Trends in Analytical Chemistry 61 (2014) 40–48

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Trends in Analytical Chemistry

j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / t r a c

Review of progress in solvent-extraction techniques for the

determination of polyaromatic hydrocarbons as airborne pollutants
Jan E. Szulejko a, Ki-Hyun Kim a,*,†, Richard J.C. Brown b, Min-Suk Bae c
a Department of Civil & Environmental Engineering, Hanyang University, 222 Wangsimni-Ro, Seoul 133-791, Korea
b Analytical Science Division, National Physical Laboratory, Teddington, UK
c Department of Environmental Engineering, Mokpo National University, Mokpo, Korea

A R T I C L E I N F O A B S T R A C T

Keywords: In this review, we concentrate on sample-pretreatment options with the main emphasis on all aspects
Airborne pollutant of solvent extraction prior to GC-based analysis of airborne polyaromatic hydrocarbons (PAHs). To this
Cold-fiber solid-phase microextraction end, we review developments in these applications covering many different approaches that have com-
Determination
monly been used or introduced recently.
Green chromatography
Particulate matter
Generally, sample pretreatment comprises
Polyaromatic hydrocarbon (PAH) (1) solvent extraction of PAHs from filters and sorbents;
Quick, Easy, Cheap, Effective, Rugged, and (2) extract concentration;
Safe (QuEChERS)
(3) some form of liquid, or solid, chromatography clean-up;
Sample pretreatment
(4) eluent concentration; and
Solvent extraction
Solvent usage (5) injection into a GC for analysis.
Recent developments in these areas include: cold-fiber solid-phase microextraction of PAH ex-
tracts; the “Quick, Easy, Cheap, Effective, Rugged, and Safe” (QuEChERS) extraction technique; and, using
vehicle-engine air-intake filters to collect airborne particulate matter. We also discuss some aspects of
“green chromatography”, used in recent years to reduce solvent usage.
© 2014 Elsevier B.V. All rights reserved.

Contents

1. Introduction ........................................................................................................................................................................................................................................................... 41
2. The collection of PAHs in air ........................................................................................................................................................................................................................... 41
3. Extraction methods for PAHs .......................................................................................................................................................................................................................... 42
3.1. General aspects of extraction: solvent type and solubility ..................................................................................................................................................... 42
3.2. The effect of polarity on extraction ................................................................................................................................................................................................. 42
3.3. Solvent extraction of gaseous PAHs captured on sorbents ..................................................................................................................................................... 42
4. Development of improved/alternative extraction methods for PAHs ............................................................................................................................................... 43
4.1. Cold-fiber solid-phase microextraction (CF-SPME) of extract solutions ............................................................................................................................ 43
4.2. Quick, easy, cheap, effective, rugged, and safe (QuEChERS) method ................................................................................................................................... 43

Abbreviations: ACN, Acetonitrile; aiu, Arbitrary intensity unit; ASE, Accelerated solvent extraction; BaP, Benzo[a]pyrene; BaPeq, Benzo[a]pyrene equivalent; BSTFA,
Bis(trimethylsilyl)trifluoroacetamide; BTV, Breakthrough volume; CF-SPME, Cold fiber solid-phase microextraction; DCM, Dichloromethane; DDT, Dichlorodiphenyltrichloroethane;
Hact, Arrhenius activation enthalpy for PAH desorption of a sorbent into gas-phase; DSWE, Dynamic subcritical water extraction; EC, European Commission; ECD, Electron-
capture detector (for a GC); FID, Flame-ionization detector (for a GC); GC, Gas chromatograph(y); GFF, Glass-fiber filter; HAP, Hazardous air pollutant; HPLC, High-
performance liquid chromatography; HRMS, High-resolution mass spectrometry; HS, Headspace; HVAS, High-volume air sampler; IARC, International Agency for Research
on Cancer; IS, Internal standard; LOD, Limit of detection; LOQ, Limit of quantitation; MAE, Microwave-assisted extraction; MEF, Mutagenic equivalency factor; MDL, Method
detection limit, MS, Mass spectromet(er or ry); MW, Molecular weight; NIST, National Institute of Standards and Technology; PAH, Polyaromatic hydrocarbon; PFE, Pres-
surized fluid extraction; PM, (airborne) Particulate matter; POP, Persistent organic pollutant; ppm, parts-per-million; PUF, Polyurethane foam; QFF, Quartz-fiber filter; QuEChERS,
Quick, easy, cheap, effective, rugged, and safe; SC-CO2, Supercritical CO2; SFE, Supercritical fluid extraction; SPE, Solid-phase extraction; SPME, Solid-phase microextraction;
SRM, Standard reference material; TEF, Toxic equivalency factor; TPM, Total particulate matter; UV(F), Ultra-violet (fluorescence); XAD-n, a type of sorbent (n = 1, 2, . . . n).
* Corresponding author. Tel.: +82 2 2220 2325; Fax: +82 2 2220 1945.
E-mail address: kkim61@hanyang.ac.kr or kkim61@nate.com (K.-H. Kim).
† Previously at: Dept. of Environment & Energy, Sejong University, Seoul, Korea.

http://dx.doi.org/10.1016/j.trac.2014.07.001
0165-9936/© 2014 Elsevier B.V. All rights reserved.
 J.E. Szulejko et al./Trends in Analytical Chemistry 61 (2014) 40–48 41

4.3. Miscellaneous extraction techniques .............................................................................................................................................................................................. 43

5. Clean-up, concentration, and standardization of PAHs .......................................................................................................................................................................... 44
5.1. Basics of clean-up for extracted solution ...................................................................................................................................................................................... 44
5.2. Sample losses during PAH extraction and concentration of extracts .................................................................................................................................. 45
5.3. Standardization ...................................................................................................................................................................................................................................... 45
6. Comparison of different studies: extraction efficiencies and breakthrough effects ..................................................................................................................... 45
7. Conclusion and recommendations ................................................................................................................................................................................................................ 46
Acknowledgments ............................................................................................................................................................................................................................................... 47
References .............................................................................................................................................................................................................................................................. 47

