend in environmental remediation of nitroamines and nitroaromatics explosives [21].

1.3. Chemical/physical properties of explosives

Listed properties are depicted in conjunction with their potential to exist in the envir-
onment, as pollutants: Henry’s law constant for volatility, photolysis rate, water solubility,
vapour pressure, organic-carbon partitioning coefficient (Koc) and soil/sediment water
partition coefficient (Kow). Generally, these explosives have low Henry’s Law constant
values of 10−7 to 10−15 atm m3/mol; hence, they have low tendency to volatilise from a
liquid solution into the gas phase. Compounds such as DNB, TNB, DNT, TNT, RDX, HMX
and PETN will not sublime or volatilise easily from water surface. However, NB is known
to exhibit slow volatilisation from surface water [4]. Their presence in surface waters
depends on the photolysis rate. When exposed to sunlight some of the compounds will
decompose yielding to by-products; hence, they will only be present at trace levels.
Water solubility constants cover a large range from 6.63 mg/L for HMX to 1900 mg/L for
NB. Octanol-water partition coefficient is a measure of hydrophobicity. Simulation
studies on water columns showed that some of these compounds will adsorb to
suspended solid/sediment (Koc dependent), while some, depending on their octanol-
water partition coefficient, will mostly reside in the water phase [15].
There are many nomenclatural synonyms associated with these compounds, as listed
in [17]. Structure, formula, physical properties and their potential presence in diverse
waterbodies are presented in Table 1.

1.4. Aims of this review

There are scarcely available papers on commonly used organic secondary explosives listing
comprehensive extraction methods coupled to chromatographic separation and mass spec-
trometry/ultraviolet detection. A fairly recent review deals with trace explosives analysis in
water samples; nonetheless, the writing had been limited to gas/liquid chromatographic
separation with mass spectrometry detection [23]. An earlier publication [1] brings in few
sections of sample preparation rather more complete than the previous one, although
omitted to evaluate the complexity of liquid-liquid micro-extraction (LLME), solid-phase
micro-extraction (SPME) and other special extraction techniques. A collection of gas chroma-
tography (GC), high pressure liquid chromatography (HPLC), capillary electrophoresis (CE),
thermal desorption (TD), ion mobility spectrometry (IMS), mass spectrometry (MS) and IMS/MS
analytical methods, which mostly concentrate on post-blast debris samples, is outlined in that
publication [1].
Table 1. Physical properties of selected explosives and probability in environmental waters.
Molecular Presence in
weight Vapour suspended
MW (g/ pressure P Water solubility S solids or Presence in Presence in
Category Formula CAS mol) (mmHg)a (mg/L)b Log Kocc Log Kowd sediment surface water ground water
Nitroaromatic (polar)
Nitrobenzene (NB) C6H5NO2 98-95-3 123.1 1.50×10−1 1900@ 20°C 1.56 1.87 Trace level Maybe f [126] Maybe f [126]
@ 20°C

1,3 Dinitrobenzene (DNB) C6H4N2O4 99-65-0 168.1 1.46×10−4 533 2.17 1.49 Trace level Yes Yes

1,3,5 Trinitrobenzene (TNB) C6H3N3O6 99-35-4 213.2 6.44×10−6 278 2.02 18 Trace level Yes Yes

e
2,4,6 Trinitrotoluene (TNT) C7H5N3O6 118-96-7 227.1 8.2×10−6 115 3.2 1.86 Yes [16] Maybe f [16] Trace level

e
2,4 Dinitrotoluene (DNT) C7H6N2O4 121-14-2 182.2 2.2×10−4 200 1.75–3 1.60; 1.99 Maybe [16] Yes Yes

Nitroamine (very polar)

e
Hexahydro-1,3,5-trinitro- C3H6N6O6 121-82-4 222.3 4.1×10−9 59.7 1.6; 2.2 0.87 Maybe [16] Maybe f [16] Yes
1,3,5-triazine (RDX)

Octahydro-1,3,5,7-tetranitro- C4H8N8O8 2691-41-0 296.2 2.41×10−8 6.63 @20°C [127] 1.5; 2.5 0.06;0.26 Trace level Maybe f [16] Yes
1,3,5,7-terazocine (HMX)

Nitroesters (less polar)

Penta-erythrtol tetranitrate C5H8N4O12 78-11-5 316.1 1.36×10−7 43 0.54 2.38 Trace level Yes Yes
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY

(PETN)
5

All references, except noted are from citation [128].

a
All @ 25°C, except noted; range: 1.0×105 > P > 1×10−9; different values are reported in literature [129]; b range: 1.0×104 > S > 1.0×10−3; c range: 7>log Koc>-3; d range: 7>log Kow>-3; e level
dependent on the organic carbon fraction; f level dependent on the photolysis rate.
6 C. VERESMORTEAN AND A. COVACI

The purpose of this review is to fill in lacking information of precursor reviews, on

explosives extraction from water entities existent in the proximity of military establish-
ments and its pertaining methods of analysis.

2. Experimental considerations on sample preparation

Knowledge about sample and analyte type, matrix of provenience, amount of sample
available, previous existence of analytical methods or the need to develop new ones,
instrumentation, materials available, etc., are among important factors to be evaluated
prior to planning an analysis [24]. Nowadays, as groups are switching towards a greener
and cheaper method, improved sample preparation methods are essential [25].

2.1. Sample collection and preservation

Trace evidence of explosives in environmental samples such as, soil, sediment, air, water,
dust and melted snow [26] has become an intensely researched topic. Collection of
samples from the contaminated sites, such as military establishments, practice ranges,
ammunition plants, dumping areas and burials, demolition zones, snow avalanche
control areas, etc., must follow well-established guidelines [27]. The guidelines must
emphasise on conservation of sample’s chemical, physical and biological attributes and
be processed with minimal contamination [28]. Solutions that contain trace level quan-
tities of organic explosives must be kept in silanised glass containers, at below 4°C, in
the absence of light. A water effluent sample should be acidified to pH 3.5 and 10%
acetonitrile added. Some of the compounds such as DNT will be retained by plastic
containers, not determined with TNT, RDX and HMX [29]. A useful approach for surface-
and groundwater sampling is given in [30]. Passive sampling is a novel method of
analyte enrichment from environmental water, presenting many advantages over the
already established sampling procedures: larger volumes, rapid collection, reduced field
sampling variability, ease of handling, etc. The sampler coating polymer can be tailored
to selectively concentrate TNT and RDX from marine systems [31].

