Journal of Chromatography A, 1334 (2014) 118125

Contents lists available at ScienceDirect

Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma

Rapid and sensitive method for the determination of polycyclic

aromatic hydrocarbons in soils using pseudo multiple reaction
monitoring gas chromatography/tandem mass spectrometry
Dayue Shang a, , Marcus Kim b , Maxine Haberl a
a
Pacic and Yukon Laboratory for Environmental Testing, Science and Technology Branch, Pacic Environmental Science Centre, Environment Canada,
North Vancouver, British Columbia, Canada
b
Agilent Technologies Inc., Mississauga, Ontario, Canada

a r t i c l e

i n f o

Article history:
Received 30 October 2013
Received in revised form 24 January 2014
Accepted 27 January 2014
Available online 3 February 2014
Keywords:
GC/MS/MS
GC/MS
Polycyclic aromatic hydrocarbons
Rapid extraction
Pseudo MRM
Soil and sediment

a b s t r a c t
A method for the rapid determination of 18 polycyclic aromatic hydrocarbons (PAHs) in soil has been
established based on a simplied solvent extraction and GC/MS/MS operated in pseudo multiple reaction
monitoring mode (PMRM), a technique where the two quadrupoles mass monitor the same m/z. The
PMRM approach proved superior to the classic single quadrupole technique, with enhanced sensitivity,
specicity, and signicant reduction in time consuming sample clean-up procedures. Trace level PAHs
could be readily conrmed by their retention times and characteristic ions. The limit of quantitation in
soil was observed to be 20 ng/g for 16 EPA-priority PAHs and 2 additional PAHs specic to Environment
Canada. The developed method was linear over the calibration range 204000 ng/g in soil, with observed
coefcients of determination of >0.996. Individual PAH recoveries from fortied soil were in the range 58.1
to 110.1%, with a precision between 0.3 and 4.9% RSD. The ruggedness of the method was demonstrated
by the success of an inter-lab prociency test study organized by the Canadian Association for Laboratory
Accreditation. The present method was found to be applicable as a rapid, routine screening for PAH
contamination in soil, with signicant savings in terms of preparation time and solvent usage.
Crown Copyright 2014 Published by Elsevier B.V. All rights reserved.

1. Introduction
Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous
hydrophobic compounds originating from natural or anthropogenic sources. These compounds are widely distributed in the
environment and detected in soils and sediments, mainly due to
atmospheric deposition processes [2]. All PAHs in the environment
are an ecological and human-health concern. Of the one hundred
and twenty-six Environment Protection Agency Priority Pollutants
listed by the Clean Water Act, sixteen are PAHs, with seven being
known carcinogens [1]. It is recognized that an increase in the relative amount of two to four ring compounds, such as naphthalene,
uoranthene, and phenanthrene, is usually a good indication of the
presence of petrogenic hydrocarbons [1]. Larger PAHs such as the
5 and 6-ringed compounds are indicative or pyrogenic sources [3].
The reserves of oil sands bitumen in Northern Alberta, Canada,
are estimated at 1.7 trillion barrels, with 173 billion estimated
to be economically recoverable. Oil exploration in this region has
been intensied over the past 20 years, with production increasing

Correspondingauthor. Tel.: +1 604 903 4462; fax: +1 604 903 4408.

E-mail address: dayue.shang@ec.gc.ca (D. Shang).

from 100,000 barrels per day to about 1.5 million barrels per day
currently [2]. Close monitoring of PAH concentrations in soils and
sediment has become critical, and large scale surveillance is being
implemented by government agencies. The characterization and
knowledge of PAH concentrations in soil and sediments can be
instrumental in tracing an oil spill source and enabling remediation efforts. A rapid, sensitive, and robust analytical method for the
determination the PAH concentrations in soil is urgently needed
[2].
Traditional sample preparation techniques for the determination of PAHs in soil are time consuming and generally require large
volumes of toxic solvents, together with multi-step extraction and
silica gel or Florisil column clean-up procedures. To address these
issues, and as an alternative to the classic Soxhlet solvent extraction methods, various techniques have been developed and used in
the analysis of PAHs from soil. Alternative processing includes pressurized liquid extraction or accelerated solvent extraction (PLE or
ASE), ultrasonic extraction, supercritical uid extraction (SFE), and
microwave-assisted extraction (MAE) [46]. An automated Soxhlet
method has recently been developed with corresponding reduction
in soil extraction time [7,8]. Despite intensive method development in this area, some of the referenced techniques suffer one
or several shortcomings, including low recovery, expensive initial