1. Introduction ticulate matter (PM) in both ambient air and from more potent sources
(e.g., tobacco smoke). Davis et al. [20] reviewed many important issues
Polyaromatic hydrocarbons (PAHs) are ubiquitous byproducts of involved in sampling PAHs in air [i.e., the choice of filters and sor-
incomplete combustion or pyrolysis of carbonaceous and organic bents [e.g., polyurethane foam (PUF), Tenax, and XAD-2], and active
matter (e.g., tobacco, coal, charcoal, diesel, gas, and wood) [1]. PAHs versus passive sampling]. These authors covered the period 1977–
are hydrocarbons with two or more fused aromatic rings and there 83 and described experimental artifacts, especially losses due to
are several hundred of these compounds. gaseous desorption of low-molecular-weight (MW) PAHs from PM
Zhang and Tao [2] reviewed the 2004 PAH emissions inventory and then prototype PAH-detection methods for near real-time spec-
both globally and by country, as Gg.y−1 of benzo[a]pyrene (BaP) equiv- troscopic analysis. Liu et al. [21] reviewed the developments of the
alent (BaPeq) (together with the major sources): Global 8.5 (biofuel analytical methods used to determine airborne PM PAHs (e.g., sam-
57%), China 2.81 (biofuel 56%), India 1.56 (biofuel 91%) and the USA pling and pretreatment methods) during 2000–05. Pandey et al. [1]
0.20 (waste incineration 24%). The 1999–2004 levels of atmospher- extensively reviewed the techniques for the determination of PAHs
ic PAHs in several Asian countries have also been reviewed; in China, in air with particular attention to collection methods, solvent-
cooking is the major source of PAHs in indoor air [3]. extraction efficiencies, limits of detection (LODs), and analytical re-
PAH emissions in Europe over the past 300 years have been re- producibility. Cecinato et al. [22] presented a short review of the
constructed by analyzing snow and ice samples collected in the high sampling and analytical methods for assessing PAHs, phthalates, and
Alpine regions; from ~1700–1900, PAH emissions were low but in- psychotropic substances in the atmosphere; they summarized sample
creased dramatically after ~1900 to peak during the 1940s. They type, collection, extraction and recovery, clean-up and separation,
decreased considerably until ~1970s and have only moderately and analytical instrumentation. Cullum et al. [23] provided an over-
increased until the early 2000s [4]. Similarly, Wang et al. [5] view of high temperature (150–600°C) fluorescence and other in
determined the historical trends (~1965–2005) of DDT, situ spectroscopic measurements of PAHs in flames and ambient air.
hexachlorocyclohexanes, and PAHs in an ice core from a Mount Everest Indeed, spectroscopic approaches for detection and quantitation of
glacier, central Himalayas, China and found good correlations with PAHs may be an important area for future research.
Indian economic and regulatory activities. Over the past decades, analysts have introduced many options
The toxicity of PAHs is well known. Indeed, they are the key com- for post-sampling treatment prior to the analysis of airborne PAHs.
ponents of the 189 hazardous air pollutants (HAPs) in the U.S. Clean Despite such developments, solvent-extraction techniques remain
Air Act Amendments [6]. Their structure is complex enough to the most common option for PAHs in particle or gas phases.
include not only compounds consisting of just carbon and hydro- In this article, we provide a review of the solvent-extraction tech-
gen but also a wide range of nitro-(N-), oxy-(O-), and thio-(S-) related niques for the analysis of airborne PAHs. Our discussion mainly focuses
PAHs [7]. The nitro- and oxy- derivatives deserve special attention on sampling and treatment of particulate PAHs, while focusing on
due their harmful health effects. It is suggested that these are po- the most important issues for the sampling of vapor-phase PAHs.
tentially mutagenic and/or carcinogenic [8,9]. PAHs and their as- This is because measurements of vapor-phase PAHs are not made
sociated (more polar) heteroatom derivatives are present in not only commonly – unless the study targets certain industrial sources such
ambient particles but also urban dust [10]. Furthermore, through as solvent factories [24]. In future work, we will turn our attention
long-range transport of polluted air masses, PAHs, particularly in to other emerging pretreatment methods for PAH analysis (e.g.,
the fine PM fraction, can be transported to receptor sites far from thermal desorption of PAHs off filters or sorbents and cryofocusing).
their original sources [11].
Based on laboratory tests on animals and human epidemio- 2. The collection of PAHs in air
logic studies, a number of PAHs are known or suspected carcino-
gens and mutagens [12]. There is strong causal evidence (based on The principal stages in the measurement of PAHs in ambient air
IARC criteria) that PAHs are lung cancer carcinogens and sus- generally consist of sampling, extraction, sample clean-up, and anal-
pected carcinogens for bladder, laryngeal, and prostate cancers [13]. ysis. The sampling may be performed with a variety of samplers,
PAHs are shown to be male reproductive endocrine disruptors [14] both low- and high-volume sampling rates and even passive sam-
and to induce lung cell tumorigenesis in mammals [15]. A number plers. Sampling media include quartz-fiber [25], glass fiber [26],
of PAHs have been assigned toxic equivalency factors (TEFs) for Teflon-coated glass fiber [27], and Teflon-membrane filters [28].
cancer [16] and mutagenic equivalency factors (MEFs) [17] rela- Quartz-fiber filters (QFFs) are commonly annealed at high tem-
tive to BaP to provide a more accurate risk assessment from envi- peratures for several hours to lower blank levels associated with
ronmental PAH exposure (e.g., for young children in New York City, the new filters. Materials used for sample handling, transport, and
NY, USA) [18]. The mutagenicity and the carcinogenicity of PAHs ambient sampling equipment must be free from organic sub-
in rodents has been assessed [19]. Bostrom et al. [12] reviewed in strates, although this is rarely a major problem. Because the PAHs
detail the lifetime cancer risk for various PAHs; these were found are only extracted from the PM on a filter without the whole PM
to be in the range 23–430 × 10−6 per ng.m−3 of BaP, thus showing and filter material being digested, as is the case for inorganic anal-
wide epidemiological variability. ysis of elemental metals content, blank levels from extraction of
There have been a number of reviews in recent years concern- unloaded filters are usually well below the LOD. It is worth
ing the sampling and the quantitation of PAHs in gaseous or par- pointing out the 3–5 ringed PAHs, which have relatively high vapor
42 J.E. Szulejko et al./Trends in Analytical Chemistry 61 (2014) 40–48
Table 1
Breakthrough volume (VB) and linear uptake sampling period for selected PAHs on XAD-2 and PUF
PAH VB (m3) PUF VB (m3) PUF VB (m3) PUF/
(20°C) (−10°C) XAD/PUF (20°C)
Naphthalene 0.75 7.6 6.9
Benzo[a]pyrene 2.6E + 06 3.9E + 08 2.7E + 06
Perylene 2.1E + 06 2.9E + 08 2.4E + 6
pressures, are not properly retained on PM filters, so they can be
lost to the gas phase. Often, a back-up sorbent is used to capture
