Pahs

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Trends in Analytical Chemistry, Vol. 30, No. 11, 2011
A review of techniques for the determination of polycyclic aromatic hydrocarbons in air

Sudhir Kumar Pandey, Ki-Hyun Kim, Richard J.C. Brown
We provide an extensive review of the common methodologies employed in the analysis of airborne polycyclic aromatic hydrocarbons (PAHs). The review focuses on gas-chromatography-based approaches, in the light of their universal application with excellent separation, resolution, and sensitivity. We rst describe collection methods for airborne PAHs in the gas and particle phases. We then evaluate the efciency of extraction techniques employed for separating target PAHs from sampling media, using conventional solvent-based and emerging thermal-desorption approaches. We also describe commonly employed analytical methods with respect to their applicability to PAHs in gas and particle phases, collected from diverse environmental settings. As an essential part of basic quality assurance, we examine each method with special emphasis on key parameters (e.g., limit of detection and reproducibility). Finally, we address the likely directions of methodological developments, their limitations, and the future prospects for PAH analysis. 2011 Elsevier Ltd. All rights reserved.
Keywords: Airborne polycyclic aromatic hydrocarbon; Analytical discrepancy; Analytical methodology; Extraction; Gas chromatography; Limit of detection (LOD); Polycyclic aromatic hydrocarbon (PAH); Reproducibility; Solvent-free; Thermal desorption
1. Introduction
Sudhir Kumar Pandey+, Ki-Hyun Kim* Atmospheric Environment Laboratory, Dept. of Environment & Energy, Sejong University, 98 Goon Ja Dong, Gwang Jin Goo, Seoul 143-747, Republic of Korea Richard J.C. Brown Analytical Science Division, National Physical Laboratory, Hampton Road, Teddington TW11 0LW, UK
Corresponding author. Tel.: +82 2 3408 3233; Fax: +82 2 3408 4320; E-mail: khkim@sejong.ac.kr + Presently at: Dept. of Botany, Guru Ghasidas Central University, Bilaspur (C.G.), 495009, India
Polycyclic aromatic hydrocarbons (PAHs) are a group of over 100 different chemicals that are known to be formed typically during incomplete combustion of organic matter at high temperatures [1]. Their major sources in the atmosphere include industrial processes, vehicle exhausts, waste incineration, and domestic heating emissions, while they can also be released naturally {e.g., forest res [2]}. They are ubiquitous in the environment and contain two or more fused benzene rings in linear, angular or cluster arrangements. In addition to the frequency with which they occur in the environment, proof of their mutagenicity and carcinogenicity led to some of them being selected as priority pollutants (e.g., 16 PAHs) by the US Environmental Protection Agency (EPA) (Table 1). The World Health Organization (WHO) added 17 additional PAHs to make a total of 33 PAHs under its regulation [3]. (In Table 1, these 33 compounds are listed with their three-capital-letter
acronyms). In Europe, ambient air legislation targets benzo[a]pyrene (with an annual target value of 1 ng/m3) because this compound carries the highest toxic load (dened as concentration multiplied by toxicity) of any airborne PAH. Because of their thermally stable structure, PAHs generally exhibit a high melting point, a high boiling point, and a low vapor pressure. In the atmosphere, they are distributed between gas and particlebound phases [49]. This phase partitioning is largely regulated by changes in atmospheric conditions (e.g., temperature and relative humidity), and the physical properties of the PAHs themselves [10 13]. Consequently, lighter PAHs tend to be preferentially enriched in the gas phase, while the heavier ones show almost complete association with particles [14] indeed, in Europe, air-quality legislation to limit PAH concentrations in air sets target values for only particulate-bound PAHs (benzo[a]pyrene in the PM10 particulate phase). For these reasons, it is a challenge to acquire an accurate prole of these
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0165-9936/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.trac.2011.06.017
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Table 1. Brief description of the 33 most common target polycyclic aromatic hydrocarbons (PAHs) (16 + 17 compounds) Order PAHs Abbreviation Chemical formula CAS number Number of fused benzene rings Molar mass (g/mol) Structure
[A] 16 priority PAHs designated by the US Environmental Protection Agency (EPA): most commonly referred in this review 91-20-3 2 128 1 Naphthalene NAP C10H8 2 3 4 5 6 Acenaphthylene Acenaphthene Fluorene Anthracene Phenanthrene ACN ACL FLR ANT PHN C12H8 C12H10 C13H10 C14H10 C14H10 208-96-8 83-32-9 86-73-7 120-12-7 85-01-8 3 3 3 3 3 152 154 166 178 178
Fluoranthene
FLT
C16H10
206-44-0
202
Pyrene
PYR
C16H10
129-00-0
202
9 10 11
Benzo(a)anthracene Chrysene Benzo(a)pyrene
BAA CHY BAP
C18H12 C18H12 C20H12
56-55-3 218-01-9 50-32-8
4 4 5
228 228 252
12 13
Benzo(b)uoranthene Benzo(k)uoranthene
BBF BKF
C20H12 C20H12
205-99-2 207-08-9
5 5
252 252
14
Benzo(ghi)perylene
BGP
C22H12
191-24-2
276
15 16
Indeno[1,2,3-cd]pyrene Dibenz(a,h)anthracene
ICP DBA
C22H12 C22H14
193-39-5 53-70-3
6 6
276 278
[B] 17 PAHs based on their probable carcinogenic and mutagenic behavior by the World Health Organization (WHO) 17 18 1-Methylphenanthrene Benzo[a]uorene MPT BAF C15H12 C17H12 832-69-9 238-84-6 3 4 192 216
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Table 1. (continued) Order 19 PAHs Benzo[b]uorene Abbreviation BFR Chemical formula C17H12 CAS number 243-17-4 Number of fused benzene rings 4 Molar mass (g/mol) 216 Structure
20
Benzo[ghi]uoranthene
BGF
C18H20
203-12-3
226
21
Cyclopenta[cd]pyrene
CCP
C18H10
27208-37-3
226
22
Benzo[c]phenanthrene
BCP
C18H22
195-19-7
228
23
Triphenylene
TPN
C18H12
217-59-4
228
24
5-Methylchrysene
MCS
C19H14
3697-24-3
242
25
Benzo[j]uoranthene
BJF
C20H12
205-82-3
252
26
Benzo[e]pyrene
BEP
C20H12
192-97-2
252
27
Perylene
PRL
C20H12
198-55-0
252
28
Anthanthrene
ATT
C22H12
191-26-4
276
29
Coronene
COR
C24H14
191-07-1
300
30
Dibenzo[a,e]pyrene
DAP
C24H14
192-65-4
302
31
Dibenzo[a,h]pyrene
DHP
C24H14
189-64-0
302
32
Dibenzo[a,i]pyrene
DIP
C24H14
189-55-9
302
33
Dibenzo[a,l]pyrene
DLP
C24H14
191-30-0
302
harmful substances in environmental matrices, including the atmosphere. For the analysis of PAHs in air, gas chromatography (GC) has been the most common analytical separation mechanism in combination with a number of sampling
approaches and sample-preparation steps. The preference for GC over other systems [e.g., liquid chromatography (LC)] has been demonstrated by such factors as its greater selectivity, resolution, and sensitivity [3]. To improve selectivity and to ensure the robustness of
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sample identication and quantication, GC is often used in combination with mass spectrometry (MS) to produce very powerful GC-MS coupled techniques, which are able to yield even lower limits of detection (LODs) than GC alone. This review offers a critical evaluation of the stateof-the-art information on the methodological choices available for, and recent developments in, PAH analysis in air. We discuss the procedures involved in sampling and/or preconcentration, sample preparation, and nal determination (or detection) of PAHs in air, in order to assess and to review the nature of GC-based applications for their analysis. To this end, we initially discuss conventional solvent-based sample collection along with standard preparation methodologies. Moreover, we also evaluate simplied solvent-free methods, as alternatives to solvent-based methods, and compare for their applicability in this area. Finally, we give a detailed description of most of the essential components involved in the basic quality-assurance procedures required for the determination of PAHs in air.