0021-9673/$ see front matter. Crown Copyright 2014 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.chroma.2014.01.074

D. Shang et al. / J. Chromatogr. A 1334 (2014) 118125

119

investment, frequent equipment malfunction, and lack of robustness or ruggedness. Very recently, a new promising approach of
microextraction has emerged using MAE combined with solvent
bar [9]. While this approach is both green and effective, wide
application of this method remains to be seen. An elegant approach
to the issue would be to take advantage of the modern instruments
enhanced capability of handling less processed sample extracts and
use a dilute and shoot approach. Perhaps more importantly, simplied sample processing improves method ruggedness, which is
critical for routine analysis.
Presently the two most frequently employed techniques to
determine PAHs are HPLC with uorescence, UV, or diode array
detection [10,11] and GC with MS detection [1,7,8,10]. The HPLC
based methods are usually fast in comparison to the GC/MS
methods; however, the disadvantages of the HPLC method are
heavy dependence on chromatographic retention time for compound identication and the HPLC methods are typically an order
of magnitude lower in sensitivity than GC/MS [12]. In complex
matrices, such as soil extract, peak identication based solely on
retention time is subject to interference from other components,
making trace level PAH contamination difcult to characterize.
For this reason, over 15 years the GC/MS technique has become
established as the accepted method for PAH determination in
the environment [7,8]. Despite numerous improvements to single quadrupole MS instrumentation however, performance cannot
match the sensitivity and specicity offered by triple quadrupole
MS. As a consequence, an increasing number of peer reviewed
publications have applied GC/MS/MS techniques to PAH analysis. However, due to the unique structure stability of the PAH
compounds, the traditional Multiple Reaction Monitoring (MRM)
approach has been hampered by generally weak fragmentation
ion responses for this group of compounds [1315]. Considering the well-established GC/MS single quadrupole method, the
application of the triple quadrupole presently does not provide
adequate improvement in sensitivity and specicity to initiate a
change from proven procedures. In this regard we challenged this
conclusion and successfully applied GC/MS/MS techniques to PAH
analysis.
In this paper, we present a rapid analytical method for the
analysis of PAHs in soil and sediments, based on a one step, low
volume solvent extraction followed by GC/MS/MS in pseudo MRM
mode. Long extraction time, large solvent volume consumption,
and extensive silica gel column clean-up were eliminated. This
was made feasible by the increased sensitivity and specicity
achieved by pseudo MRM mode GC/MS/MS. Compelling results will
be presented to support the favoring of this pseudo MRM mode
GC/MS/MS over that of single quadrupole procedures, even for
difcult-to-fragment compounds like PAHs. The present method
was validated and applied successfully during an inter-lab prociency study organized by The Canadian Association for Laboratory
Accreditation Inc. (CALA).

NJ). This solution was stored at 20 10 C in amber glass and

had a shelf life of 12 months. An internal standard solution of
Naphthalene-d8, Acenaphthene-d10, Phenanthrene-d10, and
Perylene-d12 was purchased from Supelco (Oakville, Ontario).
This internal standard was employed both in the preparation
of calibration standards and in fortifying soil samples for spike
recovery.
Calibration standards were prepared in dichloromethane by
serial dilution of primary standard to provide nal concentrations of 10, 20, 40, 100, 500, 1000, 1500 and 2000 ng/mL. Internal
standard at a nal concentration of 200 ng/mL was added to all
calibration standards.
Disposable centrifuge lter tubes (15 and 50 mL, Polypropylene/Polyethersulfone) were supplied by Pall Corporation (Port
Washington, NY). Disposable 50 mL polypropylene centrifuge tubes
were purchased from Sarstedt (Numbrecht, Germany). Florisil
adsorbent (60100 mesh) was from Fisher Scientic (Fairlawn, NJ.
USA). OmniSolv solvents dichloromethane (DCM), acetone (ACE),
hexane, isopropanol (IPA), acetonitrile (ACN), pesticide grade, were
purchased from EM Science (Gibbstown, NJ. USA).

