Talanta 54 (2001) 427– 438

www.elsevier.com/locate/talanta

Determination of nitroaromatic, nitramine, and nitrate ester

explosives in soil by gas chromatography and an electron
capture detector
Marianne E. Walsh *
US Army Cold Regions Research and Engineering Laboratory, 72 Lyme Road, Hano6er, NH 03755 -1290, USA

Abstract

Hazardous waste site characterization, forensic investigations, and land mine detection are scenarios where soils
may be collected and analyzed for traces of nitroaromatic, nitramine, and nitrate ester explosives. These thermally
labile analytes are traditionally determined by high-performance liquid chromatography (HPLC); however, commer-
cially available deactivated injection port liners and wide-bore capillary columns have made routine analysis by gas
chromatography (GC) possible. The electron-withdrawing nitro group common to each of these explosives makes the
electron capture detector (ECD) suitable for determination of low concentrations of explosives in soil, water, and air.
GC-ECD and HPLC-UV concentration estimates of explosives residues in field-contaminated soils from hazardous
waste sites were compared, and correlation (r \0.97) was excellent between the two methods of analysis for each of
the compounds most frequently detected: 2,4,6-trinitrotoluene (TNT), hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX),
2,4-dinitrotoluene (2,4-DNT), 1,3-dinitrobenzene (1,3-DNB), 1,3,5-trinitrobenzene (TNB), and octahydro-1,3,5,7-te-
tranitro-1,3,5,7-tetrazocine (HMX). The analytes were extracted from soils with acetonitrile by 18 h of sonication in
a cooled ultrasonic bath. Two soil-to-solvent ratios were evaluated: 2.00 g:10.00 ml and 25.0 g:50.0 ml. GC-ECD
method detection limits were similar for the two soil-to-solvent ratios and were about 1 mg kg − 1 for the di- and
trinitroaromatics, about 10 mg kg − 1 for the mono-nitroaromatics, 3 mg kg − 1 for RDX, 25 mg kg − 1 for HMX, and
between 10 and 40 mg kg − 1 for the nitrate esters (nitroglycerine [NG] and pentaerythritol tetranitrate [PETN]). Spike
recovery studies revealed artifacts introduced by the spiking procedure. Recoveries were low in some soils if the
amount of soil spiked was large (25.0 g) compared to the volume of spike solution added (1.00 ml). Recoveries were
close to 100% when 2.00-g soil samples were spiked with 1.00 ml of solution. Analytes most frequently found in soils
collected near buried land mines were the microbial transformation products of TNT (2-amino-4,6-dinitrotoluene
[2-Am-DNT] and 4-amino-2,6-dinitrotoluene [4-Am-DNT]), manufacturing impurities of TNT (2,4-DNT, 2,6-DNT,
and 1,3-DNB), and TNT. The microbial reduction products of the isomers of DNT and of 1,3-DNB were also
detected, but the ECD response to these compounds is poor. © 2001 Elsevier Science B.V. All rights reserved.

Keywords: Explosives; Soil; Compounds

* Tel.: +1-603-646-4666; fax: + 1-603-646-4785.

E-mail address: marianne@crrel.usace.army.mil (M.E. Walsh).

0039-9140/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 3 9 - 9 1 4 0 ( 0 0 ) 0 0 5 4 1 - 5
428 M.E. Walsh / Talanta 54 (2001) 427–438
1. Introduction
Traditionally, determination of explosives in
soil served either forensic or hazardous waste
investigations. More recently, there is interest in
ultrasensitive methods to determine the chemical
signature associated with buried land mines [1].
Gas chromatography (GC), a valuable analytical
technique for most organic environmental con-
taminants, has not been used routinely for quanti-
tative determination of explosives residues in soil.
However, these thermally labile analytes may be
accurately determined by gas chromatography by
using direct injection into a deactivated liner and
a short (6-m) wide-bore capillary column [2]. Re-
cently an analytical method for determination of
explosives in drinking water was developed that
was based on solid phase extraction (SPE) and
determination by GC with electron capture detec-
tion (ECD) [3]. This paper describes the analysis
of soil extracts using gas chromatographic condi-
tions similar to those used to analyze water
extracts.
GC detectors suitable for determination of ex-
plosives were reviewed by Yinon and Zitrin [4]
and include the flame-ionization detector (FID),
mass spectrometer (MS), nitrogen-phosphorus de-
tector (NPD), electron capture detector (ECD),
and thermal energy analyzer (TEA). Selectivity
and sensitivity are achieved with those detectors
responsive to the nitro group common to ni-
troaromatic, nitramine, and nitrate ester explo-
sives. The most selective detector for explosives is
the TEA, which detects only compounds that
produce NO or NO2. The NPD is slightly less
selective than the TEA, but insensitive to nitrate
esters [5]. The ECD, widely used for the determi-
nation of halogenated compounds, is less selec-
tive, but is more sensitive for nitroaromatics than
the TEA [6] or NPD [7,8].
The ECD was chosen because of its routine use
in environmental laboratories and its compatibil-
ity with acetonitrile, the preferred solvent for ex-
traction of explosives from soils [9]. The ECD
contains a source of beta particles (63Ni) that
collide with the detector make-up gas (nitrogen or
argon/methane) to produce many low energy elec-
trons per beta particle. These low energy electrons
are collected at the detector anode and produce a
small background or reference current. When
electron-capturing analytes (halogenated, nitro-
genated, or oxygenated compounds) elute from
the chromatographic column, they form nega-
tively charged ions, which are swept out of the
detector. Concurrently, the voltage across the cell
electrodes is pulsed to collect the remaining free
electrons. The pulse rate changes to maintain a
constant cell current; the change in pulse fre-
quency is proportional to the analyte concentra-
tion [10]. For di- and trinitroaromatic explosives,
ECD detection limits of 1 pg have been reported
[11].
To evaluate the performance of the ECD for
the analysis of explosives residues in soils, concen-
tration estimates obtained by GC-ECD were com-
pared to those obtained by the standard method.
Jenkins et al. [12] developed the standard method
for explosives in soil (SW-846 Method 8330 [13])
to characterize military sites contaminated with
explosives residues from the production or use of
high-explosives munitions. For this standard ana-
lytical method, a 2.00-g soil sample is extracted by
18 h of sonication with 10.00 ml of acetonitrile
(AcN). The AcN extract is mixed 1:1 (v/v) with
aqueous calcium chloride to flocculate fines prior
to filtration and analysis by high-performance
liquid chromatography with an ultraviolet detec-
tor (HPLC-UV). Explosives concentrations of 1.0
mg kg − 1 (1.0 ppm) or higher may be determined
using this procedure, and detection limits are
sufficiently low for human health or ecological
risk assessments. Jenkins et al. [12] chose HPLC-
UV rather then GC for several reasons: compati-
bility of the thermally labile analytes with room
temperature chromatographic separation, large
linear range of the detector, ruggedness of the
method, ability to analyze high concentration (\
40 mg l − 1) water samples by direct injection, and
compatibility of the solvent (acetonitrile) used to
extract soils with reversed-phase HPLC.
In the 1970s, Jenkins, Leggett, and Murrmann
used GC-ECD when they characterized the va-
pors from military-grade TNT in conjunction
with efforts to detect buried land mines by sam-
pling the atmosphere [14 –16]. Some solvent (ben-
zene) extracts of soil were analyzed as well.
 M.E. Walsh / Talanta 54 (2001) 427–438 429