Table 2. Common collection methods (media) for the analysis of airborne polycyclic aromatic hydrocarbons (PAHs) in particulate phase Collection/sorbent material [A] Solvent-based extraction (i) Glass ber lter (GFF) A B C E (ii) Quartz ber lter (QFF) B C D E (iii) Teon lters C (iv) Mixed lters XAD-4 coated glass denuder Teon-coated glass ber lter [17,40] [37] [36,39] [38]b [57] [29] [30,31,34,58] [25,32,54,55] [33] Target PAHs modea Ref.
B E
[47] [35]
2. The collection of PAHs For the collection of airborne PAHs in both vapor and particle phases, large volumes of air must be sampled to concentrate them on the sorbent material (vapor phase) or a suitable lter material (particulate matter). This is because their concentration in air at most locations is relatively low (of the order of ng/m3). The most common sorbent used for gas-phase enrichment is polyurethane foam (PUF). However, other sorbent materials (e.g., XAD-2, XAD-4, Carbopack C, and Tenax) have also been employed occasionally [1518] (Table 2). High-volume samplers are operated at sufciently high ow rates (34 1250 L/min) and for a long enough to guarantee sufcient sample volume for quantitative analysis (e.g., 150 900 m3 for gas phase and sometimes up to 3000 m3 for particle phase). Gas-phase samplers are usually protected from any particulate-phase material in the air sampled by the addition of a pre-lter at the start of the sampling train. In some situations where the aim of the study is analysis of both gaseous and particulate phases, this pre-lter may then be used for analysis of PAHs in the particulate phase, although the size-fraction characteristics of the collected particulate material will generally be unknown and unregulated (unless a size-selective inlet is employed). In addition, gas-phase PAHs may be sampled using traditional PM10 air samplers, where the sizefraction characteristics of the particulate phase sample are well known. In this case, the PUF cartridge sits in a tube beneath the lter that collects the PM10 particulate material. This is currently done at a limited number of monitoring sites as part of the UK PAH air quality
[B] Solvent free analysis (thermal desorption) (i) QFF A B (ii) Teon lter
a
[63] [23,59,61] [20]
Describes the combination of target PAHs commonly selected in many previous studies (A = some of 16 priority PAHs of US EPA, B = some of 16 + some extra, C = 16 PAHs only, D = 16 PAHs + some extra, and E = All PAHs except 16 PAHs). b Sampling with personal pumps.
monitoring network [19] (which assists the UK to comply with the European Fourth Air Quality Daughter Directive, that requires Member States to monitor for B[a]P and six other PAHs). Upon completion of air sampling, these sorbents and lter materials are treated with organic solvents (e.g., dichloromethane, toluene, hexane, acetonitrile, and methanol) either individually or in combination to extract target PAHs. Extraction can be performed by manual washing or via automated setups (e.g., Soxhlet extraction or accelerated solvent extraction). It is important to extract the PAHs from the sorbent material using as little solvent as possible in order to maximize the mass fraction of analyte in the solvent, thereby improving the overall method LOD. The nal determination of PAHs is then made, preferably with GC-MS. Many studies aiming to monitor PAHs in air have attempted to measure both particle and gas-phase PAHs simultaneously (Figs. 1 and 2). There are also a number of studies that have focused only on either one of the two, while many studies show a preference for the particulate phase [2026]. As the distribution of airborne
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Detection
MS
FID
ECD
Target PAHs
(A) Some of 16 PAHs
(B) Some of 16 PAHs + extra
(C) 16 priority PAHs only
(D) 16 priority PAHs +extra
(E) All extra
(E) All extra
Urban area
GFF + solvent desorption [29 ], QFF + TD [59]
GFF+ solvent based desorption[ 30, 58] Teflon & QFF +TD [23, 64]
QFF [36, 39], PTFE [17], GFF [25] + solvent desorption
GFF [31, 32, and 58] + solvent desorption
Teflon coated GFF [35], GFF + solvent desorpti on [33]
QFF + solvent desorption [39]
GFF + solvent desorption [33]
Industrial area
QFF + solvent desorption [38] QFF + solvent desorpti on [57] Teflon + solvent desorption [40]
Rural area
Indoor area
Lab and others
QFF + solvent desorption [37]

Figure 1. Plot of all possible combinations of detection and sampling methods for polycyclic aromatic hydrocarbons (PAHs) in the particle phase.
Detection
MS
FID
Target PAHs
(A) Some of 16 PAHs
(B) Some of 16 PAHs + extra
(D) 16 priority PAHs +extra
(E) All extra
(C)16 priority PAHs only
Urban area
Carbopack [15] and PUF [29] + solvent desorption
PUF and XAD + solvent desorption [47, 58]
XAD and PUF + solvent desorption [17, 36]
PUF + solvent desorption [ 31, 32]
PUF + solvent desorption [25]
PUF/XAD -2/PUF + solvent desorption [48]
Industrial area
Rural area PUF + solvent desorption [57] Indoor area XAD + solvent desorption [18] & GC-columns +TD [50] PUF + solvent desorption [40]
Lab and others
PDMS traps +TD [62]
PDMS alone & Mixed (PDMS +Tenax bed) + TD [49, 68]
Figure 2. Plot of all possible combinations between the detection and sampling methods for polycyclic aromatic hydrocarbons (PAHs) in the vapor phase.
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PAH basically occurs in both gas and particle-bound phases, all the sample-collection methods are designed to cover (1) each of the two fractions individually or (2) their sum fractions at the same time [27,28]. 2.1. Collection of particle-phase PAHs Because of complexities involved in the analysis of PAHs, some studies were simply conned to the particulate fractions to explore the distribution behavior of PAHs. For the collection of both particle-bound and particle plus gaseous PAHs in air, glass-ber lter (GFF) and quartz-ber lter (QFF) were used commonly (Table 3). However, on rare occasions, some other materials (e.g., Teon) were also employed individually or in combination (Table 3). When particulate-phase PAHs are sampled, it is usually the PM10 particulate phase of ambient air that is considered, since this is currently the size fraction most relevant to human-health studies and to regulation. Note that lter materials often used to
collect particulate samples for metals analysis (e.g., cellulose membranes) rarely have sufcient strength or porosity to sustain the very high ow rates used for sampling particulate-phase PAHs without damage or lter clogging. 2.1.1. Glass-ber lter (GFF). GFFs are the most frequently employed collection devices for particle-phase PAHs. The target PAHs mainly include 16 priority PAHs and their derivatives but are occasionally extended to additional PAHs; their sampling by GFFs has been made from diverse locations from rural to industrial areas. Although the total sample volume and ow rate set for their collection differ between studies, most have passed sufciently large volumes of air through these lter materials to ensure enrichment (for sufcient extraction) with the common analytical methods. Gustafson and Dickhut [29] made measurements of PAHs in air at four sites representative of rural,
Table 3. Common collection methods (media) for vapor-phase polycyclic aromatic hydrocarbons (PAHs) in air Collection/sorbent material [A] Solvent based (i) Polyurethane (PUF) B C D E (ii) XAD XAD-4 coated glass denuder XAD-2 (iii) Combination of PUF and XAD PUF/XAD-2/PUF (IV) Others Carbopack C (30 mesh, 400 mg)c Glass wool lter, condenser, glass ber lter, Teon lter, and a Tenax trapd [B] Solvent free (thermal desorber) (i) XAD XAD-2 (ii) Polydimethylsiloxane (PDMS) Quartz multi-channel PDMS traps PDMS traps (iii) Mixed sorbents Mixed sorbent beds ((PDMS foam + PDMs particle + Tenax bed) (IV) Others Fan-Loy sampler (SPB-5 GC columns (0.75-mm i.d. and 7-lm lm thickness)
a
Target PAHs modea
Ref.
[58] [29,36,40,55]b [31,32] [25,57]
B C
[47] [17]
[48]
A C
[15] [16]
[18]
A C
[62] [68]
[49]
[50]
Describes the combination of target PAHs commonly selected in many previous studies (A = some of 16 priority PAHs of US EPA, B = some of 16 + some extra, C = 16 PAHs only, D = 16 PAHs + some extra, and E = All the PAHs except 16 PAHs). b Personal monitors. c Diffusion-based sampling. d On-line.