2.2. Preparation techniques for water samples in environmental forensics

2.2.1. Preliminary processing
Schramm et al. developed an LC/MS method for DNB, TNB, TNT, DNT, HMX, RDX and
PETN analysis in groundwater samples from a military site, without a pre-concentration
step. Samples were filtrated through syringe filters and placed directly into the auto-
sampler [22,32]. Mu et al. (2012) followed the same approach of filtration using a
0.22 µm nylon membrane, with direct injection into the LC/MS system [33,34].
Similarly, other groups have opted for minimal sample preparation, in quantifying TNT
and RDX present in water samples. Analytes are extracted with an organic solvent, which
then is separated from aqueous phase and injected directly into the chromatographic
system [35]. Other preliminary processing steps include centrifugation, solvent
exchange, desalting, evaporation, freeze drying, evaporation, distillation, microdialysis,
sieving and grinding (for solid samples) [36].
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 7

2.2.2. Conventional extraction methods overview

Among the extraction methods of high usage for liquid samples (statistical data of 2002)
are conventional SPE (solid-phase extraction), conventional LLE (liquid–liquid extraction),
supercritical fluid extraction (SFE) or SFC (supercritical fluid extraction) and column
chromatography. USE (ultrasonic extraction) technique is mainly employed for soil and
sediment extraction, although some publications list sonication coupled with HF-LLME
(hollow fiber liquid–liquid microextraction) to monitor the fate of explosives in water
samples [37]. Following on another publication, an ultrasonic titanium probe was dipped
into a reaction mixture of water sample and extracting solvent, to aid in extraction of NB
and TNT [38]. Conventional SLE (solid-liquid extraction), a seldom used replacement
method for LLE, will solve some of the disadvantages of LLE by using a highly purified,
high-surface area, inert DE (diatomaceous earth) sorbent. SFE can be directly applied to
either air, solid or liquid matrices. A combination of SPE and SFE had been used for DNT
extraction from well and surface water samples [39]. All of the common, old-fashioned
extraction techniques employ high or relatively high volumes of solvent. They had
gradually been replaced by safer techniques, with minimal solvent usage.
A comprehensive collection of sample preparation techniques for chromatography is
presented in Scheme 1, to aid the reader in a better understanding of abbreviations and
classifications used throughout the literature.

Scheme 1. Classification of Extraction Techniques.

8 C. VERESMORTEAN AND A. COVACI

2.2.3. Microtechniques overview

Flowing with the new trend towards solvent-less applications, LLE has been scaled down to
LPME (liquid-phase microextraction) by using microvolumes of extracting phase, and SPME
has been introduced as a fast, solventless extraction method for trace level analysis.
LLEs comprise of a multitude of microtechniques (membrane-assisted, single
drop, drop in drop, fibers, ionic liquids, vortex/microwave assisted, continuous
flow, directly suspended and floating drop), where the ratio of sample/solvent is
very high. Enrichment factor (analyte concentration in the processed sample/ana-
lyte concentration in the initial sample) can reach 100 times higher values. Included
in the same class are: membrane-assisted, salting-out, electrochemically modulated
and cloud-point extractions [24,36].
Similarly, SPEs include microtechniques (fibers, stir-bar, thin-film, in tip, syringe, in-
tube) with diverse materials used as sorbents and other techniques such as matrix
dispersion and QuEChERS. SPME can be automated and hyphenated with GC/MS or
LC/MS techniques [40]. The fibre is either immersed into a liquid, where from the analyte
is adsorbed, or is placed in the headspace of the vial filled with sample. Volatile analytes
sorb onto fibre of diverse polarities and either thermally desorb inside a GC injector or
solvate into a mobile phase of an LC system [41].
A comprehensive diagram with different modes of SPME is outlined by Bagheri et al.
in 2014 [42]. LPME and SPME are extensively used for NB, DNB, TNB, TNT and DNT
extraction in soil and water samples (Table 2). Variations of these techniques are out-
lined in a review of Padron et al. [43].

2.2.4. LLE and LLME functionalised interfaces

Conventional or common LLEs have been described earlier in this paper. A timeline
review of LPME and a very detailed description of the variations of the technique are
given in a chapter written by Fernández and Vidal [44]. Choice of solvents as extraction
phases in LPME is illustrated by Dadfarnia and Haji-Shabani [45].

2.2.4.1. Conventional LLE method. Nitrobenzene has been extracted from water
samples by the means of funnel extraction separation. The organic layer was collected
and a small volume directly injected into a GC/MS instrument. Calculated recovery
reported was 108% [46].
EPA method 3650B lists DNBs and 2,4 DNT being extracted in organic solvents, by
liquid–liquid partitioning method [47].
Discontinuous and continuous LLE has been applied for enrichment of water samples,
in the area of former ammunition plants in Germany, by the German group of Lewin
et al. in 1997. Their data show recoveries of 76–78% for DNT isomers. The limit of
detection for HMX and RDX is 20ug/L and 35ug/L, respectively. By-products and meta-
bolites of TNT had been evaluated [48].

2.2.4.2. Membrane assisted. This type of extraction involves two liquid phases,
organic and aqueous separated by a membrane, which can also function as sensor/
biosensor and are suitable for compounds containing nucleophilic groups, such as TNT
and RDX. Detection range for TNT and RDX in this displacement immunoassay used is at
the femtomole level [49,50].
Table 2. Concentration of target analytes in waterbodies, surrounding military bases and other contaminated sites worldwide.
Method/
instrument Method
Target Extraction Analysis detection limite (µg/L) Concentration (µg/L) recovery (%) Reference
NB _ 0.3–13.8 a _ [126]
[
SPE (EPA 3535) GC/MS 1.9 210–250b 40–102 b 4, 126]d
1400b
SPE HPLC/UV 7.1 _ 32.6a [74]
SPME GC/MS 0.0025–0.005 _ 79–108a [87]
D-µSPE HPLC/UV 0.46 _ 82–98c, 84–102a [89]
DUSA-DLLME GC/MS 0.03–0.91 3.0–6.6a 83–109a [38]
2.3–7.2h 56–88h
IL-LPME HPLC/DAD 1.38 374–396h 91–95h [52]
1,3 DNB _ _ _ 0.6–6.6a _ [130]d
0.74–704b
Amberlite XRD GC/ECD <0.1 1.2–195b 80–88c [13]d
SPE APCI(-) LC/MS 0.02 - 80–120g [59]d
SPE APCI(-) LC/MS 0.107; 0.034 - 97b [60]d
SPE HPLC/UV 3.8 - 88g [74]
HF-LPME GC/MS 0.4 45.1–54.9a _ [37]
44.2–53.8a
MW-CNT, HF-SLPME GC/MS 0.03–0.94 _ 95c, 94a, 94b [88]
Filtration APCI(-) LC/MS 0.5 - 100–105b [32]
SPME, SPE HPLC/UV 7.2; 0.03 - 114–117g [66]
1,3,5 TNB Amberlite XRD HPLC/UV 50 0.8–7720b, 2000a 85–102a [13]d
_ _ _ 0.2–7720 b [130] d
3.0–97 a
Filtration APCI(-) LC/MS 0.02 - 95–105b [32]
SPE APCI(-) LC/MS 0.01 - 80–120g [59]d
MW-CNT, HF-SLPME GC/MS 0.03–0.94 _ 95c; 93a; 95b [88]
SPE ESI(-) LC/MS 0.142; 0.013 _ 71a [60]d
SPME, SPE HPLC/UV 3.3; 0.1 _ 122; 113f [66]
HF-LPME GC/MS 0.57 45.9–56.1c _ [37]
43–52.9a
2,4 DNT _ _ _ 11b; <10a _ [12]d
- - - 300b - [2]
Filtration APCI(-) LC/MS 0.5 - 90–105b [32]
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY

SPE APCI(-) LC/MS 0.08 - 80–120g [59]

SPE APCI(-) LC/MS 0.092; 0.022 - 87a [60]
(Continued )
9
 10

Table 2. (Continued).
Method/
instrument Method
Target Extraction Analysis detection limite (µg/L) Concentration (µg/L) recovery (%) Reference
SPE HPLC/UV 8.6 - 102g [74]
HF-LPME GC/MS 0.45 42.1–49.9c _ [37]
44.9–53.1a
SPME, SPE HPLC/UV 0.44; 0.14 104; 112f 93; 98f [66]
D-µSPE HPLC/UV 0.53 _ 89–97C [89]
92–100a
MW-CNT, HF-SLPME GC/MS 0.03–0.94 _ 97c; 95a; 96b [75]
SPE APCI(-) LC/MS 0.048 225h; 303h; 279h 63–91h [65]
_
2,4,6 TNT _ _ 1600b _ [2]
_
_ _ 0.4–21,960 b _ [130] d
1.0–3,375a
C. VERESMORTEAN AND A. COVACI

SPE APCI(-) LC/MS 0.01 - 80–120g [59]

Filtration APCI(-) LC/MS 0.02 39; 40b 95–110b [32]
SPE ESI(-) LC/MS 0.116; 0.016 - 110a [60]
DUSA-DLLME GC/MS 0.03–0.91 2.4–5.6a 66–94a [38]
MW-CNT, HF-SLPME GC/MS 0.03–0.94 _ 96c; 94a; 94b [75]
SPME HPLC/UV 1.4; 0.12 _ 93–110f [66]
HF-LPME GC/MS 0.45 39.1–48.9c _ [37]
38.2–47.8a
c
Filtration ESI(-) LC/MS 0.5e; 0.7a, 101a, c _ [33]
SPE APCI(-) LC/MS 0.033h - 114–134h [65]
RDX _ _ _ 0.73–7.6a _ [128]
4.4–249b
- - - 0.5–36,000b - [130]d
2.6–224a
- - - 1000b - [2]
SPE APCI(-) LC/MS 0.01 - 80–120g [59]
Filtration APCI(-) LC/ME 20 _ _ [32]
ESI(-) LC/MS 0.047; 0.004 <70a 86a [60]
SPE HPLC/UV 0.29 108f 87.3–106g [66]
c
Filtration ESI(-) LC/MS 0.02; 0.05e; 0.15a, 101c; 99.8a - [33]
SPE APCI(-) LC/MS 0.04h - 79–103h [65]
HMX _ _ _ 67a _ [14]
0.53–821b
(Continued )
Table 2. (Continued).
Method/
instrument Method
Target Extraction Analysis detection limite (µg/L) Concentration (µg/L) recovery (%) Reference
- - - 1.9–67a - [130]d
1.3–4200b
- - - 400b - [12]
SPE APCI(-) LC/MS 0.01 - 80–120g [59]
Filtration APCI(-) LC/MS 20 - - [32]
SPE ESI(-) LC/MS 0.037; 0.009 20a 130a [60]
SPE HPLC/UV 106f 106f 94.5–100.5 [66]
c
Filtration ESI(-) LC/MS 0.025; 0.05e; 0.15a, 99.1c; 98.9a _ [33]
SPE APCI(-) LC/MS 0.039h - 73–103h [65]
PETN SPE APCI(-) LC/MS 0.4 - 80–120g [59]
Filtration APCI(-) LC/MS 20 - - [32]
_ _ _ 85,000a; 3.9b _ [127]
Filtration ESI(-) LC/MS 0.25e; 0.3c; 0.4a 101c; 99.2a _ [33]
SPE APCI(-) LC/MS 23h _ 114–134h [65]
a b d e g h
Surficial water; groundwater; c tap water; US data; IDLs (=3σ; standard replicates); MDLs (water extraction/analysis); f salt water; water; wastewater.
INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY
11
12 C. VERESMORTEAN AND A. COVACI

2.2.4.3. Ionic liquid based and other dispersants. Ionic and polymeric ionic liquids
(ILs/PILs) have been extensively used in many applications and as dispersants for SPME
extraction of DNT and TNT from water samples. An imide-based IL is employed as an
extracting solvent, showing high recovery percentages of 97–101% for DNT and TNT
from surface water samples. The recoveries are dependent on the NaCl concentration,
mass of the IL, dispersant volume and type [51].
NB extraction methods using IL are characterised of being robust (due to stability of the
ILs), reliable and selective, yielding high recoveries of 91–95%. For this study, an imidazolium
phosphate-based IL was used, to make it compatible with the HPLC column [52].
A combination of an anionic and cationic sorbent, in a two-column SPE combination,
is being utilised to extract/separate DNB, DNT and TNT from the ionic liquid phase they
have been dissolved in, prior to be analysed by LC/TOF/MS and GC/MS. The study was
done to prove that the ILs have excellent properties, as green and tunable solvents. The
Corley group (2015) report mostly qualitative data with their experiments [53].