Instrumentation at that time was not conducive to
quantitative determination of explosives in soil,
especially on a routine basis. Improvements in
injection port liners, GC columns, and most re-
cently the ECD detector [11] have led us to reex-
amine the utility of the GC-ECD for
determination of explosives in soil for both haz-
ardous waste site characterization and land mine
detection.
Analytes of interest differ somewhat for haz-
ardous waste characterization and land mine de-
tection (Table 1). Soils that were contaminated by
the manufacture or use of explosives most likely
contain TNT and RDX [17], the most common
found of the military-grade explosives. Co-con-
taminants such as manufacturing by-products and
biodegradation products may also be present.
More recently, HMX has been found at high
concentrations in soils from antitank firing ranges
where octol-filled (70% HNIX:30% TNT) rockets
have been fired [18,19]. For land mine detection,
the analytes of interest were predicted to be the
constituents of TNT vapor, principally the iso-
mers of DNT, DNB and TNT [20].
2. Experimental methods
2.1. Matrices
Field-contaminated soils were from Iowa AAP
(Army Ammunition Plant), Milan AAP (TN),
Nebraska Ordnance Plant, Monite (NV), Eagle
River Flats OB/OD (Open Burning/Open Detona-
tion) (AK), Raritan Arsenal (NJ), Savanna Army
Depot (IL), Chickasaw Ordnance Works (TN),

Table 1
Analytes of interest for two applications of analytical method for explosives in soil: hazardous waste characterization and mine
detection