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semi-urban, urban, and industrialized areas (southern Chesapeake Bay, USA). These authors actively passed 172365 m3 of air (ow rate = 510750 L/min) though GFFs to collect particle-phase PAHs. They were able to characterize 14 out of 16 priority PAHs over a wide concentration range (pgng/m3). Omar et al. [30] also collected 16 priority PAHs in airborne PM10 on GFFs from urban roadside and rural location (Kuala Lumpur, Malaysia). However, they used comparatively large sample volumes [i.e. $1612 3224 m3 (at ow rate of 1120 L/min)] to ensure their quantication at sub-ng/m3 level. In another report made by Mandalakis et al. [31], 20 PAHs (16 priority PAHs + Me-phenanthrenes, dimethylphenanthrenes, Me-chrysene, and COR) were collected on GFFs from diverse locations (an urban center, a background site, and the adjacent coastal area). These authors collected 450900-m3 air samples to ensure the enrichment of the particle-bound PAHs on GFFs. In a similar study, Tsapakis and Stephanou [32] collected 24 (16 priority + 8 others) particle-bound PAHs by passing 900 m3 of urban air (ow rate = 600 L/min) from an urban area in Heraklion, Greece, through GFFs. GFFs have also been employed to collect a number of PAH derivatives [e.g., oxy-PAHs and nitro-PAHs (often formed by PAH degradation see later)], apart from 16 priority PAHs. Castells et al. [33] used GFFs as the collection media for seven oxy-PAHs and nitro-PAHs present in urban-aerosol samples in Spain by using a very large sampling volume of 1440 m3 (ow rate = 1000 L/ min). In another study, diverse PAH components in PM (25 PAHs + 12 nitro-PAHs + four oxy-PAHs) were quantied via GFF sampling from a heavily trafcked square in Basel, Switzerland (sample volume = 960 m3 at a ow rate of nearly 666 L/min) [34]. On rare occasions, modications of GFFs have also been used for the collection of particle-bound PAHs. Dimashki et al. [35] used Teon-coated GFFs (often referred to as Emfab) to collect particle-phase PAHs from urban atmospheres in Birmingham, UK, and Damascus, Syria. The total volume of air passed through these collection devices was 9001000 m3 (ow rate = 650 750 L/min). 2.1.2. Quartz-ber lter (QFF). QFF is another preferred medium for the collection of particle-bound PAHs. Park et al. [36] collected 16 priority PAHs on QFFs (102 mm diameter) in an urban area of Seoul (Korea) using an active sampling method. Lottmann et al. [37] collected particulate PAHs (eight priority PAHs + COR) on QFFs (150 mm diameter) by drawing a total volume of 720 m3 (1250 L/min) at a university campus (Strasbourg, France). QFFs have also been employed to collect particle-phase PAHs with relatively low sampling volumes. Chaspoul et al. [38] attempted to collect 16 priority PAHs and six
nitro-PAHs simultaneously from industrial workplaces at a ow rate of 1 L/min on QFFs (total sample volume $0.5 m3). Chantara and Sangchan [39] used QFFs with a mini-volume air sampler to collect PAHs in PM10 from diverse urban areas. Note that QFFs can also be suitable as collection media for solvent-free methods [e.g., thermal desorption (TD)] {e.g., PAHs (many of the 16 priority PAHs) and oxy-PAHs in PM2.5 were collected on QFFs (sample volume = 24 m3 at a sampling ow rate of 1000 L/min) from an urban area of Germany (Augsburg City) prior to thermal desorption GC-MS analysis [23]}. 2.1.3. Teon lters and other media. Although not as common as other ber-type lters, Teon lters (e.g., 37mm diameter) are often reported for particulate-PAH collection. As one example, these lters were mounted in personal environmental monitors for the collection of PAHs in PM2.5 (sampling duration of 8 h). Their sampling was made from indoor locations divided into smoking and non-smoking zones [40]. The ow rate of these personal sampling pumps was 4 L/min (with a variability of 5%). In the light of its high thermal conductivity, aluminum foil has also been tested to sample particle-phase PAHs along with other semi-volatile organic compounds [41]. The authors collected urban PM10 samples on an aluminum-foil substrate installed in an Andersen eightstage cascade impactor at a ow rate of 28.3 L/min (50h duration). Prior to use, the aluminum foils were heated to 500C for 24 h. The authors stated that aluminum foil has very high efciency for thermal desorption, while QFF can suffer from pyrolysis of long-chain compounds during the thermal-desorption process. 2.1.4. Degradation of PAHs during sampling. It has been known for some time that, once particulate-bound PAHs become immobilized on air lters following sampling, they become much more susceptible to degradation from oxidizing compounds, particularly ozone, but also NO2, present in the sampled air, which are drawn through the collected PM. PAHs can be oxidized upon the reaction with ozone and NO2 to produce oxy-PAHs and nitroPAHs, respectively [42]. Such post-sampling reactions have been shown by Schauer et al. [43] to result in conversion of up to 50% of the sampled PAHs. This, in turn, may result in a substantial underestimation of the concentrations of PAHs present in ambient air. In order to determine the quantity of degradation present in the sampled PM, the analysis of oxy-PAHs and nitro-oxyPAHs must be undertaken which is considered more challenging [34]. In addition, there is expected to be a small quantity of these compounds present in ambient air as a result of gas-phase reactions between particulate-bound PAHs and oxidizing compounds in air. The degradation of PAHs on sampled lters is one of the main reasons that it is prudent to limit the length of sampling
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periods for each PAH sample so as to minimize the effect of oxidizing gases. Indeed, the European Fourth Daughter Directive [44] mandates Member States to use sampling periods of 24 h. Whilst the effect of degradation may be noticeable on short-term monitoring studies, it is thought that the effect on annual average values (e.g., those produced by xed air-quality networks) is likely to be small. As the annual variations in the concentration of PAHs and ozone are in anti-phase, there is very little effect on measured PAH concentrations. For example, in the winter (e.g., increased fuel use), PAH concentrations become high whilst ozone concentration is low. Conversely, in the summer when the ozone is high, PAH concentrations are low. Hence, although relative degradation rates can rise, these have little effect on the annual average. Moreover, judicious timing of the automatic lter-changeover facility on many of the current air-quality-monitoring samples can allow lter changes to occur at dawn, to take advantage of the diurnal variation in ozone concentrations and to achieve a large period of time during the night prior to sample changeover when ozone is low. Thus, the degradation to PAHs collected during the day, and subsequently overnight, is minimized. A full understanding of the role of ozone in PAH degradation is still being developed [45]. Recent developments to solve the ozone-degradation problem have included use of an ozone denuder in combination with the PM10 sampler [46]. This innovation removes ozone from the sampled air and prevents degradation of PAHs within the sampled PM. However, these devices may be less effective in humid and wet conditions, so the same group is currently working on an internal heater for the ozone scrubber to solve this problem. 2.2. Collection of gas-phase PAHs If we review the literature available for airborne-PAH analysis, the dominant portion is found to cover 16 target PAHs (of the US EPA) in both particulate and vapor phases. As the collection devices for particle-phase PAHs have been aforementioned, we now focus on the substances used for the collection of gas-phase PAHs in the following sub-sections. Because of the low concentrations of PAHs present in air, their collection usually relies on pumped sampling (where a known volume of air is drawn through the sorbent) rather than diffusive sampling (where vapor is allowed to diffuse into the sorbent). This is because diffusive samplers are in many times not simple to calibrate for quantitative analysis. 2.2.1. Polyurethane foam (PUF). PUF has been utilized as the most common means of enriching gas-phase PAHs. It is applicable for a wide range of PAHs (16 priority PAHs and many others, especially their nitro and oxy derivatives). Gustafson and Dickhut [29] collected gas-phase PAHs (14 out of 16 priority PAHs) on 1724
two PUF plugs by passing 172365 m3 of air (ow rate = 510750 L/min) at both rural and industrial sites. Mandalakis et al. [31] used a PUF plug (length = 8.0 cm, diameter = 7.5 cm) to enrich 20 PAHs (16 priority PAHs + four others) by passing 450 m3 and 900 m3 of air from diverse locations (an urban center, a background site, and the adjacent coastal area). In a similar study, Tsapakis and Stephanou [32] collected 24 airborne PAHs (16 priority PAHs + eight others) by passing 900 m3 of urban air (ow rate = 600 L/min) through PUF. The applicability of PUF samplers has also been demonstrated in the determination of diverse PAH derivatives (e.g., nitro-PAHs and oxy-PAHs) in the vapor phase. Dimashki et al. [35] used PUF (80 mm diameter, 75 mm depth, density = 0.02 g/cm3) to collect vaporphase PAHs; they used a sampling volume of 900 1000 m3 at a ow rate of 650750 L/min from two urban locations (Birmingham, UK, and Damascus, Syria). 2.2.2. Collection on XAD. As an alternative to PUF, Possanzini et al. [47] tested an XAD-4 (2060 mesh) coated-glass denuder (with QFF for particle) for the collection of gas-phase PAHs. They assessed collection efciency (and capacity) over 6-h sampling at an air ow rate of 6 L/min. The collection efciencies of two-ring and three-ring PAHs were found to exceed 90% [e.g., 90% (PYR)97% (NAP)]. 2.2.3. Mixed sorbents/others. For the collection of gasphase PAHs, PUF samplers have been used most intensively in combination with other sorbents (e.g., XAD-2). Lee et al. [48] used a glass cartridge containing a 5-cm PUF plug, followed by 3-cm XAD-2 resin, and nally a 2cm PUF plug to collect the gas-phase PAHs from an area affected by trafc activities. Bertoni et al. [15] proposed a molecular diffusion-based sampling device for the determination of gaseous PAHs in air. These authors used Carbopack C as the adsorbing material to enrich the PAHs for the GC-MS analysis after two months exposure of the sorbent in urban or suburban air. Wauters et al. [49] used a mixed sorbent bed {polydimethylsiloxane (PDMS) foam (1 cm), PDMS particles (120 mg), and a Tenax TA (60 mg)} for the collection of 16 priority PAHs by a personal air pump at a ow rate of 100 mL/min for 24 h. They compared their method to the classical method relying on high-volume sampling onto a PUF sampler for 24 h. The total volumes of samples collected by these methods contrasted between 144 L (mixed bed) and 1296 m3 (classic method). However, they found the new approach superior to the conventional method, as the new approach yielded much higher recoveries ranging from 1.2 times better for PHN to 35 times better for NAP despite the much smaller sampling volume.