these (e.g., PUF or XAD-2). Loss of sampled PAHs due to
photodegradation and reactions with gaseous oxidants [e.g., O3 (with
denuders sometimes used for removal of these oxidants)] are dis-
cussed in the literature.
The breakthrough volumes (BTV or VB) (as m3 per typical PUF
or PUF/XAD-2/PUF sorbent units in passive air samplers) and the
corresponding linear uptake range (for 25% sequestering, in days)
for selected PAHs (pyrene, acenaphthylene, fluoranthene, fluo-
rene, naphthalene, phenanthrene, anthracene, benzo[a]anthracene,
chrysene, benzo[a]pyrene and perylene) have been determined
(Table 1) [29]. Grosjean [30] compared the performance of Teflon
and glass fibers and QFFs in sampling PM-bound PAHs in Los Angeles,
CA, USA; the collection efficiencies of glass fibers and QFFs were
significantly lower (e.g., 85–90%) than those of Teflon fibers. However,
Hart and Pankow [31] reported that QFFs gave higher recoveries than
Teflon fiber filters, the effect being attributed to higher gaseous PAH
absorption on quartz compared to Teflon.
Common transportation and field-sampling procedures use pre-
annealed aluminum foil to transport sampling media to the field,
metal devices for handling sampling media, and pre-annealed glass
jars, and Teflon sealing tape and lid liner to minimize potential
contamination of samples. In addition to these common consider-
ations, the key requirement during sampling is to keep the sam-
pling time (between the change of samples) to a minimum to avoid
the on-filter degradation of collected PAHs by gaseous oxidants
[32,33]. Indeed, European legislation limits PAH sampling to 24-h
periods [34].
The vapor phase is collected only if suitable sorbent materials,
such as PUF or resin traps, are located after the filter. As a general
rule, the PAHs with the highest TEFs (the product of concentra-
tion and toxicity) are found predominantly in the particulate phase.
Of these, BaP is often used as a marker compound representative
of the total PAH load because of its high toxicity, relatively high con-
centration in PM and negligible presence in the vapor phase, making
it relatively easy to sample and to measure.
3. Extraction methods for PAHs
3.1. General aspects of extraction: solvent type and solubility
Alves [35] presented an overview of the characterization of
solvent-extractable organic compounds in atmospheric PM, includ-
ing a section on PM-bound PAHs and a scheme showing the common
sampling, extraction, and GC-MS analysis procedures for organic at-
mospheric aerosols. Alves also discussed the range of available ex-
traction methods [e.g., Soxhlet, ultrasonication, and supercritical fluid
extraction (SFE)].
A variety of solvent suites have been used and are often opti-
mized for the compounds of interest. Common solvent suites include
hexane plus 2:1 benzene:isopropanol [36], methanol and DCM
[37], and DCM and acetone [38]. In most cases, extracts are con-
centrated using rotary evaporation, which involves evaporating
the solvent with a high-purity inert sweeping gas such as N2 or using
reduced pressure. Chilled dead-volume evaporators are increas-
ingly common and allow the concentration to proceed
VB (m3) PUF/ Linear uptake Linear uptake
XAD/PUF (−10°C) range (days) XAD-2 range (days) PUF
41 2.4 0.05
3.9E + 08 39,400 156,000
2.9E + 08 110,000 129,000
unattended with no chance of evaporation of the sample to dryness
(which could lead to degradation of the PAHs).
Generally PAHs have low solubility in water, as expected from
their non-polar character. Solubilities decrease dramatically in going
from the 2- and 3-ring compounds (naphthalene 31.0 ppm and
acenaphthene 3.8 ppm) through the 3- and 4-ring semi-volatile or-
ganics (fluoranthene 0.26 ppm, benzo[a]pyrene 0.004, and coronene
0.0001 ppm) [39]. However, reactions of PAHs in ambient air to form
more polar species, such as nitro-PAHs and quinones, greatly enhance
their solubility in aqueous systems. This has major implications when
one considers the distribution of PAHs and their atmospherically
formed PAH derivatives, in the air, water, and soil environmental
compartments. These increases in solubility following derivatization
are important from not only an environmental chemistry perspec-
tive but also possible impacts on public health and natural ecosys-
tems of exposure to PAHs.
3.2. The effect of polarity on extraction
Analysis of polar PAHs in atmospheric PM is of interest for a
variety of reasons including the need to measure the highly polar
oxidation products of photochemical reactions, tracking primary par-
ticle sources that contain polar organic species [40], and evaluat-
ing the impact of water-soluble compounds in the activation of
aerosol particles into cloud droplets [41]. The analysis of polar organic
compounds requires tailoring of the analytical extraction process
to the polarity of the analyte. Analytical techniques to quantify polar
organic compounds generally fall into two categories: extraction in
water [42] and extraction in solvent [43].
For organic speciation, most GC techniques are not well suited
to the analysis of polar organic compounds extracted with water
and/or organic solvent, due to the binding of polar functional groups
to the stationary phase of the GC column. To overcome this issue,
derivatives of specific polar functional groups are formed as their
non-polar analogues; this is accomplished through conversion of
acids to methyl esters by reaction with diazamethane [44] or re-
action of organic acids and alcohols to trimethylsily esters by re-
action with bis(trimethylsilyl)trifluoroacetamide (BSTFA).
Other GC approaches have been applied using polar capillary
columns for quantifying organic acids from PM without derivatization
[26] or water extraction followed by polar-compound derivatization
with analysis by GC-MS [45]. Several methods have been used for
the analysis of water extracts of PM, including electrophoresis [46],
anion-exchange chromatography [47], and traditional HPLC [48–51].
3.3. Solvent extraction of gaseous PAHs captured on sorbents
Extraction methods for gas-phase PAHs are very similar to those
employed for the extraction of particulate-phase PAHs. If resin car-
tridges are used for collection, then only certain extraction methods,
such as microwave or accelerated solvent extraction (ASE), are ef-
fective; often, these will be designed specifically for extracting PAHs
from the proprietary resin cartridge used [52]. Indeed, it is wise to
perform efficiency studies on the sorbent intended for use to un-
derstand its collection efficiency [53]. Gentler techniques, such as
Soxhlet or reflux, may not adequately remove the PAHs from the
sorbent – although the addition of deuterated PAH analogues to act
 J.E. Szulejko et al./Trends in Analytical Chemistry 61 (2014) 40–48
as extraction standards can help correct for any reduction in
recovery. Resin cartridges are also amenable to direct thermal de-
sorption extraction for both vapor-phase [54] and particulate-
phase PAHs [55].
Primbs et al. [56] discussed the effect of polarity and hydrogen
bonding capability of the solvent on PAH extraction efficiency off
PUF (medium polarity and hydrogen bonding) using a Hansen sol-
ubility plot. Pure hexane (low polarity and hydrogen bonding