Analyte Class Abbreviation CAS numbera Hazardous waste Mine detection

characterization

Octahydro-1,3,5,7-tetranitro-1,3,5,7- Nitramine HMX 2691-41-0

tetrazocine
Hexahydro-1,3,5-trinitro-1,3,5-triazi Nitramine RDX 121-82-4

ne
1,3,5-Trinitrobenzene Nitroaromatic TNB 99-35-4

1,4-Dinitrobenzene Nitroaromatic 1,4-DNB 100-25-4

1,3-Dinitrobenzene Nitroaromatic 1,3-DNB 99-65-0

1,2-Dinitrobenzene Nitroaromatic 1,2-DNB 528-29-0

2,4,6-Trinitrophenylmethylnitramine Nitroaromatic/nit Tetryl 479-45-8

ramine
Nitrobenzene Nitroaromatic NB 98-95-3

2,4,6-Trinitrotoluene Nitroaromatic 2,4,6-TNT 118-96-7

4-Amino-2,6-dinitrotoluene Amino-nitroarom 4-Am-DNT 1946-51-0

atic
2-Amino-4,6-dinitrotoluene Amino-nitroarom 2-Am-DNT 355-72-78-2

atic
2,4-Dinitrotoluene Nitroaromatic 2,4-DNT 121-14-2

2,6-Dinitrotoluene Nitroaromatic 2,6-DNT 606-20-2

2-Nitrotoluene Nitroaromatic 2-NT 88-72-2

3-Nitrotoluene Nitroaromatic 3-NT 99-08-1

4-Nitrotoluene Nitroaromatic 4-NT 99-99-0

3,5-Dinitroaniline Amino-nitroarom 3,5-DNA 618-87-1

atic
Nitroglycerine Nitrate ester NG 55-63-0

Pentaerythritoltetranitrate Nitrate ester PETN 78-11-5

a
Chemical abstract service registry number.
430 M.E. Walsh / Talanta 54 (2001) 427–438
US Naval Ammunition Depot (GA), Camp
Shelby (MS), Fort Ord (CA), CFB-Valcartier
(Québec), and Fort Leonard Wood (MO).
Blank matrices were Ottawa sand, an Army
Environmental Center standard soil obtained
from Rocky Mountain Arsenal (CO), a soil from
Fort Leonard Wood, and a silt obtained locally in
Hanover, NH.
2.2. Calibration
Standards were prepared from standard analyt-
ical reference material (SARM) from the US
Army Environmental Center, Aberdeen Proving
Ground, MD, or obtained commercially from
Supelco (Bellefonte, PA) and Restek (Bellefonte,
PA). All solutions were prepared in acetonitrile
(Burdick and Jackson, Muskegon, MI). Calibra-
tion standards were prepared fresh each day over
the range 0.40 to 100 mg l − 1 from 10.0-mg l − 1
combined stock solutions that were stored at
− 22°C in the dark.
2.3. Extraction
Archived field-contaminated soils were chosen
based on previous HPLC analysis that indicated
the presence of several of the Method 8330 ana-
lytes over a wide concentration range (B 1.0 to
50000 mg kg − 1). Following the soil extraction
procedure specified by Method 8330, 2.00-g soil
subsamples were extracted with 10.00 ml acetoni-
trile (with no internal standard) for 18 h in a
cooled sonic bath. To compare concentration esti-
mates obtained by GC to those obtained by
HPLC-UV, the extracts were split. For GC-ECD
analysis, a portion of each acetonitrile extract was
filtered through a Millex SR filter unit (Millipore,
Bedford, MA) prior to injection into the GC. For
HPLC-UV analysis, another aliquot of each ace-
tonitrile extract was mixed with an equal volume
of aqueous calcium chloride to flocculate fine soil
particles, and the mixture filtered through a
Millex SR filter unit prior to injection into the
HPLC.
Additional archived soils that had trace ana-
lytes (less than detection limit as determined by
previous HPLC analyses) were extracted using a
higher soil-to-solvent ratio (25.0 g soil:50.0 ml
acetonitrile). For each soil, duplicate 25.0-g sub-
samples were extracted with 50.0 ml acetonitrile in
a cooled sonic bath for 18 h. If enough soil was
available, matrix spikes (MS) and matrix spike
duplicates (MSD) were also prepared and ex-
tracted. Soils (25.0-g) were spiked with 5.00 ml of
a spike solution (50.0 mg l − 1 nitroaromatics and
200 mg l − 1 RDX) and left to air-dry for 24 h in a
fume hood. The spike solution contained the ana-
lytes of interest for mine detection (Table 1). The
spiked concentration in soil was 10.0 mg kg − 1 for
nitroaromatics and 40.0 mg kg − 1 for RDX. All
samples were extracted with 50.0 ml acetonitrile
containing 3,4-DNT (25.0 mg l − 1) as an internal
standard. These samples were also extracted for
18 h in a cooled sonic bath. Prior to GC-ECD
analysis, extracts were filtered through Millex SR
filter units. Prior to HPLC-UV analysis, 0.50 ml
of each filtered acetonitrile extract was mixed with
2.00 ml reagent-grade water (MilliQ).
Soils collected from an experimental mine field
at Fort Leonard Wood were extracted without
air-drying using 2.00 g soil:5.00 ml acetonitrile
and/or 20.0 g soil:50.0 ml acetonitrile.
2.4. Method detection limits and spike reco6ery
Method detection limits and spike recoveries
were determined using the two soil:solvent ratios
used for the extraction of field samples. Following
the Method 8330 protocol, seven replicate 2.00-g
soil samples (either Ottawa sand or AEC standard
soil) were spiked with 1.00 ml of 10.0- or 100-mg