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An online sampling system was also designed to collect the 16 priority PAHs emitted from a coal-red uidized bed combustor (sample volume = 60 L at a ow rate of 2.5 L/min). This system was built to combine a glass-wool lter (to remove particles), condenser (to remove water), GFF, Teon lter, and a Tenax trap (as the trapping device for PAHs) [16]. In addition, for assessing personal exposure to PAHs in urbancommunity settings, Fan et al. [50] prepared a honeycomb-like sampler with 320 sections of 1-cm long SPB-5 GC columns (0.75-mm i.d. and 7-lm lm thickness) and collected gaseous PAHs (NAP, ACN, ACL, FLR, PHN, ANT, FLT, and PYR) on the inner surfaces of the columns by molecular diffusion. Their method was sufcient to enrich these gas-phase PAHs for further analysis with TD-GC-MS.
3. Evaluation of recoveries for different extraction techniques As the analysis of PAHs generally relies on collection media for pre-concentration, regardless of their phase, one needs to know how effectively their extraction proceeds in the sampling stage. It has always been a challenge to extract all the target PAHs with sufciently good efciency due to large variations in their physicochemical properties (e.g., volatility and reactivity). The use of surrogate standards directly spiked to the sorbent or lter material before sampling (or after sampling if the samples are measured as received and losses during sampling are not considered) is usually recommended for recovery calculations. For example, the best surrogate standards are isotopically-labeled congeners (e.g., deuterated analogues of the PAHs being measured) [3]. It is important to bear in mind that, whilst isotopicallylabeled PAH congeners are expected to mirror almost exactly the physical and chemical properties of their non-isotopically labeled counterparts, because they are spiked onto collected PAHs, they can never exactly replicate the matrix of the as-collected sample. This is especially true for PAHs bound to particulate matter. The recovery of isotopically labeled congeners may, therefore, be slightly higher than that for the sampled PAHs although the inherent variability of recovery data makes it very difcult to draw such conclusions with condence. Although many studies dealing with PAH determination do not provide the full details of recovery data, numerous efforts have been directed to the estimation of extraction efciencies [51,52]. The results of such efforts can be examined for both the gas and particle phase. 3.1. Recoveries of solvent-based extraction for particlephase PAHs After the collection of airborne particulate PAHs, the lter samples are treated with a range of organic solvents
(e.g., hexane, dichloromethane, acetone and methanol) individually or in combination. Moreover, to enhance the recovery of PAHs from the lter materials, solventbased extraction is done by specialized apparatus (e.g., Soxhlet, microwave extraction, or ultrasonication) or other techniques (e.g., pressurized uid extraction) [53,54]. Gustafson and Dickhut (28) extracted PAHs from GFF samples by combining acetone, petroleum ether, and dichloromethane as extractants in a Soxhlet apparatus. The recoveries of surrogate PAHs (i.e. Anth-d10, BaAd12, and BaP-d12) were 92.6 22.1%, 103.1 9.5%, and 79.3 13.5%, respectively. Omar et al. [30] estimated recovery of particle-phase PAHs on GFFs with ultrasonication in dichloromethane as 50.899.7%. However, these authors also reported that the lighter PAHs (NAP, ACN, ACL, and FLR) could not be accurately identied by this method due to low recoveries and poor reproducibilities. By contrast, Zhang et al. [55] extracted particle-phase PAHs on GFF with hexane and cyclohexane and observed superior recovery rates of 84.5% (NAP) to 108% (BAP). The European Committee for Standardization (CEN) Working Group (TC264 WG21), which developed and wrote the reference method for benzo[a]pyrene measurement in air (the PAH subject to target-value assessment in Europe), found relatively little difference in performance between a number of solvents tested for their extraction ability. Indeed, most solvents and solvent combinations are allowed by the standard method, as long as they achieve satisfactory recoveries when analyzing NIST Standard Reference Material 1649a. However, their standard does make the following recommendations for preferred solvents, depending on extraction technique [56]: (1) Extraction under reux: toluene (2) Soxhlet extraction: toluene, dichloromethane, 1:1 hexane:acetone mixture (3) Microwave extraction: 1:1 hexane:acetone mixture (4) Accelerated solvent extraction: toluene, dichloromethane, 1:1 hexane:dichloromethane mixture (5) Ultrasonic extraction: toluene, dichloromethane As summarized in Table 2, many researchers have attempted to describe the extraction efciency of priority PAHs. Extraction efciencies may also be adversely affected if solid-phase extraction (SPE) and/or sample clean-up procedures are required prior to analysis. These are regularly required for ambient air samples because of frequent instances of carbonaceous and particulate contamination after extraction. However, unlike those common target PAHs, it has been an even greater challenge to acquire optimum recoveries for their derivatives (e.g., oxy-PAHs and nitro-PAHs) [34]. For instance, nitro-PAHs and oxy-PAHs from GFF lters were extracted in methanol/acetone with the assistance
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of a microwave [34]. They were further puried with SPE and analyzed by semi-preparative high-performance liquid chromatography (HPLC). The GFF recovery rates of nitro-PAHs and oxy-PAHs were in the range 8090%. Dimashki et al. [35] found relatively good recovery rates of particle-bound PAHs on GFFs in the range 6198%, when extracted via Soxhlet with dichloromethane. Albinet et al. [57] used QFFs for collecting nitro-PAHs and oxy-PAHs in the particulate phase. They extracted all the samples in dichloromethane and proceeded with an LC purication procedure on an SPE cartridge. The recovery rates of nitro-PAHs in the whole analytical procedure were estimated as 14% (1-nitronaphthalene) to 84% (7-nitrobenz[a]anthracene), while those of oxyPAHs were from 5% (1-naphthaldehyde) to 83% (benzo[b]uorenone). It is usual practice in particulate-based PAH studies to correct the nal results based on the recovery of the surrogate standards spiked into the real samples. Where there is a direct isotopic analogue measurement available for the target PAH in question, this is simple. Where there is no direct isotopic analogue measurement available for the target PAH in question, expert judgment needs to be used to choose the most appropriate isotopically-labeled PAH for performing the recovery correction. This is likely to be most chemically similar and closely-eluting isotopically-labeled PAH from the gas chromatogram. 