2. Material and method

2.3. GC-MS analysis

2.1. Reagents and standards

A gas chromatograph (GC) HP 7890A from Agilent Technologies

(Palo Alto, CA., USA) equipped with an Agilent 7693B automatic liquid sampler with 10 L syringe was used for the separation of PAHs.
Analysis employed a 1 L sample injection in pulsed splitless mode
(pulsed pressure at 50 psi with the split valve closed for 1 min). All
analytes were separated on a Restek Rtx-5MS with Integra-guard
column (30 m x 0.25 mm id, 0.25 m). A 4 mm i.d. single tapered,
deactivated inlet liner with glass wool at the bottom (Agilent Technologies) was installed into the injector. The oven temperature
program was as follows: initial temperature at 50 C (hold 2 min),
then 6 C/min to 310 C, hold for 20 min. The total run time was

The 18 PAHs analyzed in this study were Acenaphthene (ACE),

Acenaphthylene (ACY), Anthracene (ANT), Benzo(a)anthracene
(BAN), Benzo(a)pyrene (BAP), Benzo(e)pyrene (BEP), Benzo(b)
uoranthene (BBF), Benzo(g,h,i)perylene (BGP), Benzo(k)
uoranthene (BKF), Chrysene (CRY), Dibenz(a,h)anthracene
(DBA), Fluoranthene (FLA), Fluorene (FLU), Indeno(1,2,3-cd)pyrene
(IND), Naphthalene (NAP), Perylene (PER), Phenanthrene (PHE)
and Pyrene (PYR). A certied standard solution of the 18 PAHs
(2000 g/mL each) was provided by SPEX CertiPrep (Metuchen,

2.2. Sample extraction and clean up

Aliquots of 10 0.1 g of air dried free ow homogeneous
soil sample were weighed and placed into a 50 mL polypropylene centrifuge tube with screw caps. To the sample, 200 L
of 20 ppm internal standard mixture were added, followed by
5 g of sodium sulphate (pre-dried at 350 C). The mixture was
then hand-shaken to mix sodium sulphate with the soil sample, with occasional spatula use to break any soil lumps to
ensure homogeneity. After mixing, 15 mL of dichloromethane
was added and the mixture was vortexed briey. The slurry
was further shaken for 10 min at room temperature using a
mechanical wrist action shaker. The sample was centrifuged at
5000 rpm (4696 g) for 5 min. The supernatant was decanted and
retained in a clean 50 mL polypropylene centrifuge tube. The
remaining pellet was subjected to a second extraction in 5 mL
dichloromethane (breaking up the pellet cake with a spatula if
necessary), employing only a 5 min shaking time. Supernatant from
both extractions were pooled and the volume adjusted to 20 mL
with dichloromethane.
An aliquot of the 20 mL extract was transferred to a 15 mL
centrifuge lter tube with 0.2 m lter device. Following centrifugation for 5 min at 5000 rpm (4696 g), the ltrate extract
was ready for GC/MS/MS analysis. Refer to Fig. 1 for a owchart
of sample extraction steps. For soils contaminated with lube
oil, vegetable oil, or animal oil and grease, the lter insert
of the centrifuge tube may be pre-packed with approximately
3 g of Florisil to improve clean up. These materials may lower
analyte recovery and the inclusion of an isotope dilution
technique may be required to compensate (Supplementary materials).

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D. Shang et al. / J. Chromatogr. A 1334 (2014) 118125

QC

Add 10 g bank soil to a 50 mL PP

centrifuge tube. Spike in 0.2 mL of
surrogate. Add 5 g sodium
sulphate.

Add 10 g of sample to a 50 mL PP
centrifuge tube. Spike in 0.2 mL of
surrogate. Add 5 g of sodium
sulphate.

Real
Sample

Add 15 mL of DCM. Vortex mix.

Wrist-action shake the sample and solvent for 10 minutes.

Vortex mix. Centrifuge at 5000 rpm for 5 minutes. Decant into a clean 50 mL
centrifuge tube.

Add 5 mL of DCM to solid cake. Break up with manual agitation (with spatula if
necessary). Shake for 5 minutes.