l − 1 spike solutions to yield 5.00- and 50.0-mg
kg − 1 samples containing the analytes of interest
for hazardous waste site characterization (Table
1). After 1 h, 9.00 ml of acetonitrile was added
and the samples extracted for 18 h in a cooled
sonic bath. At 2 h into the sonication period, a
small aliquot of the extract was taken for analysis
to determine the stability of NG and PETN in a
cooled sonic bath.
A second set of Ottawa sand samples was
spiked by adding either 1.00 or 5.00 ml of a
50.0-mg l − 1 solution to 25.0-g soil samples to yield
2.00- and 10.0-mg kg − 1 samples for the nitroaro-
matics of interest for mine detection (Table 1).
 M.E. Walsh / Talanta 54 (2001) 427–438
The spike solution also contained RDX at a
concentration four times greater than the ni-
troaromatics. The samples spiked with 1.00 ml
were aged uncapped for 1 h prior to extraction.
The samples spiked with 5.00 ml were aged 24 h
uncapped. All samples were extracted with 50.0
ml, acetonitrile containing 3,4-DNT (25.0 mg l − 1)
as an internal standard. These samples were also
extracted for 18 h in a cooled sonic bath.
2.5. Instrumentation
2.5.1. GC-ECD
Initially, an HP 5890 equipped with an
Ni63ECD was used. Later, an HP 6890 equipped
with a micro cell Ni63ECD was used. For both
GCs, direct 1.0-ml, injections at 250°C were used.
The injection port liner was a deactivated Restek
Uniliner. The analytical columns were 6.0-m×
0.53-mm ID fused-silica, 1.5-mm film thickness of
either 100% polydimethylsiloxane (J and W DB-1)
or (5% phenyl)methylsiloxane (HP-5). The GC
oven was temperature programmed as follows:
100°C for 2 min, 10°C per min ramp to 200°C,
20°C per min ramp to 250°C, hold 5 min. The
carrier gas was hydrogen or helium at 12–15 ml
per min. The makeup was nitrogen (30 – 40 ml per
min). Confirmation columns were Restek
RTX-200 (Crossbond trifluoropropyl methyl-
polysiloxane) and Restek RTX-225 (50%
cyanopropylmethyl – 50% phenyl methylpolysilox-
ane). A pre-column was not used because extra
column length results in degradation of HMX [2].
2.5.2. HPLC-UV
Initial studies used the HPLC separation spe-
cified in Method 8330. A 25-cm by 4.6-mm (5-mm)
octadecyl (Supelco LC-18) column was eluted
with 1.5 ml per min 1:1 methanol:water. Two
alternative separations to achieve resolution of
DNB, DNT, and Am-DNT isomers used either a
25-cm by 4.6-mm (5-mm) octadecyl (Burdick and
Jackson OD5) column eluted with 1.4 ml min − 1
33:13:54 methanol:acetonitrile:water or a 15-cm
by 3.9-mm (4-mm) Nova Pak C8 (Waters Mil-
lipore) column eluted with 1.4 ml per min 15:85
isopropanol:water. The confirmation separation
was on a 25-cm by 4.6-mm (5-mm) cyano (Supelco
431
LC-CN) column eluted with either 1.5 ml per min
1:1 methanol:water or 1.2 ml per min 12:13:62
methanol:acetonitrile:water. Injection volume for
each separation was 100 ml. Following these
HPLC separations, absorbance was recorded at
254 nm on a Spectra Physics Spectra 100 variable
wavelength UV detector.
3. Results
3.1. Field-contaminated soils: concentration
estimates by GC-ECD and HPLC-UV
3.1.1. Wide concentration range
To test the feasibility of using GC-ECD for the
analysis of soil extracts, 24 archived field-contam-
inated soils were chosen that contained several of
the analytes of interest over a wide range of
concentration (based on previous HPLC-UV
analysis) and a variety of sites across North
America. Because some of these soils were ana-
lyzed by HPLC-UV over a decade ago, another
HPLC-UV analysis was performed at the same
time as the GC-ECD analysis, and extract splits
were used from 2.00-g soil aliquots extracted with
10.0 ml acetonitrile. The standard HPLC separa-
tion was used initially, then for those soils con-
taining isomers of DNT and Am-DNT, extracts
were reanalyzed using one of the alternative
HPLC separations described above.
For GC, extracts were analyzed on the HP5890
where the ECD had a very limited linear range.
All extracts were diluted by at least of factor of 10
and some up to 106 to be within the calibration
range. These large dilutions probably minimized
the deposition of high boiling point residues in the
injection port liner and on the head of the GC
column, a potential problem that concerns us
when GC is used routinely for the analysis of soil
extracts.
Details of the results of these analyses are re-
ported in [21]. The GC-ECD concentration esti-
mates were correlated with those obtained by
HPLC-UV for those analytes that were detected
ten or more times out of the 24 samples. The most
frequently detected analytes were TNT (18 times),
RDX (11 times), 2,4-DNT (15 times), TNB (19
432 M.E. Walsh / Talanta 54 (2001) 427–438