3.2. Solvent-based recoveries of gas-phase PAHs As for lter materials for collecting particulate PAHs, sorbent materials for collecting gaseous PAHs can also be subject to extraction by organic solvents with the modication of various treatment techniques. Gustafson and Dickhut [29] estimated recoveries of surrogate PAHs (i.e. ANT-d10, BAA-d12, and BAP-d12) in PUF plugs. These authors found recovery rates of 89.3 18.5%, 100 20.7%, and 87.2 19.8%, respectively, based on Soxhlet treatment with acetone, petroleum ether, and dichloromethane (as extractants). Simcik et al. [58] achieved recovery rates of 78101% from surrogate standards treated on PUF after extraction with dichloromethane. Zhang et al. [55] collected gas-phase PAHs on PUF plugs and then extracted them with hexane and cyclohexane. They were able to yield recovery rates of 63.2% (Nap) to 108% (BaP). Supercritical uid extraction (SFE) with dichloromethane (plus ultrasonication) was employed to extract gas-phase PAHs from PUF [36]. The recovery rates of this application were 6995% (mean = 83%). For the analysis of gas-phase nitro-PAHs (from PUF), Dimashki et al. [35] employed Soxhlet apparatus in dichloromethane and found recovery rates of 5792%. By contrast, the recovery of PAHs from Carbopack C ranged from 53% (NAP) to 100% (CHY), when they
were extracted by a single solvent (toluene) at ambient temperature [15]. According to the above comparison, the recovery rates of gaseous PAHs vary over a wide range, depending upon both the types of extraction technique and the individual PAHs. However, compounds of low molecular mass with relatively high volatility (e.g., NAP) tend to show the lowest recoveries, regardless of phases (gas and particle). 3.3. Extraction efciency of solvent-free or thermaldesorption methods In recent years, many efforts were made to nd an alternative analytical procedure for PAHs. As most of the previous analyses generally relied on the classic, solventbased approach, more recent studies were directed toward use of solvent-free methods (e.g., TD systems). Datasets on the extraction efciency of these solvent-free methods are still scarce. In most cases, the reliability of such techniques cannot be assessed directly against those of conventional solvent-based methods, regardless of PAH-phase type. 3.3.1. Particle phase. Drooge et al. [59] evaluated recovery ratios of some particle-bound PAHs collected via QFFs based on comparative analysis between the standardized liquid extraction (LE) method and the TD method. In case of PHN and ANT, they found recovery ratios in the TD method higher than those in the LE method. However, the recovery of other PAHs in the TD method was comparable to those in the LE method. Bates et al. [60] were able to achieve their TD recoveries in the range 95.5% (BGP) to 99.1% (BAA) for samples collected on QFFs. In other research, Gil-Molto et al. [61] estimated the recovery ratios of 12 PAHs (NIST SRM1649a urban dust) on QFFs through comparative analysis by the TD method. They found the recovery ratios of particulate PAHs in the range 95.01% (ICP) to 99.59% (PHN). 3.3.2. Gas phase. In solvent-based methods, extractions of gaseous PAHs have been conducted almost solely from PUF. However, the solvent-free techniques (i.e. the TD method) are sufciently advanced to allow comparison between diverse sorbent materials. Wei et al. [18] used a microwave-assisted desorption (MAD) coupled to headspace solid-phase microextraction (HS-SPME) as a onestep sample-preparation method for PAHs with XAD-2 adsorbent. Although their method cannot be regarded as fully solvent-free, they were able to exclude the use of any toxic organic solvent. The eight target PAHs (out of 16 priority PAHs) on XAD-2 were then desorbed into ethylene glycol and evaporated into the headspace via microwave irradiation. These PAHs were then absorbed directly on an SPME ber in the headspace for nal
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detection by MS. Their study achieved a recovery rate of >80% under optimized extraction conditions. Fan et al. [50] estimated >85% recovery of eight gaseous PAHs (NAP, ACN, ACL, FLR, PHN, ANT, FLT, and PYR) from a honeycomb-like passive sampler (320 sections of 1-cm long SPB-5 GC columns) by a TD method. However, large variabilities were observed in the recoveries of FLT and PYR with relative standard deviations (RSDs) of 36% and 30%, respectively. These unstable trends were suspected to come from temperature inhomogeneity in the thermal-desorption system. Wauters et al. [49] found the recovery of 16 priority PAHs in the range of 80.5% (NAP) to 118% (BGP) through combined application of a mixed sorbent-bed and solvent-free TD-GC-MS analysis.
4. The solvent-based analysis of PAHs Most of the previous studies aiming to investigate the distribution of airborne PAHs (particle or gas phase) have relied on solvent-based analysis, once the initial collection of PAHs is completed on a suitable lter or sorbent material. The PAHs bound on those media are then extracted with organic solvents (in liquid phase) for the nal determination, preferably with GC-MS. These conventional methods have been employed successfully to describe the distribution pattern, source apportionment, and phase distribution (gas or liquid) of PAHs from diverse environmental settings (rural, urban, industrial, indoor, workplace, and laboratory conditions). In this section, we discuss the common and modied approaches adopted in the solvent-based determination of PAH concentrations, based on the key phase-classication criteria (i.e. particle and gas), as we did for sample-collection methods (Tables 4 and 5). 4.1. Solvent-based analysis of particle-phase PAHs Gustafson and Dickhut [29] were able to analyze 14 out of 16 priority PAHs using samples collected from diverse locations around southern Chesapeake Bay, USA. These authors conducted GC-MS analysis on particle-phase PAHs collected on GFFs after extraction in dichloromethane with the aid of ultrasonication. The GC-MSbased determination yielded PAHs in a concentration range of 0.58 pg/m3 (DBA at a rural site) to 0.86 ng/m3 (CHY in an industrial area). Omar et al. [30] reported BGP and COR as the most abundant PAHs in airborne PM10 from urban roadside and rural location (Kuala Lumpur, Malaysia) based on the GC-MS analysis after solvent-based extraction of PAHs on GFFs. Concentrations of 16 priority PAHs bound with PM10 samples (from diverse urban areas) were determined by a GC-MS method after extraction in acetonitrile with an ultrasonicator [39]. The MS was operated in single-ion monitoring (SIM) mode to quantify characteristic ions of