2.2.4.4. Surfactant (micelle)-based interface. Some compounds have a tendency to

precipitate out of an aqueous solution when temperature increases, giving the appear-
ance of a cloudy solution. Nonionic and ionic surfactants, such as Triton, CTAB/CTAC
(cetyl-trimethyl ammonium bromide/chloride), SDS (sodium dodecyl sulphate), etc., are
added in certain concentration to the analyte solution. Parameters affecting extraction
efficiency are temperature, surfactant concentration, pH, amount of salt added, incuba-
tion and centrifuge times [24,54]. The technique is named CPE (cloud-point extraction)
and can be combined with SPME and other techniques [55].
A direct application of SDS to the RDX and HMX study is presented by Gaurav et al. in
2008, where recoveries from water samples are enhanced by 1.7-fold. LODs are lower than
those obtained by the EPA Method 8330, being situated at 1.5 and 3.8 µg/L level [56].
TNT’s colour reaction in the presence of trioctylmethylammonium chloride as dis-
perser in an alkaline medium, followed by chloroform extraction, yields to good extrac-
tion percentages. Recoveries from surface water and wastewater are reported in the
range of 95–104%. Linear range, LOD and precision have been compared to other
methods, demonstrating a rapid and efficient method of extraction [57].
The research group of Babaee and collaborators (2010) have successfully employed
CPE to extract TNT, HMX, RDX and PETN from river and well water samples in Iran. The
new method developed by them shows better recoveries (range 97–101%) than EPA
methods, lower detection limits than SPME HPLC/UV (0.08–0.40 µg/L) and comparable to
SPE HPLC/UV (0.09–0.29 µg/L) and RSD % (relative standard deviation) superior to all
other methods tested [54].

2.2.4.5. Nanofiber-based membrane/films. Electrospun nanofibres have picked up

interest in the applied materials and interfaces field. Fluorescent films of desired mor-
phology are prepared by electrospinning pyrene-doped polymers dissolved in DMF/THF,
to sensitively and selectively detect explosives in aqueous solutions. Nanomolar limits of
detection are reported for TNT, DNT and RDX [58].
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 13

2.2.5. SPE and SPME sorbents and functionalised interfaces

2.2.5.1. Polymer-based formats. Water samples subjected to explosives analysis
are routinely pretreated with SPE cartridges. ABSciex et al. used the Waters
Porapak RDX phase bed for DNB, TNB, TNT, DNT, HMX, RDX and PETN elution
with acetonitrile. Their collected water samples showed no trace of explosives;
therefore, a matrix spike test was conducted. LODs are situated at 0.01–0.4 µg/L
and reported LOQs range from 0.04 to 1.4 µg/L [59]. The same Porapak RDX has
been used by Cassada et al. in 1999 in the extraction of DNB, TNB, TNT, DNT, HMX
and RDX from military sites’ groundwater, giving better signals in ESI over APCI
with sub-ppb detection limit and recoveries between 71% and 130% [60].
Thurman and collaborators (2012) opted for a polymeric RP cartridge, with methanol as
an eluting solvent. Spiked samples of water with DNB, TNB, TNT, DNT, HMX, RDX and PETN
showed recoveries between 80% and 101% [61]. Swiss researchers worked on lake and
river water and used as pretreatment Strata X PVB resin SPE cartridges, manufactured by
Phenomenex. The elution solvent for TNT, HMX, RDX and PETN was methanol [62].
In 2013, Detata et al. did studies on spiked solvent, using different SPE cartridges and
several adsorbents for column clean-up. Among the cartridges tested, Oasis HLB fabri-
cated of PVP-DVB polyvinyl-pyrrolidone-divinylbenzene copolymer by Waters
Corporation demonstrated superior to Porapak RDX and silica gel cartridge. Recoveries
of NB, DNB, TNB, TNT, DNT, HMX, RDX and PETN in acetonitrile were around 94%, with
only 7% RSD. A clean-up procedure on Alumina/Florisil column yielded recoveries
greater than 75% for all analytes, except TNB and HMX [63]. In 2008, Tachon et al.
concluded that polymeric sorbents with small specific area used as SPE phases retained
explosive compounds better than the ODS phase [64].
Oasis HLB displays good recovery efficiency between 78% and 124% for DNB, DNT,
TNT, HMX, RDX and PETN. These recoveries were obtained in the post-elution step,
without evaporation of samples. When evaporation is employed, NB seems to be lost
due to volatilisation and is not detected by HPLC/UV. Other analytical conditions, such as
pH, solvent type and volume, sample volume and evaporation parameters, were tested.
A variety of sorbents, such as silica based, graphitic carbon, copolymers and alumina,
were tested and recoveries reported [65].
Monteil-Rivera et al. had given a comparison of two modes SPE and SPME and three
sorbents: Porapak RDX, Carbowax and PDMS (polydimethylsiloxane) for the analysis of
DNB, TNB, TNT, DNT, RDX, and HMX. Carbowax had proven to be the best SPME sorbent
with high recovery yields, although sensitivity was found to be inferior to SPE.
Nitrocompounds with different polarities were successfully quantified in water samples.
Optimisation of the extraction process was carried out [66].
In 2011, Moore et al. have used HS-SPME (polydimethylsiloxane fibre) for GC/MS baseline
separation of DNT isomers. In their experiment, they were trying to measure the volatile
profile of explosives and to design a field technique for canine training. Results obtained
were only qualitative; more experimental work and better design were proposed [67].
Improvements on SPME extraction have been later made in maximising the surface
area of the SPME fibres of a planar geometry (PSPME) [68,69].
Total vaporisation (TV) SPME, pioneered by a group of Purdue University, IN, was
applied for extracting volatile compounds in explosives. Eliminating the existence of a
two-phase system in HS-SPME (liquid–gas) by bringing all solid samples to the gas
14 C. VERESMORTEAN AND A. COVACI

phase, some of the equilibrium complexity is removed. Consequently, figures of merit

for the newly developed method are much improved (LOD of 100 pg/L). Polymer fibres
tested were non-polar, bipolar and polar [70].
An older method of Waters Corporation employs Porapak RDX SPE cartridge and two
chromatographic columns of different polarities in series. Recoveries from water samples for
NB, DNB, TNT TNB, DNT, RDX and HMX are found to be in the range from 98% to 102% [71].
SBSE is a promising solid-phase extraction technique giving the advantage of a large
polymeric surface adsorption area, coated onto a stir bar. A drawback of the procedure is
the lack of stationary phases available on the market [72]. In 2011, Makinen et al. claimed
that SBSE has been rarely applied to explosive analysis, although Loknauth et al. in 2006
successfully detected TNT in water samples by coupling the SBSE to IMS [1,73].
An elaborate study of the extraction variables/parameters using SBSE, along with
investigations of matrix effects for spring water, mineral water, and groundwater, is
presented by Schramm et al. in 2016. SBSE for DNB, TNB, TNT, DNT and PETN detection,
coupled to APCI(-) LC/MS analysis, was proven to be more sensitive than SPE, being less
time-consuming and with less chemicals usage. The coated polymethysiloxane poly-
ethylene glycol stir bars have shown an increase of 38% in recovery, compared to the
pure polymethylsiloxane stir bars [22].