Table 2
Correlation of concentration estimates obtained by GC-ECD to those obtained by the standard HPLC-UV procedure

Analyte Site type Concentration range (mg kg−1) n Slope r

TNT Hazardous waste 0.28–27100 18 1.35 0.992

RDX Hazardous waste 0.28–13200 11 1.24 1.00
2,4-DNT Hazardous waste 0.10–95100 15 1.25 0.999
1,3,5-TNB Hazardous waste 0.15–570 19 0.81 0.976
1,3-DNB Hazardous waste 0.05–325 12 1.04 0.998
HMX Hazardous waste 3.5–2020 10 0.65 0.978
TNT Hazardous waste 0.02–0.27 10 1.14 0.997
2,4-DNT Hazardous waste 0.02–8.59 16 1.12 0.997
2,4-DNT Mine field 0.027–14.8 36 1.04 0.996
4-Am-DNT Mine field 0.10–1.51 26 1.05 0.956
2-Am-DNT Mine field 0.11–1.83 26 0.99 0.951

times), DNB (12 times), and HMX (ten times).
All correlation coefficients were greater than 0.97.
However, with the exception of DNB, slopes of
the least squares regression models were signifi-
cantly different from the expected value of 1.00.
For TNT, RDX, and 2,4-DNT, slopes were all
greater than 1.00 (Table 2). This difference in
slope may be an artifact of the experimental error
associated with the large dilutions required for
GC-ECD and the dominance of high values on
the slope obtained from a least-squares model.
Concentrations for each of these analytes spanned
over six orders of magnitude. Two other problems
were the considerable scatter in TNB data and the
underestimation of HMX by GC-ECD. The TNB
scatter is most likely due to TNB’s instability in
solution, and the underestimation of HMX is
likely due to thermal degradation during the GC
analysis. Although accurate GC analysis of HMX
is possible, the first peak to degrade in shape
following multiple injections of water or soil ex-
tracts is the HMX peak. Despite these problems,
GC-ECD analysis of soil extracts was judged
feasible. The GC-ECD offered two significant ad-
vantages over the standard HPLC method: lower
detection levels and improved chromatographic
resolution of the isomers of DNT and Am-DNT.
One important advantage of using both HPLC
and GC analysis is the ability to independently
confirm analyte identities in complex chro-
matograms. This advantage was apparent for one
of the Monite soils. Chromatograms from previ-
ous HPLC analyses were thought to show a peak
for TNT, but TNT was not detected by GC.
Rather the GC showed peaks for several isomers
of DNT, one of which (3,4-DNT) co-elutes with
TNT using the standard HPLC analytical separa-
tion and another (3,5-DNT) coelutes with TNT
using the standard confirmation HPLC
separation.
3.1.2. Trace concentrations
Another series of archived soils was selected for
extraction and analysis. For land mine detection,
very low (1 mg kg − 1) concentrations may need to
be detected, and soils were selected for which
previous HPLC-UV analysis had either shown
trace (less than the HPLC-UV detection limit of
200 mg kg − 1) concentrations of either TNT, 2,4-
DNT, or RDX, or the soils were collected near
samples that had trace concentrations. For the
extraction of these soils, 25.0-mg soil subsamples
and 50.0 ml of acetonitrile containing 25.0-mg l − 1
3,4-DNT as an internal standard were used. If
enough soil was available, matrix spikes/matrix
spike duplicates (MS/MSDs) were also prepared.
The GC analysis was conducted on an HP6890
equipped with a micro-ECD. Example chro-
matograms of a real soil extract are shown in Fig.
1. No dilutions were performed for the GC-ECD
analysis because of the expanded linear range of
the micro-ECD [11]. For the HPLC analysis, the
Nova Pak C8 (Waters Millipore) separation de-
scribed previously was used.
 M.E. Walsh / Talanta 54 (2001) 427–438
TNT was detected by GC-ECD in all 13 ex-
tracts ranging from 1.3 to 273 mg kg − 1 [21]. For
Fig. 1. Example GC-ECD chromatograms of a field-contami-
nated soil using (a) HP-5; (b) RTX-225; and (c) RTX-200
columns. The soil was collected from the Nebraska Ordnance
Plant and contains analytes most frequently found at haz-
ardous waste sites contaminated with explosives residues. (a)
HP-5 ([5%-phenyl]methylsiloxane), injector 250°C, 100°C for 2
min, 10°C per min ramp to 200°C, 20°C per min ramp to
250°C, hold 5 min, detector 280°C. (b) RTX-225 ([50%
cyanopropylmethyl–50% phenyl]methylpolysiloxane), injector
200°C, 100°C for 2 min, 10°C per min ramp to 250°C, hold 6
min, detector 220°C. (c) RTX-200 (Crossbond trifluoropropyl
methylpolysiloxane), injector 250°C, 100°C for 1 min, 5°C per
min ramp to 190, 1°C per min ramp to 200°C, 20°C per min
ramp to 250°C.
433
duplicates, the median relative percent difference
(RPD%) was 11%. One sample (Camp Shelby)
showed very poor agreement between replicates.
This sample had 2,4-DNT as the highest concen-
tration analyte, and the TNT, in this case, was
probably present as in impurity in 2,4-DNT, not
as a high-explosives residue. 2,4-DNT was found
in 11 of the 13 extracts, over the concentration
range 0.94 –8600 mg kg − 1. Two of the soils
showed extreme heterogeneity for this analyte
with concentration estimates of 36 and 8600 mg
kg − 1 in duplicates for one sample, and 145 and
4100 mg kg − 1 in duplicates for another sample. At
the sites where these soils (Eagle River Flats
OB/OD and Camp Shelby NE Quad) were col-
lected, propellant grains were scattered across the
soil surfaces. 2,4-DNT is a propellant ingredient,
and such extreme heterogeneity is consistent with
particulate contamination, such as from a propel-
lant grain fragment. In the samples with relatively
high 2,4-DNT concentrations, 2,6-DNT and 3,4-
DNT were detected as well by GC-ECD. These
two isomers co-eluted on the HPLC separation.
Thus, 3,4-DNT is not suitable as an internal
standard for extracts from soils contaminated
with high concentrations of 2,4-DNT.
The Am-DNT isomers were detected by GC in
ten of the 13 soils. For the samples from Fort
Ord, several unidentified peaks eluted near the
Am-DNTs on the GC analysis and made quantifi-
cation difficult. Similar interferences were not ob-
served in other soils, although a large unidentified
peak did elute after 2-AmDNT from four other
soils. Subsequent analyses led us to believe the
peak was a phthalate ester.
The only DNB isomer detected was 1,3-DNB,
which was found in two of the soils at around 5.0
mg kg − 1.
Recoveries from the MS/MSD samples were
excellent in some samples and low in others.
Matrix effects are discussed later.
TNT and 2,4-DNT concentrations above 20 mg
kg − 1 were quantifiable by HPLC, and the GC
concentrations estimates were correlated with
those newly obtained by HPLC using splits of the
same extract (Table 2). Again, good correlation
434 M.E. Walsh / Talanta 54 (2001) 427–438