Vortex mix. Centrifuge at 5000 rpm for 5 minutes and decant into the same tube from
the first extraction.

Make volume up to 20 mL with DCM. Vortex mix.

Add 5 mL of sample to a 15 mL disposable centrifuge filter tube and centrifuge at

5000 rpm for 5 minutes.

Discard filter insert and transfer 1.5 mL to a GC vial.

GC/MS/MS Analysis
Fig. 1. Schematic of sample preparation procedure.

65.33 min. High purity helium gas (>99.999%) was used as carrier
gas with the constant ow rate of 1.0 mL/min. Detection of the
analytes employed an Agilent Technologies 7000 triple quadrupole
mass spectrometer (MS) operated in electron impact positive mode
ionization at 70 eV. Analyte ions were monitored in either Classic
Multiple Reaction Monitoring (CMRM) or Pseudo MRM (PMRM)
mode. The GC/MS transfer line and inlet temperatures were set
at 300 and 320 C respectively. Ion source temperature was set
at 325 C and quadrupole temperature at 150 C. A solvent delay
of 4.5 min was employed. Table 1 lists the PAHs along with their
observed retention times and their characteristic quantitation and
qualier ions. The N2 collision cell and He Quench Gas ows were
both set to 1 mL/min.
Quantication employed the integrated peak area ratio of the
target ion to internal standard. A weighted (1/x) linear regression of the calibration standard responses was employed to
dene the calibration curve from which measured concentrations were calculated. The PAH analytes were identied by their
target ions and retention time order. Retention times had to
be within 0.1 min of the expected time for positive conrmation.

2.4. Method validation

The linearity of the analytical GC/MS/MS PMRM method was
assessed by analyzing duplicate calibration standards prepared at
10, 20, 50, 100, 500, 1000, 1500 and 2000 ng/mL (equivalent to
soil samples spiked at PAH concentrations from 20 to 4000 ng/mL).
Linearity using weighted (1/x) least-squares regression was considered acceptable when the correlation coefcient (r) was >0.995.
The limit of quantitation (LOQ) and limit of detection (LOD)
of the method were assessed based on the signal to noise (S/N)
response of the relevant analyte peak response at the lowest
standard concentration of 10 ng/mL. A S/N of >10:1 and >3:1 for LOQ
and LOD respectively were considered acceptable for each analyte.
Method accuracy (expressed as percent recovery) and precision
(expressed as percent relative standard deviation (%RSD)) were
determined by recovery studies in PAH-free soil samples spiked
at low, mid, and high PAH concentrations. Eight replicate soil samples spiked with PAH standard at 20, 200 and 2000 ng/mL were
processed and analyzed. Results showing an accuracy of 60% to
120% recovery from nominal concentration and a precision of <20%
RSD were considered to be acceptable. The percent recovery was

D. Shang et al. / J. Chromatogr. A 1334 (2014) 118125

121

Table 1
List of PAHs and pseudo MRM acquisition parameters.
Compound name
Time Segment 1: 14.50 min
d8-Naphthalene
Naphthalene
Time Segment 2: 21.00 min
Acenaphthylene
d10-Acenaphthene
Acenaphthene
Time Segment 3: 23.00 min
Fluorene
Time Segment 4: 27.00 min
d10-Phenanthrene
Phenanthrene
Anthracene
Time Segment 5: 31.00 min
Fluoranthene
Pyrene
Time Segment 6: 37.00 min
Benz(a)anthracene
d12-Chrysene
Chrysene
Time Segment 7: 41.00 min
Benzo(b)uoranthene
Benzo(k)uoranthene
Benzo(e)pyrene
Benzo(a)pyrene
d12-Perylene
Perylene
Time Segment 8: 45.00 min
Indeno(1,2,3-cd)pyrene
Dibenz(a,h)anthracene
Benzo(g,h,i)perylene

ISTD

Indicative RT (min)

15.19
15.26

136 > 136

128 > 128

137 > 137

129 > 129

21.32
21.94
22.06

152 > 152

163 > 163
153 > 153

153 > 153

162 > 162
154 > 154

76 > 76

24.02

166 > 166

27.61
27.69
27.86

Precursor> product ion

Qual ion 1

Qual ion 2

Dwell (ms) quant/qual

CE (V)