strength) and acetone (very high polarity and hydrogen bonding
strength) are poor solvents, whereas a 1:1 mixture of hexane and
acetone is an excellent solvent, as its polarity and hydrogen-
bonding properties are close to those of PUF. DCM is marginally
within the PUF solubility range, so it is also potentially a useful
solvent. In summary, the polarity and hydrogen-bonding proper-
ties of the chosen solvent should closely match those of the sorbent.
For collecting gaseous PAHs on PUFs (which are generally soft
and malleable), special care must be taken not to deform the foams
prior to analysis; this is important to prevent loss of the gaseous
phase component. In these cases, it is also essential to spike such
samples with deuterated surrogate as soon as possible (so that any
losses may be subsequently corrected), while keeping these samples
in a freezer to prevent further loss of volatiles. For large vapor-
phase PUFs, such as those used with high-volume samplers, it may
be necessary to use more improvised techniques for extraction, such
as gentle immersion in hexane following by gentle heating and slow
deformation of the foam to release the PAHs into the solvent [57].
In such cases, because these large foam traps can soak up a large
amount of solvent, it is very important to ensure that they are ad-
equately drained after extraction. Otherwise, a large proportion of
the PAHs collected may remain as the solvent/foam mixture – es-
pecially if not using a deuterated surrogate correction method. The
same principle is true for any technique where the filter or vapor
cartridge remains in the solvent after extraction (e.g., reflux), al-
though the volumes absorbed are generally much smaller. For tech-
niques where the solvents drain past the filter or vapor cartridge
(e.g., Soxhlet), this is generally not a consideration, although sur-
rogate correction is generally still beneficial [52].
4. Development of improved/alternative extraction methods
for PAHs
In recent years, there has been a growing effort to reduce or to
eliminate solvent use when extracting analytes of interest from
various matrices and hence limit the impact of waste solvent on
the environment. Solvent-less or low-volume, solvent-extraction pre-
treatment for environmental analysis has emerged (e.g., thermal de-
sorption and single-drop microextraction). However, discussion on
the pretreatment of airborne of gaseous and PM PAHs was very
limited with no specific examples given [58]. Some examples of more
environment-friendly extraction methods include supercritical-
CO2 (SC-CO2) and dynamic sub-critical water-solvent extraction. The
following sub-sections give details of other extraction methods using
various solvents.
4.1. Cold-fiber solid-phase microextraction (CF-SPME)
of extract solutions
Guo et al. [59] briefly discussed CF-SPME efficiency in terms of
the thermodynamics of PAH partition coefficients between the gas
phase (headspace above heated certified soils) and the SPME coating;
increased soil temperature and extraction time greatly improved
extraction efficiency. The Arrhenius parameters (i.e., the apparent
ΔHact) for PAH desorption from solid matrices (sand, silica gel, and
soils) into the gas phase were determined and discussed; silica
showed the largest ΔHact, hence the slowest desorption rates [60].
Menezes and de Lourdes Cardea [61] monitored the CF-SPME and
43
SPME PAH uptake as a function of extraction time and the temper-
ature of the solvent (20 mL H2O + 0.15 mL of 1:1 DCM:acetone) cov-
ering spiked filter and blank filter sections. They found that
naphthalene and acenaphthylene had very low uptakes (peak area
~0.2 aiu), whereas benzo[a]anthracene had a very high uptake (peak
area ~4.5 aiu). The corresponding CF-SPME LOQ (ng) was in the range
0.05 (naphthalene)–3.86 (benzo[k]fluoranthene), as determined
by GC-MS in SIM mode (in apparent contradiction of the previous
sentence).
The developments in SPME up to mid-2008 were recently re-
viewed, including CF-SPME of HS above heated soil and sediment
samples [62]. A Web of Science search (12 December 2013) using
“polycyclic aromatic hydrocarbons” “cold fiber” (or “cold fiber”) terms
yielded 11 results; this should be compared to the 478 results re-
turned using the terms “polycyclic aromatic hydrocarbons” “liquid
extraction”. Nonetheless, HS-CF-SPME is an emerging method with
potential for PAH uptake from solvent extracts of PAHs from sam-
pling filters and sorbents.
4.2. Quick, easy, cheap, effective, rugged, and safe (QuEChERS)
method
A Web of Science search (12 December 2013) using the terms
“polycyclic aromatic hydrocarbons” and “QuECHERS” yielded only
27 results; of those results, only one was specifically for airborne
PM PAHs [63], whereas the other 26 were to cover biota samples.
One reason for this may be that the standardization of methods used
in Europe for regulatory measurement of PAHs in ambient air has
reduced the number of allowable extraction techniques to produce
air-quality data for submission to the European Union (EU). These
conditions should have reduced the quantity of research into these
topics at many European air-quality reference laboratories. Albinet
et al. [63] gave a brief introductory overview and history on
QuEChERS (e.g., the total extraction and clean-up time is ~1–
5 min) and claimed to be the first to use QuEChERS for airborne PAHs.
PM samples were collected on QFFs using a HVAS (70 m3 h−1 for 24 h)
in an urban area in France. For QuEChERS, QFF sections were placed
in centrifuge vials, immersed in 7 mL of DCM, ACN, or 5:2 v/v ACN/
H2O and vortexed for 30–120 s. Next, the vials were centrifuged at
4500 rpm for 5 min and 1 mL supernatant was collected for direct
analysis by HPLC-UVF. Another 3 mL was also collected, and reduced
under N2 to 1 mL in less than 2 min, filtered, and cleaned up using
Florisil. Adding salts (e.g., Na2SO4) to the solvent was investigated.
The performance of QuEChERS was compared to ASE using the same
QFF and SRM 1649a. Overall, the recoveries were comparable –
QuEChERS (61–111%) and ASE (78–119%). ASE used about 30 mL
DCM and required ~20 min.
4.3. Miscellaneous extraction techniques
Tollbäck et al. [64] examined the feasibility of using solid-
phase Empore membranes to capture fine airborne PM (10–800 nm)
and dynamic subcritical water extraction (DSWE) of PAHs from the
fine PM. During sampling, the PM in the air entering and leaving
the Empore membrane (up to 20 L.min−1 and 24 h) was monitored
using a scanning mobility particle sizer; no evidence of PM break-
through was noted). An urban dust sample from NIST (SRM 1649a)
loaded on the Empore membranes was used to evaluate the DSWE
method. The Empore membranes were spiked prior to air sam-
pling with liquid standards containing 16 PAHs in c-hexane and a
mixture of C8–C33 n-alkanes. Analysis was done by GC-FID. The basic
DSWE set-up consisted of a HPLC module to pump water, an ex-
tractor cell inside a GC oven, and a vial to collect the extract. The
extractor cell contained cut-up sections of the Empore mem-
branes. Although liquid water is polar solvent under normal
conditions, its polarity decreases rapidly with temperature to
44 J.E. Szulejko et al./Trends in Analytical Chemistry 61 (2014) 40–48