(r =0.997 for both analytes) was found between Table 3

Method detection limits (mg kg−1) of nitroaromatics,
the two methods of determination, and again the
nitramines, and nitrate esters in spiked soils determined by
slopes of the least-squares models were greater GC-ECD
than 1.00 (1.14 and 1.12 for TNT and 2,4-DNT,
respectively), indicating slightly higher estimates AEC soil Ottawa sand
by GC.
Method 1a Method 1a Method 2b
There was no degradation in the GC peak
shapes or heights despite an extended run with 1,3-DNB 0.93 0.73 1.2
over 70 injections of undiluted soil extracts and 1,4-DNB 0.86
standards. 1,2-DNB 0.64
2,6-DNT 0.81 0.69
2,4-DNT 0.88 0.69 0.86
3.2. Confirmation columns
TNB 4.91 1.6
TNT 0.45 2.4c 11c
Because analyte identity is based solely on reten- RDX 3.1 3.4 2.6
tion time when using an ECD, confirmation is 4-Am-DNT 1.6 1.5 0.70
important. If concentrations are very high, a mass 3,5-DNA 2.0 2.1
2-Am-DNT 3.1 2.0 0.84
spectrometry or photodiode array detector can
NB 14 17
yield confirmation. For lower concentrations, o-NT 12 12
analysis by GC-ECD and HPLC-UV provides m-NT 11 11
confirmation based on different physical proper- p-NT 9.5 10
ties of the analytes (vapor pressure and polarity for NG 31 13
PETN 35 16
separation, and electronegativity and UV absorp-
Tetryl 66d 20
tion for detection). However, when concentrations HMX 26 25
are very low (less than 50 mg kg − 1), secondary
column confirmation by GC-ECD must be used. a
Method 1: 2.00 g soil extracted with 10.0 ml acetonitrile.
b
Two confirmation columns that are more polar Method 2: 25.0 g soil extracted with 50.0 ml acetonitrile.
c
Ottawa sand contained an interference that co-eluted with
than the HP-5 analytical column were used. They
TNT.
were a Restek RTX-200 (Crossbond trifluoro- d
AEC soil contained an interference that co-eluted with
propyl methylpolysiloxane) and Restek RTX-225 tetryl.
(50% cyanopropylmethyl – 50% phenyl methyl-
polysiloxane). Example chromatograms are shown hazardous waste characterization. Samples were
in Fig. 1. spiked at 5.00 and 50.0 mg kg − 1 because the ECD
Of these two columns, the RTX-225 was pre- response factors differ substantially for these ana-
ferred because RDX was resolved from 2-Am- lytes, being significantly higher for the di- and
DNT. These analytes co-eluted on the RTX-200. trinitroaromatics. Each matrix had interferences
Another problem with the RTX-200 was an inter- that inflated the MDLs for some of the analytes
mittent interfering peak eluting just prior to 2,4- (TNT in the Ottawa sand and 2-Am-DNT and
DNT. (This peak seemed to be associated with tetryl in the AEC soil). Nevertheless, the MDLs
plastics, but was not consistently present. Plastics (Table 3) were generally about 1 mg kg − 1 for the
contain phthalate esters, which are detected by the di- and trinitroaromatics and ten times higher for
ECD). Neither column was suitable for confirming the mono-nitroaromatics, which is consistent with
low concentrations of HMX, although a thinner the variable response factors of the ECD for these
film may have allowed this analyte to elute intact. compounds. MDLs were between 1 and 3 mg kg − 1
for the amino-nitrotoluenes, and were quite vari-
3.3. Spike reco6eries and method detection limits able for the more thermally labile nitramines and
nitrate esters.
Two blank matrices were spiked to determine Recoveries were calculated from the higher
detection limits for the analytes of interest for spikes for those analytes that had method detec-
 M.E. Walsh / Talanta 54 (2001) 427–438
tion limits less then 5 mg kg − 1. In all cases,
recoveries were near 100%. Precision was best
(B 4% RSD) for 1,3-DNB, TNT, and the DNT
isomers.
NG and PETN were not degraded during the
extended (18 h) sonication in a cooled sonic bath.
Previously in our lab, a decrease was observed in
recovery of NG in spiked soils (2500 mg kg − 1)
beyond 2 h of sonication. However, the bath at
that time was not cooled. Further kinetic studies
with field-contaminated soils are needed to verify
that 18 h of sonication in a cooled sonic bath is
not too long for acceptable recoveries of NG.
Using spiked matrices to determine precision
and accuracy of an analytical method can pro-
duce confounding results due to the differing ana-
lyte stability in newly spiked versus
field-contaminated aged soils [22]. This difference
became apparent when 25.0-g soil aliquots were
spiked with the analytes of interest for mine detec-
tion (Table 1). The first soil spiked was a silt
obtained locally. As stated above, 1.00 ml spike
solution was added to 25.0 g of soil to yield a
bulk analyte concentration of 2.00 mg kg − 1. How-
ever, this small volume of spike solution wetted
only a small portion of the soil, unlike when
2.00-g soil aliquots were spiked. When the silt was
extracted with acetonitrile containing 25.0-mg l − 1
3,4-DNT, recovery of all analytes was nil. The
peak height for 3,4-DNT, the internal standard
present throughout the extraction process, was
normal, thus the loss of the spiked analytes must
have occurred during the 1 h of aging between the
addition of the spike solution and the extraction
solvent. To see if the loss was matrix specific,
duplicate 25.0-g samples of the following were
spiked: glass beads (25 mm), Ottawa sand, AEC
soil, and the same silt where loss was observed
initially. Each matrix had interferences that co-
eluted with at least one analyte, but recoveries
bracketed 100% for analytes spiked onto the glass
beads and the Ottawa sand, bracketed 90% for
one replicate of the AEC soil and 50% for the
other replicate, and was nil again for the silt. Next
ten replicates of Ottawa sand were spiked to
obtain an estimate of method detection limits
435
(Table 3) for extraction of 25.0 g of soil with 50.0
ml acetonitrile, and the MDLs were very similar
to those obtained using just 2.00 g of soil and 10.0
ml acetonitrile. The expectation of improvement
in detection capability by using more soil in pro-
portion to the volume of extraction solvent was
negated by the small interfering peaks introduced
by the matrix.
The matrix spikes/matrix spike duplicate of
field-contaminated soils showed variable recover-
ies. Lacking extensive characterization of each of
these soils, the cause of the variable recoveries is
open to speculation. One difference that was visu-
ally obvious was grain size. The finest-grained soil
was that from Chickasaw, and this soil did show
poor recovery (41 –74%) of the spiked analytes.
However, grain size alone did not account for low
recovery in one of the Fort Ord samples, each of
which was sandy. The reason for the difference in
stability of spiked versus aged, field-introduced
analytes is beyond the scope of this study, but this
difference greatly reduces our ability to judge
method accuracy.
3.4. Mine field samples
3.4.1. Fort Leonard Wood soils
An experimental mine field was created at Fort
Leonard Wood by burying various defused anti-
tank and anti-personnel mines. The mines were
manufactured in the former Yugoslavia and each
contained TNT (0.10 –0.20 kg in anti-personnel
mines and 5.50 –5.60 kg in anti-tank mines). The
first set of soil samples was collected 2 months
after the mines were buried and revealed which
analytes are actually present in soils surrounding
emplaced land mines. Of the 143 samples re-
ceived, only 28 had detectable analytes as deter-
mined by GC-ECD with confirmation by
HPLC-UV. The most common analytes detected
were 2,4-DNT, 4-Am-DNT, and 2-Am-DNT,
which were each found in 27 out of the 28 positive
samples and each at median concentrations
greater than 60 mg kg − 1. 2,4,6-TNT was found in
24 samples and tended to be lower in concentra-
tion than the Am-DNTs, indicating that it is
undergoing microbiological transformation. Me-
436 M.E. Walsh / Talanta 54 (2001) 427–438