2.2.5.2. Nanofibre-based sorbent. Carbon nanofibres fabricated of β-cyclodextrin

results in a composite structure used to extract nitroaromatics from water samples,
collected next to a gold mine. NB, DNB and DNT were recovered from spiked samples
in the proportion of 37% to 102%. pH dependency had been evaluated, being optimal at
around 7. Recoveries from real samples were higher than 80% for DNB and DNT [74].
A combination of MW-CNTs deposited on a membrane support (hollow fibre) and
immersed into an ultrasonic bath had proven to have similar LODs (0.03–0.94 ng/L) to
DUSA-DLLME GC/MS and SPME GC/MS and lower LODs than SPME HPLC/UV and HF-
LPME GC/MS. Water samples analysed for DNB, TNB, TNT and DNT were collected from
river and underground in Iran [75]. NB has been detected in a similar way, using sol-gel
technology to fabricate an HF-nanocomposite SPME. The recovery averaged at 90% in
environmental water samples and LOD was found to be 0.1 ng/mL. A pre-concentration
factor of ~7000 verifies the efficiency of the prepared nanocomposite [76].
Cyclodextrin had been used as a guest molecule for DNT, TNT, RDX and HMX to form
inclusion complexes, which can further be desorbed by a nitrogen laser and analysed by
MALDI-TOF/MS. The research group claims the method has an advantage of avoiding
matrix interferences, although no real samples had been analysed [77].

2.2.5.3. Silica support. The pre-concentration/treatment procedure proposed by Sun

et al. can be applied with an online hyphenated LC/MS system by using an enrichment
column, which is an XDB-C18-based SPE cartridge. For SPE, the pH of the sample
solution is important, since it can change solubility and ionisation of the analytes.
Efficiency of the pre-concentration step did not influence TNT, TNB and DNT, whereas
an optimal pH of 8.1 was selected for HMX and RDX elution. A pH of 6.3 of Milli Q water
was a good compromise for all explosives. Injection volume shown to be critical for
sensitivity and was optimised to 4 mL [78].
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 15

MIS (molecularly imprinted silica) has been tested and compared to the NIS (non-
molecularly imprinted silica) for DNB, DNT, TNT and TNB extraction, yielding up to 20
times higher recoveries [79]. Two MISs were synthesised with 2,4 DNT, as template and
triethylsilane, as linker. The new interface allowed selective determination of DNT and
TNT, with high extraction recoveries (>79%) [80].
A new MIP (molecularly imprinted polymer) phase has been prepared with TNT as a
template molecule and glued to a silica fibre for selective determination on TNT and
DNT, at low concentration levels. Extraction performances were compared to a non-
imprinted SPME fibre [81].
Many advances in MIP synthesis and use had been documented up to date. Different
MIPs’ synthesis approaches, along with possibility of combining liquid membranes to
MIPs, are presented in a review paper for environmental analysis [82].
In a review paper of Yilmaz et al. in 2017, the reader will find a subsection entitled
‘Explosives’, where some of the MIPs’ experimental work is outlined, along with its
pertaining citations [83].
MEPS is a miniaturised SPE incorporated in a microvolume syringe and having the
packing sorbent a C18 silica phase. This setup reduces the sample volume from millilitres
to micro-litres. MEPS can be online coupled with LC/MS/MS, LC-DAD and GC/MS.
Extraction yields for TNT and RDX, at low and high spike, were found to be 84% and
95%, respectively. LODs LOQs and precision were evaluated [84].
Moein et al. describe in their paper in very detail the green, inexpensive MEPS
technique and give a useful comparison to SPE, SPME and SBSE [85].

2.2.5.4. Carbon-based sorbents. Anthracite was proven to be a good sorbent for NB

and DNB in river water. In 2014, Parham et al. assert satisfactory recoveries for direct
analysis of the contaminants in water. Overall, the proposed anthracite method seems to
be very simplistic, only using minimal volumes of extraction solvent [86].
Graphene composite-coated SPME fibre has been proposed by Zhang and collabora-
tors to efficiently extract NB from lake and river samples at high recoveries of 94% and
86%, respectively [87].

2.2.5.5. Hybrid sorbents. A general direction is to improve overall sensitivity of analyte

determination as new fibre coatings are developed, along with more performant meth-
ods of analysis. Sol-gel technology and carbon nanotubes (CNTs) offer interesting
perspectives for DNB, TNB, TNT and TNB identification and quantitation [88].
Hybrid materials of polymers (active phase) and magnetic nanoparticles (solid sup-
port) enable recovery of the sorbent and simplify extraction procedure. Nitroaromatics
(NB, DNB, DNT) in surface water samples have been successfully extracted with disper-
sive micro-solid phase extraction (D-µSPE), which combines polymeric microparticles
and magnetic nanoparticles [89].
The latest progress in D-µSPE, comprising of sorbents made of nanomaterials, magnetic
nanocomposites, hybrid nanomaterials and a comparison to SPE, is presented in a review
paper [90].
16 C. VERESMORTEAN AND A. COVACI