low polarity above 100°C. It thus becomes a good solvent for

non-polar organics (e.g., PAHs under pressurized conditions). Water
is also considered to be a “green environment-friendly solvent”.
DSWE at 250°C (of a spiked membrane) cleanly separated 15 of the
16 PAHs from the 26 n-alkanes, and increasing the DSWE to 275°C
eluted ~20 additional peaks [64]. Membranes spiked with SRM 1649a
were used to optimize DSWE; the optimal conditions were:

• first washing (2 mL.min−1 flow, 80°C, 55 bar);

• second washing (2 mL.min−1 flow, 130°C, 55 bar to remove
organics); and
• extraction (2 mL.min−1, 250°C at 55 bar to desorb PAHs selec-
tively, but retaining aliphatics).

Most of the PAHs were eluted in the first 18 mL of extract (re-

coveries 80–120%, best for lighter PAHs), while recoveries were less
than ~10% for the second 18 mL. The extrapolated method detec-
tion limit (MDL) for standard-volume air samples using DSWE was
in the pg m-3 range 5 (phenanthrene)–39 (benzo[a]pyrene). A GC-
MS chromatogram of an environmental air sample (0.879 m3, roof
level, central Rome, Italy) was obtained using the DSWE method,
although details of such measurements were not discussed.
The solubility and the dissolution rate of anthracene in subcriti-
cal water (120–200°C, ~50 bar) was recently reported [65]; these
authors compared their results to previous work. Anthracene sol-
ubility (as a fraction amount in mol/mol) increased from 1.6 × 10−6
at 120°C to 153 × 10−6 at 200°C. The corresponding solubility at room Fig. 1. The general procedure for analysis of polyaromatic hydrocarbons (PAHs).
temperature and 1 bar pressure is minimal. The solvation equili-
bration time of anthracene and p-terphenyl in subcritical water at
50 bar was in the range 180 min at 120°C to 20 min at 200°C. This
may have important consequences in DSWE applications, since suf- procedure for PAH analysis. To obtain sufficient sample for extrac-
ficient extraction time or higher temperatures is needed to assure tion and subsequent analysis of organic species, PM is collected on
quantitative recovery of PAHs from PM. Tollbäck et al. [64] found filter substrates in the field, often over extended time periods using
that DSWE of PAHs off SRM 1649a required 9 min at 250°C for >80% high-volume air samplers. Alternatively, filters from a low-volume
recovery. Shahpoury and Hageman [66] compared their pressur- sampler over several sampling days may be combined [37]. Prior
ized liquid DCM extraction of (water-borne) PAHs from silicone to standardization, the 2001 European Commission (EC) position
rubber passive samplers with the literature; their 40 min extrac- paper on PAHs [67] found a variety of methods in use across Member
tion time was much shorter than the typical 8–24 h extraction times. States in Europe, as shown in Table 2. Sample collection on filter
or other substrates is challenging in itself due to positive and
5. Clean-up, concentration, and standardization of PAHs negative sampling artifacts that change the composition of the
collected PM on the filter relative to what is in the air [68].
5.1. Basics of clean-up for extracted solution Beyond this, analytical techniques must be rigorously evalu-
ated to minimize introduction of contaminant sources and co-
As the extracted solutions can contain impurities and interferents, contamination between samples through extraction vessels, solvents,
they can act as the source of experimental bias in PAH quantitation. reagent, and analytical equipment. For more detail, generally samples
To reduce the source of such bias, a clean-up stage is often re- and extracts are kept in a freezer when not in use. All glassware is
quired. The methodologies involved in clean-up for particulate- baked overnight in a muffle furnace (at least 450°C or higher) before
phase PAHs vary widely with subsequent analysis by GC-FID, GC- use. All instruments (e.g., forceps) are rinsed multiple times with
MS or HPLC (with UV or MS detection). Fig. 1 presents the general dichloromethane to eliminate cross contamination.