dian 2,4,6-TNT concentration was 6.5 mg kg − 1, these analytes might be sufficiently high to make
and the maximum was over 3000 mg kg − 1 in a them valuable markers for detection of emplaced
soil collected next to a mine. The other two mines. If other research shows that these analytes
commonly found analytes were 1,3-DNB and 2,6- are important for mine detection, analytical meth-
DNT, which had median concentrations of 8.8 ods would need to be optimized for determining
and 3.1 mg kg − 1, respectively. these compounds in soils. Potentially, derivatiza-
More soils were collected 4 months after the tion via bromination or iodination could be used
mines were buried; out of 199 samples, 73 had to enhance ECD response as described for the
detectable explosives. The Am-DNT isomers were determination of aromatic amines in ammunition
the most frequently detected analytes with 71 wastewater [23,24].
detections of 2-Am-DNT and 61 detections of
4-Am-DNT. Correlation between the two meth-
ods for 2,4-DNT was similar to what has been 4. Conclusions
previously observed; the correlation coefficient
was greater then 0.99 and the slope slightly GC-ECD concentration estimates of nitroaro-
matic and nitramines in field-contaminated soils
greater than 1.00. In previous comparisons made
were compared with estimates obtained by the
between GC-ECD and HPLC-UV, there were not
standard HPLC-UV method, and there was good
a sufficient number of samples with Am-DNT
correlation between the two methods of analysis.
isomers at concentrations high enough for deter-
The GC-ECD provided improved chromato-
mination by HPLC. For this set of samples, corre-
graphic resolution and detection. Two extraction
lation coefficients were 0.951 and 0.956 for
procedures were used, both of which involved 18
2-Am-DNT and 4-Am-DNT, respectively. The
h of sonication in a cooled bath. In one method,
slopes of the least squares regression lines were
2.00 g of soil were extracted with 10.00 ml, of
not significantly different from 1.00 for either
acetonitrile, and in the second 25.0 g of soil were
analyte. The data were more scattered for these
extracted with 50.0 ml acetonitrile. Method detec-
two analytes, showing that accurate determina- tion limits were similar for these two methods
tions are more difficult to obtain than for 2,4- because matrix interferences became more pro-
DNT. Like the nitramines, the amino-DNTs are nounced when the ratio of soil to solvent was
susceptible to degradation as the GC injection increased from 1:5 to 1:2. Method detection limits
port liner becomes less and less inert with re- were around 1 mg kg − 1 for the di- and trini-
peated injections of soil extracts. On the HPLC troaromatics, about 10 mg kg − 1 for the mono-ni-
separation, these analytes elute late where the
peaks are quite broad.
Similar to the first set of samples collected from
this minefield, 2,4,6-TNT was detected generally
at lower concentrations than the Am-DNTs, ex-
cept for samples collected in contact with a mine.
The presence of the TNT biotransformation prod-
ucts implies that 2,4-DNT and 1,3-DNB biotrans-
formation products should be present as well.
These products are 2-amino-4-NT, 4-amino-2-NT,
and 3-nitroaniline, which were detected in soil
collected under a TMA-5 anti-tank mine. Unfor-
tunately, the ECD response is not strong for these
compounds because they each have only one nitro Fig. 2. GC-ECD (HP-5) chromatogram of a soil collected near
group (Fig. 2). However, the vapor pressure of a land mine.
 M.E. Walsh / Talanta 54 (2001) 427–438
troaromatics, 3 mg kg − 1 for RDX, 25 mg kg − 1
for HMX, and between 10 and 40 mg kg − 1 for
the nitrate esters (NG and PETN).
Spike recovery studies revealed artifacts intro-
duced when the mass of the soil spiked was
large (25.0 g) in proportion to the volume of
spike solution added (1.00 ml). Recoveries were
excellent (around 100%) when 2.00-g soil sam-
ples were spiked with 1.00 ml of solution. How-
ever, when 25.0-g soil samples were spiked with
5.00 ml of solution, recoveries varied from nil in
a silt to around 80% in a sand. Matrix spikes/
matrix spike duplicates of field-contaminated
soils also showed inconsistency in recovery of
the spiked analytes.
Soils collected near emplaced mines contained
residues of TNT, 2,4-DNT, and 1,3-DNB and
their various microbial transformation products.
The importance of these transformation prod-
ucts for land mine detection is uncertain at
present. The ECD is sufficiently sensitive to de-