15
10

5
5

76 > 76

10
15
10

10
5
5

165 > 165

83 > 83

10

188 > 188

178 > 178
178 > 178

189 > 189

179 > 179
179 > 179

89 > 89
89 > 89

15
10
10

10
5
10

32.35
33.17

202 > 202

202 > 202

203 > 203

203 > 203

101 > 101

101 > 101

10
10

5
10

37.92
37.98
38.08

228 > 228

240 > 240
228 > 228

114 > 114

121 > 121
229 > 229

229 > 229

10
15
10

10
10
10

41.89
41.97
42.80
42.95
43.16
43.24

252 > 252

252 > 252
252 > 252
252 > 252
264 > 264
252 > 252

253 > 253

253 > 253
253 > 253
253 > 253
132 > 132
253 > 253

250 > 250

250 > 250
250 > 250
250 > 250
250 > 250

10
10
10
10
15
10

10
15
5
10
15
5

46.40
46.50
47.10

276 > 276

276 > 276
278 > 278

277 > 277

277 > 277
279 > 279

138 > 138

138 > 138
139 > 139

10
10
10

10
10
5

114 > 114

ISTD: Internal Standard; RT: Retention Time; CE: Collision Energy.

calculated from the equation: Mean (calculated)/Mean (spiked))

100.
2.5. Application to real samples
The validated method was applied to a set of four soil samples
(labeled C-18-01, C-18-02, C-18-03 and C-18-04) supplied by the
Canadian Association for Laboratory Accreditation Inc. (CALA) as
part of a prociency testing program. The samples were analyzed by
both a well-established GC/MS single ion monitoring method and
by the new validated GC/MS/MS PMRM method. Results were compared as a demonstration of the performance of the new GC/MS/MS
PMRM procedure.

with adequate sensitivity. A representative GC/MS/MS PMRM chromatogram of a blank soil sample spiked at 0.1 g/g of PAHs standard
and extracted under these conditions is shown in Fig. 2.
For relatively clean soil samples, the main issue is the simultaneous extraction of interference components, particularly isobaric
compounds. These interferences are signicant in GC/MS analysis but could be overcome efciently by the proposed GC/MS/MS
PMRM approach. For this proposed procedure, the current elaborate routine sample clean-up and concentration steps, such as
roto-vap and nitrogen gas blow down, were rejected in lieu of a
dilute and shoot approach, with only a lter 0.2 m centrifuge
tube ltration step included to remove particulates.
3.2. GC/MS/MS determination

3. Results and discussion

3.1. Sample extraction and clean-up
For PAHs analysis, the ideal extraction solvent(s) should have
the characteristics of high extraction efciency of the targeted compounds from soil, capability of application directly to wet soils (to
prevent loss of low volatile PAHs during the drying process), and
compatibility with GC/MS. To meet these requirements, and based
on practical experience and literature review [1,8], several solvents
and their combinations were examined during the present study
(hexane, acetone, acetonitrile (ACN), dichloromethane (DCM) and
isopropanol). A detailed discussion of solvent selection and cleanup method development can be found in Supplementary materials.
The most practical approach was achieved by rst reducing soil
moisture and extraction in neat DCM solvent. The incorporation of
sodium sulfate allowed for soil moisture reduction and DCM extraction yielded consistently high recoveries at over 60% for all 18 PAH
compounds. Furthermore, all 18 PAH compounds exhibited acceptable chromatographic peak shape and were satisfactorily separated

In environmental analysis, co-eluting isobaric matrix interferences derived from soil and sediments usually make MRM the
technique of choice to achieve high signal-to-noise ratios and
method specicity. Polyaromatic hydrocarbons possess an exceptionally stable and rigid macrocyclic ring structure and yield very
little fragmentation during collision induced dissociation. Therefore, in this work PAHs were analyzed by GC/MS/MS with pseudo
MRM monitoring (GC/MS/MS PMRM), a technique where both
resolving MS quadrupole mass lters monitor for the same molecular ion m/z that is employed for quantitation. In PMRM, the target
ions are selectively transferred to the second resolving quadrupole
mass lter without collision induced dissociation.
In the present study, a systematic optimization of targeted PAH
compound ionization and daughter ion fragmentation was conducted. Results supported observations by other groups [1315] in
that the most abundant peak in the electron impact ionization (EI+ )
fragmentation spectrum was consistently the molecular ion (M+ ).
Other observed peaks were present at lower relative intensities
despite efforts to optimize conditions for fragmentation and even