Table 2
AH extraction, clean-up, and analysis methods used in several European countries in 2001, from [European Commission, 2001] [34]

Country Extraction Clean-up Analysis

UK Soxhlet with DCM, hexane or toluene Silica gel, alumina chromatography columns or solid phase HPLC-UV or GC-MS
extraction cartridges
Finland Soxhlet Liquid-liquid extraction with DMSO. Silica gel or alumina GC-MS
chromatography columns
Austria Soxhlet with hexane and diethylether (20 hours) Solid phase extraction cartridges GC-MS
Italy Ultrasonic extraction with cyclohexane Thin layer chromatography on silica gel GC-FID or GC-MS
Spain Soxhlet with cyclohexane & DCM, or DCM & acetone Silica gel or alumina chromatography columns GC-MS
Greece Soxhlet with cyclohexane or benzene. Ultrasonic Liquid-liquid extraction with DMF and water. Silica gel or alumina GC-FID, GC-MS HPLC-
extraction with DCM or hexane & cyclohexane chromatography columns fluorescence
Belgium Ultrasonic extraction with DCM None HPLC-fluorescence
France Soxhlet with DCM. Accelerated solvent extraction with None HPLC-fluorescence
DCM
Denmark Soxhlet with toluene (24 hours) Silica gel or alumina chromatography columns GC-FID or GC-MS
 J.E. Szulejko et al./Trends in Analytical Chemistry 61 (2014) 40–48
5.2. Sample losses during PAH extraction and
concentration of extracts
The concentration step of PAH analysis is needed to improve the
sensitivity of the analysis. Loss of target analytes through extrac-
tion and concentration is commonly monitored using isotopically
labeled recovery standards, such as acenaphthene-d10, pyrene-d10,
benz[a]anthracene-d12, and coronene-d12, which are spiked onto the
sample prior to extraction – often called ‘surrogate standards’ or
‘recovery standards’. Generally, they are spiked onto filters after sam-
pling but before analysis, although, when considering more vola-
tile PAHs, sometimes the surrogates are spiked onto the filter prior
to sampling [24]. Separation and detection of extracted non-polar
compounds are usually accomplished by GC-MS methods relying
on electron-impact ionization, but occasionally by negative chem-
ical ionization [69]. The more volatile lower MW PAHs (e.g., naph-
thalene) are particularly sensitive to losses during extraction and
sample concentration due to vaporization. For example, Singh et al.
[70] reported recoveries of 69% (naphthalene) to 95% (phenan-
threne). Pandey et al. [1] reviewed the solvent-based extraction re-
coveries and noted divergent results for the low MW PAHs (e.g.,
naphthalene). For example, Omar et al. [71] reported that the lighter
PAHs had poor recoveries (DCM ultrasonication of QFF and there-
fore not readily quantifiable; for other PAHs, recoveries were 50.8–
99.7%); in contrast, Zhang et al. [72] reported recoveries of 84.5%
(naphthalene) to 108% (BaP) for hexane/c-hexane PAH extraction
from GFF.
5.3. Standardization
Laboratory quantification of individual organic compounds is per-
formed by a variety of analytical techniques, depending in part on
the species to be determined. Many liquid-extraction approaches
use organic solvents or water to remove particulate organic species
from the PM collected on the filter. The extract solution is gener-
ally tailored to the polarity of the analyte to ensure efficient removal
of the desired components. Rigorous cleaning procedures are re-
quired for proper filter preparation, sampling, and subsequent anal-
ysis to identify and to quantify individual organic compounds in PM.
Note that in some cases, no clean-up step is used prior to analysis
– this is usually the case if, after the extraction, there is no evi-
dence of small particulates (from the PM or filter material) in the
extract, or if the extract is taken from locations with low concen-
trations of interfering compounds (e.g., aliphatic alcohols). Because
of the significant differences in analytical practices and the varia-
tions in results that they can cause, where measurements are to be
made in support of regional or global legislative requirements and
to compare with target values (for example, in the EU), it has been
necessary to produce a documentary standard method to ensure
the stability and the comparability of measurements made over time
and across different locations.
During the European standardization process, substantial lab-
oratory and field testing of the equivalence of these various pro-
cesses were undertaken. The criterion for the European standard
(which focused on the measurement of BaP) was that the recov-
ery of a suitable certified reference material (in this case NIST 1649a)
must be 80–120%. It was found that this condition was met for the
extraction method and solvent combinations given in Table 3 [73].
However, the standard recognizes that other approaches may be used
in combination with the surrogate standard method. This is where
a deuterated analogue of the compound(s) of interest is added to
the collected samples prior to extraction. The recovery of the deu-
terated standard is then used to correct the recovery of the non-
deuterated analogue. The EN15549 method suggests that this is
acceptable practice down to deuterated recoveries of 50%, below
which the method is considered to be not under control. Indeed,
45
Table 3
Extraction methods and solvent combinations meeting the requirements of Euro-
pean documentary standard EN15549
Extraction methods Solvent
Reflux Toluene
Soxhlet Toluene, hexane & acetone (1:1), DCM
Microwave Hexane & acetone (1:1)
Accelerated solvent Toluene, DCM, DCM & hexane (1:1)
Ultrasonic DCM, toluene
it is generally acknowledged as good practice to use these deuter-
ated surrogates in all cases.
It is important to be aware of possibly different recovery char-
acteristics between the real sample and spikes added to it. As the
chemical difference of the deuterated surrogate increases from the
compound of interest, the extraction efficiency is less likely to be
similar – this is especially important when drawing qualitative con-
clusions from the data or the values [74,75]. Although it is ideal to
add a deuterated analogue for every PAH of interest, this can be pro-
hibitively expensive. It is further noted in the European standard
[73] that the presence of reactive impurities (e.g., peroxides, acids
or radicals) from non-stabilized solvents can lead to the degrada-
tion of PAHs and deuterated PAHs during extraction [76] and that
can affect measurement results.
6. Comparison of different studies: extraction efficiencies and
breakthrough effects
The PM PAH emissions from a small, portable, diesel, electrical
power generator fueled with petroleum or two biofuel diesels were
measured under load. The exhaust was first diluted and cooled to
50–52°C and collected on a Dekati gravimetric impactor with a 1-μm