2.2.6. Mixed extraction modes

A combination of sonical degradation, followed by HF-LLME (hollow fibre liquid–liquid
microextraction) of DNB, DNT, TNB and TNT, had been explored by Psillakis et al. in 2004.
They have monitored concentration-time profile of these explosives in tap water and
surface water samples, concluding that sonication is not an effective method of remov-
ing nitroaromatics from water [37].
In 2011, Cortada et al. gave another, simpler approach to the ultrasound-assisted
LLME, for NB and TNT analysis. Water sample and added extraction solvent were directly
subjected to sonic waves, by an immersed sono-electrode. They report LODs compar-
able or even lower to other works and low recoveries between 49% and 88%, due to
significant matrix effects [38].
Salting out has been shown to yield high recoveries with explosives extraction, when
using acetonitrile/sodium chloride salting out solution. When coupled with dSPE the
method is known as QuEChERS [36]. By scaling down on the solvent volume (to µl) and
mass of added salt (to mg), the process becomes miniaturised. The method can be
coupled with UAE to monitor the sonochemical degradation of explosives in water [37].
A new approach to the analysis of explosives was developed, back in 2007: SPME-
HPLC/UV, using the salting out effect to enhance the extraction of NB, DNB, TNB, TNT,
HMX and RDX. Headspace mode and direct immersion mode (DI) into the sample matrix
were tested, concluding the latter being more efficient [91].
A RAM, porous graphitic carbon (PGC) and C18 pre-column used for sample clean-up
and enrichment, followed by a PGC analytical column, had been proven effective for
DNB, TNB, TNT, DNT and RDX extraction in surface water, with RAM yielding to higher
recoveries for the above-named compounds [92].
Another approach for explosives headspace extraction considered using a combina-
tion of methods: SPE and SFE and a PGC analytical column. Recoveries for DNB, DNT and
TNT ranged from 85% to 105%. Findings showed that DNB and DNT are largely present
in the headspace phase, whereas TNB, DNT and TNT were detected in all samples [93].
Figures of merit of the analytical methods used for extraction among different
research groups are presented in Table 2, along with recoveries and concentrations in
real water samples.

3. Chromatographic techniques
3.1. Methodology
Most commonly utilised secondary explosives contain a nucleophilic nitro group that
facilitates their analysis by traditional analytical methods: gas/liquid chromatography
mass spectrometry [94]. Combination of UV and LC would work only for analytes
containing chromophores. Despite the valuable data obtained with HPLC/UV, the
method lacks selectivity and sensitivity for trace level analysis. On monitoring fragmen-
tation ions NO2, NO and CO3 during mass spectrometry experiments, selective identifi-
cation and precise quantification of explosives are attainable [23,32,59,95].
Mainly, two chromatographic methods for explosives analysis have been encountered in
the literature: gas or liquid chromatography, hyphenated to mass spectrometry. Non-volatile
compounds, which cannot be separated by GC/MS, might be suitable for LC/MS analysis. ESI
(electrospray ionisation) and APCI (atmospheric pressure chemical ionisation) are
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 17

predominantly employed in an LC/MS analysis for low molecular mass compounds. Each can
be operated in a positive or negative mode, dependent on the analyte properties. A detailed
discussion on mass spectrometry techniques is given elsewhere [96,97].
Summaries of extraction procedures, amenable matrices, concentrations and analy-
tical methods with figures of merit and percentage recoveries are gathered in Table 2.

3.2. Separation methods

3.2.1. Method energetics comparison
Thermodynamic and energetic data for nitrocompounds give an insight on their beha-
viour under mass spectrometry conditions, e.g. fragmentation pathways, ion-neutral
reactions, proton transfer and electron capture, and are presented in Table 3. Setting
up compound/source specific parameters in the method is a crucial step in achieving
proper ion formation. Since many organic compounds have low ionisation energies (5–
15 eV), an electron is easily extracted. The excess energy is used to fragment or
rearrange the structure; therefore, if lowering the ionising energy formation of molecular
ion is possibly enhanced and less fragmentation occurs [98]. Knowing the ionisation
potential (IP) of compounds, one can predict whether ions will be formed and also
estimate on how low one can set the applied voltage.
The nitroaromatic/amine/ester target compounds have relatively high EA (electron
affinities) and expected to form negative ions in negative ionisation mass spectrometry.
These negative ions, depicted as molecular ions, are generally seen after running a full
scan for each compound of interest. For some compounds, ionisation provides with
protonated/deprotonated ions, also named quasi-molecular ions. In other case, analytes
are detected at higher sensitivity as adducts, after ionic modifiers are added to the mobile
phase. LC/MS uses softer ionisation techniques such as ESI or APCI, where the sprayed
analyte solution is subjected to a ‘dispersed’ electrical field, meaning the distance between
the two electrodes generating the electrical field is larger, compared to GC/MS.
Adjusting the sprayer voltage and position might lead to vast sensitivity improve-
ments in ESI LC/MS. The cone voltage (known also as declustering potential or orifice
voltage) might be adjusted to reduce cluster (or adduct) formation, which can be
detrimental due to their stability for fragmentation [99]. Electron-capture mechanism
is attributed to DNB, TNB, DNT and TNT, due to their positive EA. Formation of their
negative molecular ions in APCI(-) is confirmed in [59,100].
Values of gas-phase acidity indicate which analytes will go through proton–anion
dissociation, i.e. TNT and DNT; mostly form deprotonated ion, with molecular ion in

Table 3. Thermodynamic and energetic data for selected classes.

Ionization Electron
Analyte potential (eV) affinity (eV) ΔHacidity (kcal/mol) Reference
NB 9.9 <1.1 377 [131]
1,3 DNB 10.4 1.7 356 [95]
1,3,5 TNB 11.0 2.6 340 [95]
2,4,6 TNT 10.7 2.5 316 [95,132]
2,4 DNT <1.6 1.6 328 [95,132]
RDX 10.6 (based on B2PLYPD calc.) <0 >400 [95,132]
HMX 10.3 (based on B2PLYPD calc.) <0 >400 [95,132]
PETN 11.5 (based on B2PLYPD calc.) <0 [132]
18 C. VERESMORTEAN AND A. COVACI

small proportion. The lower the ΔHacidity, the easier the proton dissociation expected.
Gas-phase acidity numbers higher than 400 for some compounds, such as RDX and
HMX, will likely not lead to proton–anion dissociation. RDX, HMX and PETN will expect
form adducts with the additive of the MP. Additionally, steric effects can influence the
ionisation pattern [59,100].

3.2.2. Stationary phase selection for chromatography

Selectivity, along with efficiency and retention, can have a great impact on improving
resolution of a separation. Selectivity, which is the most powerful term in the resolution
equation can be controlled by the choice of stationary phase and mobile phase . Isomers
are indistinguishable in MS, unless coupled with a chromatographic column having a
suitable stationary phase, aim for better separation. Isomers of nitroaromatic com-
pounds exhibit similar behaviour on classical supports of C18-bonded silica and their
separation becomes a challenge. In overcoming these problems, the use of PGC column
enables a good separation, allowing retention of very polar compounds and discrimina-
tion of geometric isomers. PGC makes a good substitute for a C18-bonded silica-based
column, although desorption of non-polar compounds from carbon is a difficult task,
taking up to 33 min runtime [101]. In 2017, Rameshgar et al. have separated DNT
isomers on a 5% biphenyl-95% polydimethylsiloxane in river water samples, with excel-
lent resolution [102]. Other stationary phases, such as Poroshell EC-C18 and EC-CN,
allowed a shorter analysis time, with less solvent consumption for separation of the
isomeric forms; however, obtaining orthogonal selectivity still remains in high demand
[103]. A diol functionalised silica phase column yielded a better resolution for DNT
isomeric separation, compared to phenyl and C18 bonded phases [104].
Ion suppression, due to matrix effects, is a major concern for eluting analytes [105].
Matrix effects are not discussed in this context.