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D. Shang et al. / J. Chromatogr. A 1334 (2014) 118125

Fig. 2. Combine extracted ion chromatogram of 18 PAHs spiked in DCM at 100 ng/mL (GC/MS/MS, EI ionization, pseudo-MRM acquisition).

under extreme collision energy conditions. Other weaker intensity

ions that commonly formed were the multiply charge ions such as
[M 2H]+ or double-charged analytes M2+ . The results suggest that
the highly condensed and stable PAHs are not easily amenable to
routine MRM analysis without loss of sensitivity due to the limited
number and low response of daughter ions; especially with respect
to the low intensity qualier ions. The lack of increased sensitivity
for a triple quad over a single quad GC/MS analysis explains the
paucity of peer reviewed papers published using triple quadrupole
GC/MS/MS for PAHs analysis [1315].
The high structural stability of PAH compounds was exploited as
an advantage under the present PMRM approach. The characteristic PAH analyte parameters used in established single quadrupole
GC/MS methods for PAHs were employed for monitoring in both
the rst and third quadrupole of the GC/MS/MS. No fragmentation of the target ions was attempted, while collision energy
was ne tuned to achieve best signal to noise ratio by decreasing or eliminating co-eluting isobaric interference compounds.
In effect, the collision energy was tuned to reduce interfering
effects by fragmentation or creation of unfavorable energy transfer
for interfering compounds, while targeted ions remained relatively intact. As a result, the PMRM technique provided two main
advantages: (1) potential destruction and mass ltering of isobaric interferences; (2) the collisional focusing of the ion beam
in a high pressure RF device as described by Douglas and French
[16] to focus the ions toward the centre axis where they are better able to enter the acceptance aperture of the 2nd resolving
quadrupole mass lter resulting in better transmission at a given
resolution.
To demonstrate the utility of PMRM approach, a systematic
study of the relationship of collision energy to peak height and S/N
was conducted. All 18 targeted PAHs produced a sweet spot collision energy where the peak area and S/N were optimized (Fig. 3,
more to be found in Supplementary Fig. S1). In other words, at this
optimized collision energy, one can expect strong peak and reduced
signal to noise ratio for a particular compound. Occasionally, lower

or higher collision energy may be selected to increase either

peak height (in the case of poorly ionized compounds and clean
matrices) or S/N ratio (in the case of strong ions and dirty matrices). The present method for PAHs employed collision energies at
the S/N sweet spot with a few exceptions. Under the determined
optimized collision energy conditions for PMRM mode ion operation, it was theorized likely that the GC/MS/MS method would show
improved limit of detection (LOD) and limit of quantitation (LOQ)
for dirty samples when compared to routine GC/MS.
To illustrate this point, a GC/MS single ion monitoring method
was created based on a well-established in-house SOP for the analysis of PAHs in soil and sediments and using a single quadrupole
instrument (7890A/5975C, Agilent Technologies). An experiment
was carried out to compare the GC/MS/MS in PMRM mode to GC/MS
in SIM mode. For this experiment, a series of samples were prepared
in solvent laden soil extract spiked at various low PAH concentrations from 2 to 30 ng/g. The duplicated soil extract samples were
analyzed by both GC/MS/MS in PMRM mode and GC/MS in a wellestablished SIM mode. A summary of the results is provided in
Table 2. The advantages of PMRM over GC/MS SIM were clearly
demonstrated. A number of PAHs at 10 ppb were not detected by
the GC/MS SIM method due to severe matrix effects. The same
samples produced strong peaks for all 18 PAHs in GC/MS/MS
PMRM analysis, with excellent S/N at this trace level. Furthermore, at a 2 ng/g spiking level, minor peaks did not achieve an
adequate S/N for quantitation of any of the PAHs by GC/MS SIM
while, remarkably, GC/MS/MS PMRM still exhibited strong denitive peaks adequate for quantitation for the majority of the targeted
compounds.
In justication for the PMRM approach, one must answer the
fundamental question: how does PMRM analysis compare with
Classic MRM (CMRM) analysis in terms of specicity and sensitivity? With respect to specicity, the PMRM offers equivalent
conrmatory identication of analytes by a combination of retention times, quantitative and qualitative ions, and ion ratio between
quantitative and qualitative ions in the mass spectrum. In addition,