selected PAHs with the aid of the deuterated internal standard (closest to the analyte in molecular weight). They were able to report the mean concentrations of total PAH (sum of 16) in the range 2.7 ng/m3 (rural area) to 16.6 ng/m3 (trafc area). In another study, Park et al. [36] analyzed 16 priority PAHs in the concentration range 0.14 ng/m3 (ACL) to 4.89 (BBF) ng/m3, using GC-MS-based method after collection on QFFs and extraction in dichloromethane with ultrasonication. They used external PAH standards (16 PAHs in a mixture) to quantify the individual analytes by GC-MS analysis. Mandalakis et al. [31] monitored 20 PAHs (16 priority PAHs + Me-phenanthrenes, dimethyl-phenanthrenes, Me-chrysene, and COR) in samples collected from diverse locations (an urban center, an inland site and a coastal area). They analyzed the target PAHs in concentration range of 0.01 ng/m3 (Me-Chrysene in the inland area) to 7.48 ng/m3 (PHN in the coastal area) by GC-MS analysis in SIM mode after extracting the lter (GFFs) in hexane (Soxhlet extraction). In a similar study, Tsapakis and Stephanou [32] analyzed 24 particle-bound PAHs from an urban area of Heraklion, Greece. Extraction of PAHs collected on GFFs was done with hexane in Soxhlet apparatus, and 24 PAHs (16 priority PAHs + 8 additional ones) were quantied in a concentration range of 0.02 ng/m3 (FLR) to 3.27 ng/m3 (BGP) by GC-MS-based analysis in SIM mode. Numerous modications have also been introduced in the analytical procedures of solvent-based methods. Chaspoul et al. [38] attempted to analyze 16 priority PAHs and six nitro-PAHs simultaneously from industrial workplaces by GC-MS analysis following solventextraction (QFF samples). They used two different ionization modes in MS [i.e. electron-impact (EI) for priority PAHs and electron-capture negative ionization (ECNI) for nitro-PAHs]. These authors were able to analyze the nitro-PAHs and priority PAHs in the ranges 020414 ng/m3 and 6522180 ng/m3, respectively. Personal environmental monitors mounted with Teon lters were also used for particulate PAHs analysis from indoor locations divided into smoking and nonsmoking zones in Taiwan [40]. These authors could quantify airborne PAHs as the geometric mean of all 16 priority PAHs in particle phase (460 ng/m3) through a GC-FID-based determination. The analysis of nitro-PAHs and oxy-PAHs was accomplished by high-resolution GC combined with iontrap HRGC-MS2 [34]. This method was effective enough to monitor nitro-PAHs in the range 262 pg/m3, which was 10100 times lower than their oxy-PAH counterparts. A two-step supercritical-uid extraction (SFE) method was also developed for the analysis of oxy- and nitroPAHs present in urban aerosol samples (in Barcelona,
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Table 4. Applicability of gas chromatography (GC)-based methods in the analysis of polycyclic aromatic hydrocarbons (PAHs) in the airborne particle phase Target PAHs modea A Rural Urban Industrial B Urban Urban Urban background Urban bus terminal C Urban Urban Urban Urban Sub-urban area Indoor locations University campus D Urban Urban Urban Urban Industrial Coastal Coastal Background Rural E Urban Urban Rural
a
Environmental condition
Location Haven beach, Chesapeake Bay (USA) Hampton, Chesapeake Bay (USA) Elizabeth river, Chesapeake Bay (USA)
Period 19941995 19941995 19941995
Detection method GC-MS GC-MS GC-MS
Concentrations (ng/m3) 7.2 104 (DBA) to 0.32 (BBF) 1.98 103 (DBA) to 0.26 (BBF) 7.3 103 (DBA) to 0.43 (BBF)
Ref. [29] [29] [29]
Rome (Italy) Augsburg (Germany) Wiesbaden (Germany) USA
20022003 20022005 20062007
GC-MS GC-TOFMS GC-MS TOF-MS
0.9 (PRL) to 12 (NAP) 0.12 (Retene) to 1.06 (sum of benzouoranthenes) 0.032.36 (BAP) and 0.034.86 (Retene) 10 (PAHs) and 0.1 (nitroPAHs)
[47] [23] [59] [20]
Seoul (Korea) Campo Grand (Brazil) Chiang Mai (Thailand) Changsha (China) Beijing (China) Taichung (Taiwan) Ghent (Belgium)
19981999 1998 2004 2008 20052006 20002001 20052006
GC-MS GC-MS GC-MS GC-MS GC-MS GC-FID GC-MS
0.14 (ACN) to 4.89 (BBF) 8.94 to 62.5 (particle + gas) 0.92 to 1.70 (BAP) 0.013 (BKF) to 4.85 (PYR) 0.01 (ACN in summer) to 124 (PYR in winter) 460 (Geometric mean of 16 PAHs) 0.45 (DBA) to 116 (NAP)
[36] [17] [39] [25] [55] [40] [49]
Heraklion (Greece) Basle (Switzerland) Athens (Greece) Kuala Lumpur (Malaysia) France Chicago (USA) Athens (Greece) Athens (Greece) Kuala Lumpur (Malaysia)
20002002 1995 2000 19981999 20032004 19941995 2000 2000 19981999
GC-MS HRGC-MS/MS GC-MS GC-MS GC-MS GC-MS GC-MS GC-MS GC-MS
0.02 (FLT) to 3.27 (BGP) 3 104 (Nitro-NAP) to 0.528 (Anthroquinone) 0.05 (COR) to 0.68 (BBF) 6.28 (Total PAH) 8.5 (BAA) to 194 (ACN) lg/L 0.6945 (mean of 26 PAHs) 0.01 (DBA, COR, PRL) to 0.37 (CHY) 0.03 (ANT) to 0.22 (CHY) 0.30 (Total PAH)
[32] [34] [31] [30] [38] [58] [31] [31] [30]
Barcelona (Spain) Birmingham (UK) and Damascus (Syria) Maurienne valley (France)
2001 19951996 20022003
GC-ECD and MS GC-MS GC-MS
0.015 to 0.364 0.009 to 0.35 0.130.42 (oxPAHs) & 2 1047.67 102
[33] [35] [57]
Target mode (A = some of 16 priority PAHs of US EPA, B = some of 16 + some extra, C = 16 PAHs only, D = 16 PAHs + some extra, and E = All the PAHs except 16 PAHs).
Table 5. Applicability of gas chromatography (GC)-based methods in the analysis of polycyclic aromatic hydrocarbons (PAHs) in the airborne vapor phase Target PAHs modea A Rural Urban Urban Industrial B Urban Urban Coastal C Indoor locations Urban Urban Urban Sub-urban area University campus D Coastal Background Urban Urban E Urban Rural
a
Environmental condition
Location Haven beach, Chesapeake Bay (USA) Hampton, Chesapeake Bay (USA) Rome (Italy) Elizabeth river, Chesapeake Bay (USA)
Period 19941995 19941995 2000 19941995
Detection method GC-MS GC-MS GC-MS GC-MS
Concentrations measured (ng/m3) 5.8 104 (BAP) to 6.9 (PHE) 7.2 104 (BGP) to 124 (PHE) 2311743 (NAP), 1151 (PHN), 2.112.1 (FLT), and 9.239 1.74 103 (BKF) to 25 (PHE)
Ref. [29] [29] [15] [29]
Rome (Italy) Chicago (USA) Chicago (USA)
20022003 19941995 19941995
GC-MS GC-MS GC-MS
0.3 (BAP) to 687 (NAP) 27430 0.08 to 70
[47] [58] [58]
Taichung (Taiwan) Campo Grand (Brazil) Seoul (Korea) Tainan (Taiwan) Beijing (China) Ghent (Belgium)
20002001 1998 19981999 19911992 20052006
GC-FID GC-MS GC-MS GC-FID GC-MS GC-MS
$1010 (Geometric mean of 16 PAHs) 8.94 to 62.5 (particle + gas) 0.80 (BAA) to 15.03 (PHN) 192 (ACL) to 3040 (NAP) 0.79 (BAA in summer) to 2592.5 (NAP in Spring) 0.45 (DBA) to 116 (NAP)
[40] [17] [36] [48] [55] [49]
Athens (Greece) Athens (Greece) Athens (Greece) Heraklion (Greece)
2000 2000 2000 20002002
GC-MS GC-MS GC-MS GC-MS
0.01 (BAP) to 7.48 (PHE) 0.01 (Me-CHY) to 1.03 (PHE) 0.01 (BAP) to6.95 (Me-PHE) 0.001 (COR) to 19.8 (PHN)
[31] [31] [31] [32]
Birmingham (UK) and Damascus (Syria) Maurienne valley (France)
19951996 20022003
GC-MS GC-MS
0.01 (9-nitro-ANT) to 0.21 (1-nitro-NAP) 0.011.43 (oxi-PAHs) & 3 1042.2 102
[35] [57]
Target mode (A = some of 16 priority PAHs of US EPA, B = some of 16 + some extra, C = 16 PAHs only, D = 16 PAHs + some extra, and E = All the PAHs except 16 PAHs).