3.2.3. Hyphenated methods

3.2.3.1. Gas chromatography/mass spectrometry. Since NB is known not to be
suitable for LC/MS analysis due to its high volatility, GC/MS methods are rather
employed. The graphene-coated SPME fibre coupled to HS-GC/MS yields to low LODs
and high recoveries of NB in surface water samples [87].
Quantification of TNT and RDX in freshwater and seawater samples was performed by
the aid of NCI GC/MS [35]. Their method focuses on finding degradation products under
harsh environmental conditions, such as alkalinity and acidity of salt water, UV light
exposure or microorganisms’ presence. Moore et al. developed a training aid simulation
set for canine explosive detection. SPME GC/MS proves to be a powerful tool for
detecting target volatile compounds, although many inconsistencies were found in
the instrumental response [67]. Other groups have used GC/MS analysis in conjunction
with novel extraction methods for explosives in environmental waters [37,38,75].
A mixture of NB, DNB, DNT, TNB, TNT, RDX and HMX had been subjected to HF-LPME
extraction coupled to GC/MS identification in water samples. The method is performant
for only four of the seven listed explosives [37]. Degradation products of TNT and RDX in
saline water environment, with and without UV exposure, had been monitored with the
aid of a softer ionisation process, namely NCI GC/MS [35]. The drawn conclusion was that
salinity did not influence degradation, whereas in UV light degradation was rapid.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 19

Combining a novel interface MW-CNT/HF-LPME with GC/MS investigation for DNB,

TNB, TNT and DNT in water samples, high recoveries were obtained [75]. A fast GC/MS
determination and quantification of NB in laboratory-made water samples is given by Li
of Agilent Technologies, Shanghai [46].
Other methods of gas chromatography coupled to diverse detectors (e.g. ECD, TEA,
PD-ECD) are presented in a review work of Moore in 2004 and Makinen in 2011 [1,94].

3.2.3.2. Liquid chromatography/mass spectrometry. Nitroamines and nitroesters are

preferentially analysed by LC/MS and not by GC/MS, due to their low vapour pressure
and thermal instability.
The presence of NB, TNB, TNT, DNT, HMX, RDX and PETN in London’s wastewater was
acquired on an APCI(-) LC/MS system and all other compounds being identified, with the
exception of NB. This is a first report on a general method for trace analysis comprising
of multiple classes of explosives: nitroaromatics, nitroamines, nitroesters and peroxides.
The wide applicability of the liquid chromatography high-resolution mass spectrometry
method was tested for 17 compounds, 14 being detected at ng-µg/L level, with
recoveries from 77% to 124% [65].
In 2012, Badjagbo et al. collected all up-to-date mass spectrometric methods applied in
combination for detection of explosives in water samples. ESI and APCI are sensitive
techniques, very effective in studying the nitroaromatic compounds based on adducts.
However, impurities present in the mobile phases contribute to excessive adduct formation,
which complicates the spectra interpretation. In addition, intensities of ions may become
inconsistent, due to the variable concentration of impurities in the solution [23].
Agilent Technologies had adjusted the EPA Method 8330B, being successful in
identifying seven explosives analysed by ESI (-)/APCI (-) UHPLC/MS. Only NB was not
amenable to any of the liquid chromatography methods, due to its high vapour
pressure. APCI was confirmed to be more effective for ionisation than ESI, as confirmed
before [61]. Along NB, TNT had been also identified in waste and reservoir waters [38].
An interesting comparison of API (atmospheric pressure ionisation) variants is given
for NB, DNB TNB, TNT, DNT, HMX, RDX and PETN analysis in samples, other than water. In
this work, not all compounds were detected with all ionisation modes. HMX has not
been detected with APCI(-) LC/MS (no additive added in the MP) and NB, DNB and DNT
were not detected with ESI(-) LC/MS (ammonium acetate in MP) [106].
A stir bar extraction followed by APCI(-) LC/MS analysis was proven to be more
sensitive than SPE being less time consuming and with less chemicals usage. Among
DNB, TNB, DNT, TNT and PETN, only PETN obtained data showed less precision. ESI(-)
would be a more appropriate method for PETN [22].
Groundwater samples from the vicinity of an ammunition plant in France had been
analysed with the aid of APCI(-) LC/MS instrument, for determination of DNB TNB, TNT, DNT,
HMX, RDX and PETN and other explosives along with their degradation products. An
internal standard containing D3 and C13 was added to correct for variations in the response
and matrix effects [32].
The importance of isotopic ratio mass spectrometry is emphasised by Benson et al.
2006 and later by other groups, Benson [107]. Recently, with the need of more sophis-
ticated methods in trace level forensic analysis, isotopic dilution becomes essential [108].
20 C. VERESMORTEAN AND A. COVACI

Negative photoionisation coupled to mass spectrometry had been proposed for

organic explosives. Limit of quantitation (LOQ) for DNB, DNT, TNB, TNT, HMX and RDX
is proven to be lower two orders of magnitude, compared to APCI-LC/MS. The method
shows very good reproducibility and high intraday/interday precision [109].
Degradation products of TNT and RDX in water samples had been identified using ESI
(-) LC/MS, after analytes were exposed to UV light for several days. Minimal sample
preparation is involved, as we discussed in section 2.2.1 [35].
Surface water analysis in the ESI(-) LC/MS acquisition method had detected the
nitroesters RDX, HMX and PETN as acetate adducts and TNT as a quasi-molecular ion.
MS/MS optimisation is given, including selected MRMs for the above compounds.
Interestingly enough direct injection of samples into the LC/MS system showed no
significant difference to the SPE pre-concentration method. Therefore, direct injection
is well suitable and less time consuming for water samples having a cleaner matrix [62].
In a study published by Cassada et al. analysing well water adjacent to a US military
site, a mixture of methanol/water chromatography confirmed unsuitable for the forma-
tion of molecular or adduct ions in ESI (-). Many different buffer combinations had been
tried; the ammonium formate/IPA produced stable ion adducts with low ion back-
ground. The analysed nitroaromatics (DNB, TNB, TNT and DNT) did not give any formate
adducts in ESI (-), but high molecular ion sensitivity was confirmed in APCI (-).
Nitroamine compounds were detected as formate adducts in both ESI and APCI.
Recovery percentages were found to be between 80% and 130% [60].