tect part-per-billion concentrations of the mono-
amino transformation products of TNT, but is
insensitive to the amino-transformation products
of 2,4-DNT and DNB.
Acknowledgements
The author gratefully acknowledges funding
for this work provided by the US Army Engi-
neer Waterways Experiment Station (Ann
Strong), the Defense Advanced Research
Projects Agency (Regina Dugan), and the US
Army Environmental Center (Martin Stutz).
Technical assistance and reviews were provided
by Thomas A. Ranney, Thomas F. Jenkins,
Paul H. Miyares, and Vivian George.
References
[1] M.A. Rouhi, Chem. Eng. News 75 (1997) 14.
[2] M. Hable, C. Stern, C. Asowata, K. Williams, J. Chro-
matogr. Sci. 29 (1991) 131.
[3] M.E. Walsh, T.A. Ranney, J. Chromatogr. Sci. 36 (1998)
406.
437
[4] J. Yinon, S. Zitrin, Modern Methods and Applications in
Analysis of Explosives, John Wiley and Sons Ltd., West
Sussex, England, 1993, pp. 42 – 66 and 213– 224.
[5] Chin.-Kai Meng, Response of Nitrogen-Phosphorus De-
tectors to Different Structural Nitrogen Compounds,
Hewlett Packard Application Brief, Hewlett-Packard
Company, Wilmington, DE, USA, February 1998.
[6] J. Feltes, K. Levsen, D. Volmer, M. Spiekermann, J.
Chromatogr. 518 (1990) 21.
[7] K. Levsen, P. Mußmann, E. Berger-Preiß, A. Preiß, D.
Volmer, G. Wünsch, Acta Hydrochim. Hydrobiol. 21
(1993) 153.
[8] A.D. Hewitt, T.F. Jenkins, On-Site Method for Measur-
ing Nitroaromatic and Nitramine Explosives in Soil and
Groundwater using GC-NPD, CRREL Special Report
99-9, US Army Cold Regions Research and Engineering
Laboratory, Hanover, NH, 1999.
[9] T.F. Jenkins, C.L. Grant, Anal. Chem. 59 (1987) 1326.
[10] American Society for Testing and Materials, Standard
Practice for Use of Electron-Capture Detectors in Gas
Chromatography, E 697-96, ASTM, West Conshohocken,
PA, USA, 1996.
[11] F. David, P. Sandra, M.S. Klee, Analysis of Nitroaromat-
ics and Nitro-Polycyclic Aromatic Hydrocarbons by Cap-
illary Gas Chromatography with the HP 6890
Micro-ECD, Hewlett Packard Application Note 228-380,
Hewlett-Packard Company, Wilmington, DE, USA,
March 1997.
[12] T.F. Jenkins, M.E. Walsh, P.W. Schumacher, P.H. Mi-
yares, C.F. Bauer, C.L. Grant, J. AOAC 72 (1989) 890.
[13] USEPA, Test Methods for Evaluating Solid Waste, Phys-
ical/Chemical Methods, SW-846 Update III, Office of
Solid Waste, Washington, DC, 1997.
[14] R.P. Murrmann, T.F. Jenkins, D.C. Leggett, Composi-
tion and Mass Spectra of Impurities in Military Grade
TNT Vapor. CRREL Special Report 158, US Army Cold
Regions Research and Engineering Laboratory, Hanover,
NH, 1971.
[15] T.F. Jenkins, D.C. Leggett, R.P. Murrmann, Preliminary
Investigation of the Permeability of Moist Soils to Explo-
sive Vapor. CRREL Technical Note, US Army Cold
Regions Research and Engineering Laboratory, Hanover,
NH, 1974.
[16] D.C. Leggett, T.F. Jenkins, R.P. Murrmann, Composi-
tion of Vapors Evolved from Military TNT as Influenced
by Temperature, Solid Composition, Age, and Source.
CRREL Special Report 77-16, US Army Cold Regions
Research and Engineering Laboratory, Hanover, NH,
1977.
[17] M.E. Walsh, T.F. Jenkins, F.G. Thorne, J. Energy Mater.
13 (1995) 357.
[18] T.F. Jenkins, M.E. Walsh, P.G. Thorne, S. Thiboutot, G.
Ampleman, T.A. Ranney, C.L. Grant, Assessment of
Sampling Error Associated with Collection and Analysis
of Soil Samples at a Firing Range Contaminated with
HMX. CRREL Special Report 97-22, US Army Cold
Regions Research and Engineering Laboratory, Hanover,
NH, 1997.
438 M.E. Walsh / Talanta 54 (2001) 427–438
[19] T.F. Jenkins, M.E. Walsh, P.G. Thorne, P.H. Miyares,
T.A. Ranney, C.L. Grant, Site Characterization at the
Inland Firing Range Impact Area at Fort Ord. CRREL
Special Report 98-9, US Army Cold Regions Research
and Engineering Laboratory, Hanover, NH, 1998.
[20] T.F. Jenkins, D.C. Leggett, and T.A. Ranney, Vapor
Signatures from Military Explosives. Part 1. Vapor
Transport from Buried Military-Grade TNT. CRREL
Special Report 99-21. U.S. Army Cold Regions Re-
search and Engineering Laboratory, Hanover, NH,
1999.
[21] M.E. Walsh, T.A. Ranney, Determination of Nitroaro-
matic, Nitramine, and Nitrate Ester Explosives in Soils
Using GC-ECD, CRREL Special Report 99-12, US
Army Cold Regions Research and Engineering Labora-
tory, Hanover, NH, 1999.
[22] C.L. Grant, T.F. Jenkins, K.F. Myers, E.F. Mc-
Cormick, Environ. Toxicol. Chem. 14 (1995) 1865.
[23] T.C. Schmidt, R. Haas, K. Steinbach, E. v Löw, Frese-
nius J. Anal. Chem. 357 (1997) 909.
[24] R. Haas, T.C. Schmidt, K. Steinbach, E. v Löw, Frese-
nius J. Anal. Chem. 359 (1997) 497.