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Spain) by GC with electron-capture detection (ECD) coupled to MS [33]. The SFE method, applied to the analysis of oxy- and nitro-PAHs in urban aerosol samples, was able to identify 9-uorenone, 9,10-anthraquinone, 2-methyl-9,10-anthraquinone, benzanthrone, benz[a]anthracene-7,12-23 dione and 1-nitropyrene at a concentration range of 15364 pg/m3. Dimashki et al. [35] used Teon-coated GFFs to collect particle-phase PAHs from Birmingham, UK, and Damascus, Syria. These authors conducted the Soxhlet extraction in dichloromethane for subsequent GC-MS analysis and found nitro-PAHs in the range 0.13 0.42 ng/m3. 4.2. Solvent-based analysis of gas-phase PAHs Similar to the methods employed in the analysis of particle-phase PAHs, those developed for gas-phase PAHs have also relied on extraction of the sorbent material. Hence, gas-phase PAHs (e.g., PUF) extracted into some organic solvents can be subject to nal determination by GC-MS. Gustafson and Dickhut [29] measured gas-phase PAHs at four sites representative of rural, semi-urban, urban, and industrialized areas. They collected gas-phase PAHs on two PUF plugs. Those samples were extracted in organic solvents (e.g., acetone, petroleum ether, and dichloromethane) with Soxhlet apparatus and analyzed for 14 PAHs with deuterated PAH-surrogate standards. The extracts were then concentrated using rotary evaporation followed by evaporation under puried nitrogen. These samples were again extracted with hexane and cleaned using solid-liquid chromatography on silica gel for the nal determination using GC-MS. They characterized 14 out of 16 priority PAHs in a concentration range 0.58 pg/m3 (BAP at rural site) to 124 ng/m3 (PHN) in the urban area. In another study, Park et al. [36] collected 16 priority PAHs in gas phase using a PUF sampler in an urban area of Seoul, Korea. The analysis by a GC-MS method (in SIM mode) after extraction with dichloromethane (with ultrasonication) revealed gas-phase PAHs falling in the range 0.80 ng/m3 (BAA) to 15.03 ng/m3 (PHN). Mandalakis et al. [31] monitored 20 PAHs (16 priority PAHs + four others) in samples collected from diverse locations (urban center, an inland site and the adjacent coastal area). They could determine target PAHs in the range 0.01 (PHN) (Me-CHY in the inland area) to 7.48 ng/m3 (PHN in the coastal area) by combining extraction with hexane (in Soxhlet apparatus) and GCMS analysis. In a similar study, Tsapakis and Stephanou [32] collected samples of 24 PAHs (16 priority PAHs + eight others) in urban air on PUF, extracted them with hexane in Soxhlet apparatus, and analyzed them by GC-MS in SIM mode. They determined them in the range 0.001 ng/m3 (COR) to 19.8 ng/m3 (PHN). 1730
Bertoni et al. [15] also analyzed gas-phase PAHs in concentration range 2311743 ng/m3 (NAP), 11 51 ng/m3 (PHN), 2.112.1 ng/m3 (FLT), and 9.2 39 ng/m3 (CHY) in an urban area of Rome, Italy, with a combination of a passive sampling technique (Carbopack C as sorbent) and a GC-MS method. Dimashki et al. (35) analyzed nitro-PAHs in the gas phase by treatment of a PUF sample in dichloromethane with Soxhlet apparatus. They determined them in the range 0.01 ng/m3 (9-nitro-ANT) to 0.21 ng/m3 (1-nitro-NAP) in an urban area of Birmingham, UK, by a GCMS analysis in NICI mode.
5. Solvent-free methods for PAH analysis Solvent-based extraction methods, if employed in the determination of atmospheric PAHs, generally involve time-consuming, labor-intensive procedures, regardless of PAH-phase type. As this step requires the use of toxic organic solvents, it may cause added difculties with sample handling during the extraction stage [62]. To overcome such limitations, solvent-free methods (e.g., TD) have commonly been employed. Their applicability has been demonstrated in the analysis of VOCs and reduced sulfur compounds (RSCs) [63]. As for solventbased methods, the applicability of this technique may also be considered separately for gas-phase and particlephase PAHs. 5.1. Solvent-free analysis of particle-phase PAHs Two types of lters (i.e. QFF and Teon) have commonly been utilized for the collection of the particle-bound PAHs that are subsequently retrieved directly without using solvent. As an example of the use of a Teon lter for solventfree collection device, Bezebeh et al. [64] analyzed aerosol-particulate matter for some of the 16 priority PAHs and nitro-derivatives using laser-desorptionionization time-of-ight MS (LDI-TOF-MS). They collected aerosol particulate matter (PM2.5) on Teon lters from inside a bus terminal. The analytes were introduced into the LDI-TOF-MS by mounting a 3-mm diameter piece of the lter on a probe. The probe was rotated to allow the analysis of samples at multiple positions on the aerosol lter. The collection of a small sample volume (0.320.98 m3) and desorption and ionization with pulsed UV radiation at 266 nm resulted in detection of PAHs in the positive-ion spectra, while nitro-PAHs were detected in the negative-ion spectra. By applying this technique, they were able to quantify several priority PAHs (PYR, CHY, TPN, PRL, and DBA) and three nitroPAHs at nearly 10 ng/m3 and 0.1 ng/m3, respectively. QFFs have been employed frequently to collect particle-bound PAHs for subsequent solvent-free analysis. PM2.5 samples collected on QFFs from an urban area of
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Germany (Augsburg city) were analyzed for many of the 16 priority PAHs and oxy-PAHs by direct thermal desorption (DTD)-GC-TOF-MS [23]. For this purpose, the lter samples were cut into pieces (2.1 27 mm). Two lter sub-samples, each of which represented 1.1 m3 of sampled air, were placed into a GC-liner. Isotope-labeled reference compounds were added (for quantication), and liners were put into the cold injector. Desorption of target PAHs was accomplished at 320C (for 15 min). Based on this method, these authors quantied the target PAHs in the sub-ng/m3 range. In a similar study, a two-step TD injection system integrated into a GC-MS was applied as a solvent-free method for the determination of PAHs across a wide volatility range (PHN to BGP) from ambient air particles [59]. These authors collected PM10 samples on QFFs at high volume (720 m3 at 1250 L/min) and low volume (6.9 m3 at 38.3 L/min) from an urban location in Wiesbaden, Germany. These QFF samples were then cut into pieces, and one piece (corresponding to a high sample volume of 180 m3) was placed in a glass liner. After adding an internal standard, the lter piece was thermally desorbed in a TD unit interfaced with a GC-MS system. These authors determined PAHs in the concentration ranges of 0.032.36 ng/m3 (BAP) and 0.03 4.86 ng/m3 (Retene). Likewise, Gil-Molto et al. [61] relied on a TD method to analyze 12 (out of 16) priority PAHs on QFFs (in PM10 and PM2.5 samples), collected by low-volume samplers from the city of Elche, Spain. These lter samples were rolled and placed in TD tubes to desorb the target PAHs at 300C (for 10 min) in an automatic TD system interfaced with GC-MS. These authors successfully determined the PAHs in both PM2.5 and PM10 samples in the concentration ranges 0.020 ng/m3 (DBA) to 0.41 ng/m3 (CHY) and 0.002 ng/m3 (ANT) to 0.94 ng/m3 (BBF) , respectively. The reliability of the TD-GC-MS technique was evaluated for 46 ring PAHs collected on PM10 quartz lters [60]. Their TD device was equipped with a desorption oven connected to a Peltier-cooled, sorbent-packed, coldtrapping system. Through application of a two-stage focusing technique, they were able to achieve complete recovery of samples of a NIST urban dust [Standard Reference Material (NIST SRM 1649a)] at the 95% condence level based on the certied values supplied (except for BAA). For the speciation of organic components, including PAHs in ambient air, PM2.5 samples were analyzed by a TD-GC-MS method [65]. The authors collected PM2.5 samples on QFFs and cut two separate punches (8.1 mm in diameter, 0.518 cm2 in area) to load into the TD glass tube. The samples were then analyzed via thermal desorption combined with GC-MS. Based on this method, these authors quantied the PAHs in PM2.5 samples in