cut-off Pallflex TX40 back-up filter. The filters were weighed (before
and after sampling) and spiked prior to ASE followed by concen-
tration. Clean-up was done using SPE silica gel cartridges (recov-
eries of SPE generally 80–100%) and concentrated. Analysis was
achieved using HPLC-GC-MS. The biofuel diesels (B30 and B100) had
generally lower PAH emissions than petroleum diesel [77]. Simi-
larly, emissions of airborne PAHs in meat smokehouses were cap-
tured on separate PUF and XAD-2 sorbent cartridges placed 2 m
above the smoldering beech-wood sawdust. After solvent extrac-
tion and clean-up, the PAHs were quantified by fast GC-HRMS [78].
The feasibility of using engine air-intake filters of diesel taxis op-
erating in urban Manchester, UK, to collect airborne PAH PM was
recently reported; the filters after ~2–3 weeks’ service were removed
and taken to the laboratory for analysis. The filters were cut into
small sections (~1 g) for spiking, ultrasonically solvent extracted using
1:1 hexane/DCM three times, centrifuged, concentrated, further pu-
rified on SPE silica cartridges using 1:1 hexane/DCM mobile phase,
and finally reduced to 1 mL for GC-ITMS analysis. Recoveries were
74 ± 25%. The PM collection-efficiency limitations of air-intake filters
were briefly discussed. The main finding was that the estimated PAH
concentrations ~0.5 m above street level were up to 100 times higher
than the those officially reported by the UK Government (for
the period 2005–10); their concentrations were measured at an
national network sampling site located on the roof of four-story
building [79].
Singh et al. [70] spiked blank PUF plugs and GFFs with a stan-
dard solution containing 16 EPA priority PAHs and reported a mean
recovery of 88% (range: 69% (naphthalene)–95% (phenanthrene));
reproducibility was about ±12%. The PM on GFFs were extracted using
50 mL DCM with three 30 min ultrasonic agitation cycles, the DCM
extract reduced to 5 mL, then cleaned up using silica gel, filtered
through a membrane, and stored in vials in a refrigerator until GC-
MS analysis. The PUF plugs were subject to Soxhlet extraction with
46 J.E. Szulejko et al./Trends in Analytical Chemistry 61 (2014) 40–48
hexane for 8 h and, after extraction, the same procedure as for GFFs
was followed. Air samples collected in Delhi, India, were analyzed
to discern seasonal patterns.
A 24-h high-volume air sampler (700 L min−1) containing quartz
fiber (PM < 0.3 μm) filter and PUF sorbent was positioned 1 m above
the ground near two main roads in Tokyo, Japan. Both filter and PUF
were Soxhlet extracted in DCM for ~12 h followed by spiking, con-
centration, and purification by a two-step silica-gel column chro-
matography. Analysis was done by GC-MS. The reported recoveries
were all greater than 65%, determined using surrogate standards.
The air-sampler results were compared to DCM pressurized fluid
extraction (PFE) of gingko-tree leaves taken at 2 m, 3 m, 4 m and
8 m above the ground (at the same site). The PAH amounts in the
gingko leaves rapidly decreased with increasing leaf height, sug-
gesting the PAHs were mainly from vehicle exhausts [80].
Three adsorbents (Carbopack B, Tenax GC, and XAD-2) were
evaluated for the sampling of persistent organic pollutants (POPs)
(e.g., PAHs, PCBs, and pesticides) in the Molise region of Italy. Pyrex
6 mm i.d. sorbent tubes were packed with 300 mg of selected ad-
sorbent followed by a 65 mg back-up section (separated and held
in place by quartz wool plugs). In laboratory tests, the adsorbents
were loaded, and variable volumes of humidified air were pulled
through the adsorbents to determine recovery (breakthrough). De-
sorption of the POPs from the adsorbent was effected by 1–2 mL
CS2 and analyzed by GC-FID or GC-ECD. Carbopack B and Tenex GC
(BTV = 167 L.g −1) and XAD-2 (BTV = 1667 L.g −1) exhibited near 100%
recovery for all tested POPs (0.2 μg loading each). At BTV = 400 L.g −1,
Carbopack B, the PAH recoveries ranged from 88% (pyrene) to 100%
(anthracene); Tenax GC showed less breakthrough. XAD-2 at BTV
of 1667 L.g −1 or 5000 L.g −1, the recovery was 100% for all test POPs
(0.2 μg loading). However, at 1 ng loading and BTV = 5000 L.g−1, the
PAH recoveries were marginally reduced [e.g., 79% (benzo[a]pyrene)
to 94% (anthracene)] [81].
PM and gaseous PAH emissions from burning decorative candles
were collected on a glass filter pad (PM), cold trap (water vapor),
and a sorbent tube (50 mg XAD-2 – gaseous PAH) at a flow rate of
20 L.min-1 for a total volume of 6–10 m3. The glass filters were ul-
trasonically extracted with DCM, filtered through Na2SO4, concen-
trated, and spiked with deuterated internal standards (ISs). The
cold-trap aqueous phase was DCM extracted, dried over Na2SO4,
evaporated to dryness and dissolved in 0.125 mL IS solution. The
XAD-2 cartridge was eluted with DCM, dried over Na2SO4, evapo-
rated to dryness and dissolved in 0.125-mL IS solution. Analysis was
performed using GC-QMS in SIM mode. The extraction recoveries
were never less than 78% and generally near 100% by adding deu-
terated surrogates into the sampling line over the candle [82].
Delgado-Saborit et al. [83] explored a number of parameters ef-
fecting ASE recoveries and compared them to a simple shaker ex-
traction method using 8 mL DCM and purification over Na2SO4. They
used standards containing 9 deuterated and 16 natural PAHs to de-
termine recovery of spiked AQFA quartz membrane filters. For ASE,
two clean-up agents (deactivated Fluorisil and activated silica gel)
and three solvents (neat DCM, neat hexane, and DCM/hexane
mixture) were compared. The best overall recoveries were ob-
tained using 40 mL DCM (73%), 30 mL hexane/20 mL DCM, and the
shaker method (106%). Multiple extractions with 30 mL hexane,
30 mL DCM, and 150 mL DCM gave the lowest overall recovery of
25% (range: 10–39%). Activated silica gel (only one experiment) gave
marginally inferior recovery compared to deactivated Fluorisil. In
conclusion, the simpler shaker method performed better than ASE
and was the method of choice for the environmental samples. At-
mospheric sampling was done using a low-volume sampler (12 L.s−1
for 2 h) located in different street micro-environments (e.g., busy
roads, background streets, pedestrian streets, and parks).
Li et al. [84] evaluated six solvents (acetone, ACN, DCM,
methanol, n-hexane, and toluene) to optimize SPE of standards
containing 16 PAHs. Of the six solvents investigated, DCM, n-hexane,
and toluene generally gave recoveries in the range ~90 ± 20%, whereas
the others (acetone, ACN, and methanol) gave reasonable recover-
ies for the lighter PAHs (50–100%) but very poor recoveries of ~0–
30% for the heavier PAHs. This reflects the effect of solvent polarity