D. Shang et al. / J. Chromatogr. A 1334 (2014) 118125

123

Fig. 3. Signal to noise ratio in relation to collision energy for 3 typical PAHs. All standards were prepared in DCM and at 1000 ng/mL. The dotted line indicates the optimized
and selected collision energy used in the method. The symbol () indicates signal to noise ratio of the targeted compound at this collision energy (v). The symbol () indicates
peak area of the targeted compound at this collision energy (v).

the PMRM method was shown to be superior to CMRM with respect

to sensitivity, as a result of the reduction of interfering isobaric compounds. A comparison of S/N for the PAH analyte peaks from soil
extracts fortied 1 ppm PAH standard mixture is shown in Fig. 4
and clearly demonstrates the improved sensitivity of PMRM over
CMRM for the majority of the analytes (12 out of 18 PAHs). Although

detection of some individual PAH compounds could be signicantly

improved by the PMRM method, the elimination of isobaric compounds for all PAH analytes as a group was not complete. In certain
cases, notably Acenaphthene, Benzo(e)pyrene and Perylene, interfering compounds were observed that possessed similar chemical
stability to the target ion and the original CMRM remained the

Table 2
Instrument comparison: area counts at PAH concentrations from 220 p p b.
Agilent 7000 triple quadrupole

Agilent 5975 single quadrupole

Compound

2 ppb

10 p p b

20 p p b

2 ppb

Napthalene
Acenaphthylene
Acenaphthene
Fluorene
Phenanthrene
Anthracene
Fluoranthene
Pyrene
Benzo(a)anthracene
Chrysene
Benzo(b)uoranthene
Benzo(k)uoranthene
Benzo(e) pyrene
Benzo(a) pyrene
Perylene
Indeno(1,2,3-cd) pyrene
Benzo(g,h,i)perylene
Dibenz(a,h)anthracene

999
537
343
ND
1372
930
1325
1641
ND
1029
ND
ND
405
355
813
202
455
ND

3909
2619
1190
1551
4810
2046
3659
4056
955
2791
1859
652
1841
1159
1976
587
1531
804

8121
5758
2877
2790
6462
4213
7925
9323
2521
6306
4778
1411
3922
3230
4363
2237
3963
2293

ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND
ND

*ND = Not detected.

10 p p b
29
25
33
22
ND
ND
46
46
ND
ND
35
35
42
33
49
17
29
0

20 p p b
57
45
33
42
ND
ND
86
94
ND
ND
70
85
85
74
102
47
63
45

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D. Shang et al. / J. Chromatogr. A 1334 (2014) 118125

Fig. 4. Signal to noise comparison for pseudo-MRM and classic MRM in relation to collision energy for 3 typical PAHs. The results were obtained from a soil sample spiked at
1000 ng/g of 18 PAHs, extracted with DCM and run duplicated. The symbol () indicates signal to noise ratio of the targeted compound using pseudo MRM. The symbol ()
indicates signal to noise ratio of the targeted compound using classic MRM.

optimal choice for analysis. Nevertheless, many well established

GC/MS single quad methods may benet from this straightforward
PMRM approach without extensive new method development process.
3.3. Method validation
The linearity of calibration curves was determined by analysis
of duplicate preparations of calibration standards over the nominal concentration range of 102000 ng/mL for all PAH analytes
(equivalent to soil samples spiked at PAH concentrations from
20 to 4000 ng/g). The MS response for all analytes was observed
to be linear in this concentration range, with correlation coefcients of >0.996. The limit of quantitation (LOQ) of the method
was determined to be 20 ng/g for all the targeted compounds. Furthermore, prepared stock standard solutions and working solutions
were found to be stable when stored at 20 10 C for up to 6
months.
The precision and accuracy of the analytical GC/MS/MS-PMRM
method was conrmed employing eight soil samples spiked at
low (20 ng/g), mid (200 ng/g), and high (2000 ng/g) concentrations of PAHs (Supplementary Tables S1, S2 and S3). Accuracy for