3.2.3.3. High-resolution mass spectrometry. There is a solid history of using LCMS

instruments for measuring trace level small organic molecules and they were based on
quadrupole and ion-trap technology. An original paper, published in 2014, states that DNT
isomers are being differentiated by ESI-HRMS and their dissociation pathways are proposed
[110]. Nowadays, more and more hybrid instruments are emerging on the market, combining
powerful mass analysers, such as TOF (time-of-flight), Orbitrap, and ICR (ion cyclotron reso-
nance), with either quadrupole or ion trap. The recent advance in LC QTOF instrumentation
holds the same configuration of a quadrupole mass spectrometer, with the third quad
regarded as a drifting tube. The research group of DeTata et al. in 2013 have used APCI
TOF/MS for identification of NB, DNB, TNB, TNT, DNT, RDX, HMX and PETN and their isomeric
forms. Precursor and product ions are proposed; however, no quantitative data are reported
[63]. Although QTOF MS demonstrates fast data acquisition (500 scans/s, compared to
Orbitrap at 10 scans/s), it has lower resolving power (~60,000@FWHM) than an Orbitrap
(~100,000@FWHM) or an ICR (1,000,000@FWHM) [111]. As a result, an HRMS instrument
with high resolving power significantly eliminates possibility of a false positive response,
coming from the sample. A high resolving power is not sufficient to discriminate between
isotopic compounds; hence, there is a need of high mass accuracy instrumentation for trace
level analysis. An ICR delivers the highest mass accuracy among the three (0.1–1 ppm),
followed by Orbitrap with 0.5–1 ppm and QTOF with 3–5 ppm [111]. Hybrid instruments
captured researchers’ attention, in search, to overcome problems associated with isotopic
confirmation. In 2014, Xu et al. developed a highly selective screening of a post-blast explosive
sample, having a complicated matrix. The new hybrid instrument, which combines two
detectors (an IT and Orbitrap) with an HPLC system, was able to detect isomers of DNB and
DNT, with LODs in the pg range and mass accuracy within 1 ppm [112]. Picogram range LODs
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 21

for TNT and PETN and ng range for HMX using DART/Orbitrap-MS are evidence of a very
sensitive method for explosive analysis [113]. Drift tube ion mobility coupled to MS (DTIMS) is
claimed to be discriminative of home-made explosives from commercially available explosive
and a very sensitive tool to eliminate false positive, in the forensic analysis field [114]. Despite
their low volatility, RDX and PETN were successfully analysed by GCxGC TOF MS in a very short
time with a good resolution. Quantitative aspects were not evaluated [115].

3.2.4. Other methods

3.2.4.1. Liquid chromatography-ultraviolet detection. HPLC (high-pressure or high-
performance liquid chromatography) coupled to UV/DAD detection works well in
detecting all explosives with a chromophoric group in their structure. The following
explosives NB, TNB, TNT, DNT, HMX, RDX and PETN were tested with a HPLC/UV (DAD)
instrument to asses recoveries on SPE (Oasis HLB) during the purification step [65].
A two column in series (one polar, one non-polar) setup for nitroamines and nitroaromatic
explosives shows high recoveries and good resolution for the targeted compounds [71].
In a paper presented by Reyes-Gallardo et al., NB, DNB and DNT are subject to D-µSPE
followed by HPLC/UV (PDA) analysis, in order to evaluate the extraction procedure.
Absolute recoveries (40–70%) and figures of merit are reported for the determination
of nitroaromatics in creek water samples [89].
NB, DNB, TNB, TNT, DNT, HMX, RDX and PETN show remarkably high recoveries (80–
90%) on Oasis HLB SPE cartridge, as monitored by HPLC/UV [63].
Parham and Saeed assert satisfactory recoveries for direct analysis of NB and DNB in water.
Overall, their proposed extraction/HPLC-UV method seems very simplistic and efficient [86].
HPLC/UV is another option for quantification of TNT and RDX in groundwater sam-
ples. Optimisation of MEPS extraction and analytical method validation has been carried
out, indicating yields higher than 81% and LODs, LOQs in satisfactory ranges [84,85].
A new procedure for online enrichment of TNB, TNT, RDX and HMX in lake water
samples was published by Sun et al. Analytes were not detected in lake water and for
the method validation, spiked controls were used [78].
SPE and SPME HPLC/UV have been compared when analysing groundwater samples
from a military site in Massachusetts proving higher detection limits for SPME; nonetheless,
lower precision and accuracy. Aside, SPME introduces a shorter analysis time compared to
SPE [66]. A likewise comparison, also including an EPA method, is given by Babaee and
Beiraghi [54], among all their proposed methods showing lower LODs and good recoveries.
Direct infusion of TNT, DNT, HMX, RDX and PETN into an ion-trap mass spectrometer
provides a fast confirmation of the compounds and a guideline of possible fragmenta-
tion/adduction under ESI and APCI conditions [116].

4. Ending notes and future work

Owing the complex and complicated matrices of forensic and environmental applica-
tions, high sensitivity and selectivity of the hyphenated method deems be crucial for a
successful analysis. There are many aspects of an analytical work, where improvements
can be earned and these are (a) sample preparation, (b) compounds separation and
detection and (c) ionisation techniques. Worldwide, there is a demand to lower the
analytical detection limit to nano or pico level, while keeping a high efficiency, good
22 C. VERESMORTEAN AND A. COVACI

reproducibility, low cost and rapidity of the chosen method. Furthermore, newly devel-
oped methods should be universal, with a large scope of including a larger number of
explosives to be simultaneously measured.
Latest published work is channelled towards these trends, i.e. (a) sample preparation:
silica-gel nanocomposites as a solid-phases for extraction [117], pipet tip polymer nanofi-
bres for micro-solid-phase extraction [118], packed microvolume syringes [119], MIPs hollow
spheres for heavy matrices [120]; (b) separation: a new generation of HPLC columns with
superficially porous silica particles is on the market [121]; (c) ionisation techniques: paper
spray ionisation [122,123], alternating current corona discharge APCI [124], dual ionisation
sources ESI/APCI [123], dielectric barrier discharge DBD [125].
In writing this present paper, we aimed at unveiling the most commonly used techniques
and methods in Environmental Forensics, emphasising few recent advances in the field.

Disclosure statement
No potential conflict of interest was reported by the authors.

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