governing SPE breakthrough. The less polar solvents had smaller
breakthrough volume than the more polar solvents. Overall, DCM
gave the best SPE performance.
The recovery effectiveness of using SC-CO2 fluid extraction of PAHs
from urban PM (e.g., NIST SRM 1649a) was evaluated as a func-
tion of pressure at a fixed 50°C or 80°C temperature. SC-CO2 is a
desirable replacement for organic solvents because of its low cost
and easy recycling [85]. To improve extraction efficiency, metha-
nol (an organic modifier) was added to the SC-CO2 and the organic
analytes were extracted into hexane, acetone, or 1:1 hexane:acetone
for GC-MS analysis. Of the three organic modifiers evaluated, 5% v/v
methanol gave better recoveries than hexane or toluene. The 50°C
recovery for BaP increased from ~40% at 230 bar to ~90% at 400 bar
and then remained fairly constant up to 600 bar (the maximum pres-
sure tested) [85].
Piñeiro-Iglesias et al. [86] assessed Soxhlet, ultrasonic, and
microwave-assisted extraction (MAE) of BaP from two certified stan-
dard reference materials (SRM 1648 – urban particulate matter and
SRM 1649a – urban dust) to comply with EC directives. The sol-
vents investigated were acetone, DCM, methanol, toluene and
hexane. Analysis was done by HPLC-UVF, GC-FID or GC-MS. For SRM
1648, the BaP recoveries were near to 100% for 1:1 hexane:acetone
solvent extraction by Soxhlet, ultrasound, and MAE. However, using
the same solvent, BaP recoveries of SRM 1649a were variable: ~96%
(Soxhlet), ~84% (ultrasound), and ~81% (MAE). Using toluene, Soxhlet
extraction gave ~98% BaP recovery. The authors recommended MAE
using 1:1 hexane:acetone as a good option because of low solvent
usage and good quantitative recovery. The BaP LODs (standard
PAH mixture SRM 1647d in ACN) extrapolated to equivalent air con-
centrations based on standard sampling volumes, were seen to vary
as 0.003 pg.m−3 (HPLC-UVF), 1.7 pg.m−3 (GC-MS), and 14.2 pg.m−3
(GC-FID).
Single-puff mainstream cigarette-smoke total particular matter
(TPM) from a smoking machine (35 mL per 2 s puff) was collected
on weighed Al foil discs placed inside an impaction trap. After sam-
pling, the Al discs were weighed and the TPM dissolved in 50 mL
of 5:5:1 mixture of toluene, hexane, and i-propanol containing
1 μg.mL−1 each of the deuterated PAH standards. The TPM solvent
mixture was sonicated for 10 min at room temperature and a 1-μL
sample was analyzed by GC-MS in SIM mode; since no clean-up step
was used, the GC-MS became quickly contaminated, thus requir-
ing more frequent maintenance. For puff number 4, the relative PAH
yields (i.e., PAH peak area/IS peak area per 1 mg TPM) were: naph-
thalene (1.1), phenanthrene (0.31), fluoranthene (0.1), pyrene (0.085)
and benzo[a]pyrene (0.014) [87].
7. Conclusion and recommendations
A number of solvents and extraction methods have been used
over the years to extract PAHs from either PM or sorbents. All possess
both advantages and disadvantages in terms of ease of use, com-
plexity, choice of solvents, and analyte recovery. The range of
methods reviewed in this article demonstrates clearly that the anal-
ysis of any organic component in PM, but particularly PAHs, is
complex, because of the requirement to extract the PAH from the
PM as completely as possible but without causing degradation or
any other undesirable side reaction. This is a challenge for PAHs
because of their light sensitivity and propensity to react with gaseous
oxidants. Compare this situation to that for the analysis of PM-
bound inorganic constituents, such as metals. Here, one is gener-
ally only interested in the total elemental metal content present
 J.E. Szulejko et al./Trends in Analytical Chemistry 61 (2014) 40–48
(not the individual chemical form). Thus, one may apply very harsh
extraction techniques that result in full digestion of the PM, its con-
stituents, and the filter material itself, in order to ensure that all
the target analytes are recovered into solution. The one advantage
of the gentler, compound-specific extraction techniques used for
organic analysis of PM is that concentrations recovered from blank
filters are usually negligible, resulting in extremely low LODs.
However, the main disadvantage is that we may not fully recover
all of the target analyte.
It is clear from this review that a number of techniques may be
appropriate for the accurate measurement of PAHs in ambient PM.
Whatever extraction techniques are to be used for PAH analysis, it
is essential that they have been fully validated and can be demon-
strated to produce fully SI-traceable measurement results with a
robust statement of measurement uncertainty. This ensures that
measurements are stable over time, comparable between loca-
tions, and coherent, regardless of measurement techniques used.
To ensure SI traceability, it is essential to understand fully and to
validate the method used. To this end, one may need to conduct
the extraction of certified reference materials regularly to assess the
extraction regime. In most cases, it will be best practice to also use
isotopically labeled surrogate standards to ensure that recoveries
of less than unity may be properly corrected. Ideally there will be
an isotopically labeled surrogate for each analyte, allowing mea-
surement to help perform this requirement. It is also important to
recognize that the recovery of isotopically labeled surrogates may
not have the same characteristics as native PAHs bound in the PM;
this must be accounted for in the uncertainty budget for the
measurement.
It is clear that the technology for the extraction of PAHs from
PM is evolving rapidly, providing new and exciting opportunities
for future analysis. However, until these new technologies become
fully mature and are validated, documentary standards will
also remain a key part of PAH analysis in PM, ensuring that
current best practice in the area is formulated and crystallized,
especially when measurements are to be compared against legis-
lative values.
Acknowledgments
This study was supported by a National Research Foundation of
Korea (NRF) grant funded by the Ministry of Education, Science and
technology (MEST) (No. 2009-0093848). The views and the con-
clusions contained herein are entirely the responsibility of the
authors and should not be interpreted as necessarily representing
the official policies, or endorsements, either expressed or implied
of MEST or the Government of the Republic of Korea, nor do the
authors endorse or recommend the use of any commercial prod-
ucts or trade names and procedures (medical, analytical, or other-
wise) mentioned herein. The authors reported no conflict of interest
or financial interests.
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