determination of the PAH compounds was demonstrated by a percent recovery in the range 58.1110.1%, with an observed precision
of <5%RSD for each of the individual compounds. Results for recovery of the PAH compounds at low, mid and high levels were in line
with those reported by other authors using sonication [6,17], ASE
[7,8], SFE [4,8] or an automated Soxhlet procedures [7]. The method
showed a limit of detection limit (LOD) of between 510 ng/g for
PAH compounds extracted from the soils.

3.4. Analysis of prociency testing samples

The validated method was applied to a set of four soil samples
(labeled C-18-01, C-18-02, C-18-03, and C-18-04) supplied by the
Canadian Association for Laboratory Accreditation Inc. (CALA) as
part of a prociency testing program. Due to the high concentration of spiked of PAHs in the samples, only 1 g of each material
was processed and analyzed. Table 3 presents the typical results for
one of the samples. The results were compared with the assigned
value and found to be satisfactory (Supplementary Table S4). The
accuracy for this test with the current method ranges from 63 to
139%.

D. Shang et al. / J. Chromatogr. A 1334 (2014) 118125

125

Table 3
CALA Prociency testing sample C-18-04: measured vs. assigned concentrations.
Compound

Sample

Actual concentration (p p b)

Calculated concentration (p p b)

Accuracy (%)

Acenaphthene
Acenaphthylene
Anthracene
Benzo (a) anthracene
Benzo (a) pyrene
Benzo (b) uoranthene
Benzo (g,h,i) perylene
Benzo (k) uoranthene
Chrysene
Dibenzo (a,h) anthracene
Fluoranthene
Fluorene
Indeno (1,2,3 - cd) pyrene
Naphthalene
Phenanthrene
Pyrene

C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04
C-18-04

1119
1343
1224
6076
4007
7869
4452
4119
6784
1029
19517
1322
5045
36372
16835
13368

1161
1501
1543
5363
3222
5198
3843
4127
5947
1202
14658
1095
4400
33325
13059
14165

104
112
126
88
80
66
86
100
88
117
75
83
87
92
78
106

Measured concentrations vs. assigned concentrations in CALA PT-C-18-04.

4. Conclusions

Appendix A. Supplementary data

A sensitive and rapid GC/MS/MS method for the determination

of PAHs in soil samples has been developed. Sample extraction was
reduced to a rapid mechanical shaking procedure using just 20 mL
of solvent, and further sample clean-up was eliminated for most
samples as a result of the application of GC/MS/MS in pseudo MRM
mode. An additional Florisil clean-up was all that required in the
case of more heavy contaminated soils.
A series of experiments were conducted to compare GC/MS/MS
PMRM and GC/MS/MS CMRM detection modes for soil extract sample analysis. Results for the recovery of PAHs demonstrated the
advantage of PMRM triple quad analysis over single quad SIM mode
GC/MS. In the present study, the highly stable nature of PAH compounds was taken advantage of and the collision cell fragmentation
was optimized for fragmentation of potential interference ions,
rather than for fragmentation of the highly abundant parent ions.
In summary, the PMRM provided additional mass ltering due to
dual quadrupole ion focusing and potential reduction or destruction of isobaric interferences in the collision cell, thus improving
sensitivity for most of the targeted PAH compounds. Considering the signicant saving in time and solvent volume by PMRM
approach, we suggest that labs currently using GC/MS SIM move
to GC/MS/MS PMRM to improve method productivity and sensitivity, especially in the case of structurally stable compounds such
as alkylated PAHs, oil biomarkers, dioxins and furans, and some
pharmaceutical drugs.

Supplementary data associated with this article can be

found, in the online version, at http://dx.doi.org/10.1016/j.chroma.
2014.01.074.

Acknowledgements
The authors gratefully acknowledge the support and input of
their colleagues, notably Randy Englar, Liane Chow, Oxana Blajkevitch, Lauretta Liem and Norman Berke of the Pacic Environmental
Science Centre of Environment Canada, North Vancouver, BC.

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