the range 0.02 ng/m3 (FLR) to 1.64 ng/m3 (ICP) from an urban area (Golden BC, Canada). Falkovich and Rudich [41] reported a direct sampleintroduction (DSI) method for lter or liquid samples into a GC injector for thermal desorption and subsequent GCMS analysis to identify a number of semi-VOCs, including 16 priority PAHs. Their sampling was conducted on aluminum foil (preferred over QFFs by these authors) to be desorbed in micro-vials inside the GC injector (temperature 400450C). For quantication of target PAHs, 2 lL of the PAH standard solutions (EPA 610 mixture) contained in micro-vials were thermally desorbed and similarly analyzed on aluminum foil. In this way, they were able to quantify PAHs in the concentration range 0.005 ng/m3 (PYR) to 0.34 ng/m3 (PHN) in PM10 samples collected from an urban area in Tel Aviv, Israel. In an effort to improve a solvent-free quantication method for particle-phase PAHs, Waterman et al. [66] conducted a TD-GC-MS analysis of NIST SRM1649a (urban dust). They prepared samples with a known quantity of urban dust in a glass-lined, stainless-steel GC liner (cleaned at 600C for 5 min) for thermal desorption. The samples vaporized from the liner were then focused on a cold trap (196C with liquid nitrogen) and ash heated from 196 to 300C for 20 s for subsequent GC-MS analysis. They were able to conrm that the values that they obtained agreed with the certied values at the 95% condence interval. As a solvent-free technique, direct HS-SPME (with a PDMS ber) was also developed for the determination of particulate PAHs collected on Teon-coated GFF [67]. HS-SPME extractions were performed in 0.6 mL of 20% sodium sulfate in deionized water. The extraction was conducted in two steps: (1) equilibration of the lter (with PAH sample) and the liquid phase (sodium sulfate in water) and (2) SPME extraction at 50C for 120 min. These authors were able to quantify the 16 priority PAHs in the concentration range of 0.20 (ANT) to 1.8 ng/m3 (PYR) in PM10 samples collected from an urban area in Brazil (Sao Paulo city) by GC-MS analysis. 5.2. Solvent-free analysis of gas-phase PAHs For solvent-free analysis of gas-phase PAHs, many types of sorbent materials have been tested and evaluated, either individually or in combinations. Baltussen et al. [68] proposed an analytical method for gas-phase PAH analysis based on enrichment of the solutes on a packed bed of 100% PDMS particles, followed by TD-GC-MS. The PDMS material exhibited excellent thermal stability even after 200 consecutive runs. Using the above method, they were able to determine 16 priority PAHs in the concentration range of 0.50 ng/m3 (BAP) to 129 ng/m3 (ACL). Recently, a novel analytical method for atmospheric PAHs was developed based on laser-induced uorescence (LIF) of samples on quartz multi-channel PDMS traps
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with the aid of diffusion-based sampling. The method allowed the rapid (<5 min), cost-effective analysis of samples [62]. However, small amounts of naphthalenephotodegradation products (phenol, benzyl alcohol, and phthalic anhydride) were also identied by TD-GC-MS after >15 min irradiation. MAD coupled to headspace solid-phase microextraction (HS-SPME) has been studied for in-situ, onestep, sample-preparation step for PAHs collected on XAD-2 adsorbent for subsequent GC-MS analysis [18]. The PAHs on XAD-2 were desorbed into the extraction solution (ethylene glycol), evaporated into the headspace by microwave irradiation, and absorbed directly on a SPME ber in the headspace. PAHs were then analyzed by desorbing the ber in the injection port. This method was applied to collect smoke samples from the indoor burning of joss sticks [18]. The quantities of PAH determined via this approach were in the range 0.795 2.53 ng. Wauters et al. [49] used a mixed sorbent bed (i.e. PDMS foam, PDMS particles, and a Tenax TA bed) for the collection of 16 priority PAHs in the gas phase. Quantitative analysis of those samples was then made by TD-GC-MS. They also compared their method to the classical method that typically relies on the high-volume sampling (on GFF followed by PUF) for 24 h. These authors could monitor the 16 priority PAHs in the concentration range 0.45 ng/m3 (DBA) to 116 ng/m3 (NAP) from the sample collected inside the university campus at Ghent, Belgium. A sensitive, solvent-free method was also developed to quantify personal exposure to gaseous PAHs (NAP, ACN, ACL FLR, PHN, ANT, FLT, and PYR) via passive sampling with a lab-made sampler [50]. They were then able to analyze gas-phase PAHs in the concentration range 1.92600 ng/m3 by a TD-GC-MS-based analysis.
6. Evaluation of basic quality assurance in PAH analysis Considering that airborne PAHs are present at very low concentrations (at or below the ng/m3 range), the most important parameter for the basic quality assurance (QA) is LOD, which is often expressed in terms of absolute mass (e.g., ng) and/or mass per volume (e.g., ng/m3). Although most of the studies dealing with PAH analysis relied on GC-MS, the magnitude of LOD values varied noticeably, depending upon the analytical conditions and instrumental set-ups. Moreover, it also varied between the PAH phases (e.g., gas or particle). It is also an important consideration that, because GC-MS is a highly specic technique, whereby an analyte is only detected if it elutes from the GC at the right time, and, in addition, exhibits the molecular ion fragment being monitored in MS, LODs based on the standard formula of 1732
three times the standard deviation of the blank responses are sometimes very difcult to calculate. On occasions where the blank response is too low, other methods to calculate the LODs based on t-for-purpose uncertainty assessment, and sample adulteration with impurities have been used [69]. If the LOD values are to be expressed in concentration terms to yield a method LOD, the volume of total samples is also a critical variable to assess. In addition, the LOD will be affected by many other method parameters (e.g., the reduced volume of the nal extract and the volume injected into the GC-MS) [70]. To provide an overview of the normal detection range of PAHs across different analytical approaches, the LOD values of different studies are compared in Table 6 (particle) and Table 7 (vapor phase). As shown in Table 6, the LOD values for particle-phase PAHs varied over the ng to sub-ng range. Although these LOD values are also variable across individual PAHs, the data for each PAH are rather scarce. In addition, most studies reported a range of LOD values for their analysis instead of each individual one. Simcik et al. [58] calculated LOD values for 10 target PAHs (seven of 16 priority + three extra) in the particlephase and reported their LOD range as 0.00259 ng based on GC-MS analysis (after solvent treatment). Comparatively high LOD values were often reported for some lighter PAHs with high volatility (e.g., NAP). Possanzini et al. [47] reported an LOD value of 5.9 ng for NAP in the particulate phase, which was an order of magnitude greater than their ANT value (0.3 ng); these authors also relied on a solvent-based GC-MS analysis. Although a wide variation in LOD values was reported for many individual PAHs, some authors also found a relatively narrow range of LODs across different individual PAHs (Table 6). Van Drooge et al. [59] could achieve a limit of quantication (LOQ) value near 0.08 ng for most of the 16 priority PAHs in particle phase, based on a two-step TD and GC-MS method. In a similar study, Gil-Molto et al. [61] also found their LOD values in the sub-ng range (0.010.5 ng) for 16 priority PAHs in particle phase by TD-GC-MS analysis. According to our assessment of a large number of LOD values, the values for vapor-phase PAHs generally fell near, or below, the ng range. Lee et al. [48] reported LOD values for 16 priority PAHs in the range 0.070.15 ng with a solvent-based GC-MS analysis. In another study, Wei et al. [18] reported LOD values in the range 0.02 1 ng using an HS-SPME-GC-MS method. Possanzini et al. [47] also found relatively high LOD values in vapor phase [i.e. 1 ng (CHY) to 15.3 ng (NAP) by a GC-MS method (solvent-based)]. Likewise, Simcik et al. [58] found a comparatively wide range of LODs for vaporphase PAHs (i.e. 0.0021406 ng) in a solvent-based GCMS analysis. Apart from these PAHs, Albinet et al. [57] achieved LOD values for PAH derivatives in sub-pg
Table 6. Compilation of basic quality assurance (QA) data for the analysis of airborne polycyclic aromatic hydrocarbons (PAHs) in the vapor phase Target PAHs modea Extraction (Solventbased or Solvent free) Pretreatment and sample loading Detection method LOD Flow rate (L/min1) 510750 Sampling volume (L) 172,000 665,000 Absolute mass (ng) Concentration (ng/m3) 1.27.9 104 Precision (% RSD) Recovery (%) Ref.
A Soxhlet extraction with acetone, ether, and dichloromethane No No Ethylene glycol DI GC-MS 79.3 to 103 [29]
No Toluene
Thermal desorption Laser induced uorescence (LIF) Microwave assisted desorption & HS-SPME (PDMS-DVB ber) Thermal desorption DI
GC-MS GC-MS GC-MS 1.4 420 0.02 to 1
0.3 1000 4 to 14 80108
[62] [62] [18]
GC-MS GC-MS
12 to 25 1.0 94100, 8587, 6177, and 5359
[50] [15]
B Soxhlet extraction with dichloromethane methanol Soxhlet extracted with dichloromethane C Hexane:methylene chloride with sonication Dichloromethanemethanol with ultrasonication Hexane Dichloromethane with ultrasonication Soxhlet with hexane and cylcohexane Soxhlet extraction with mixture of n-hexane, acetone, and dichloromethane in 2:1:1 mixture) PDMS traps Sorption tubes (PDMS foam + PDMs particle + Tenax bed) DI DI GC-FID GC-MS 4 34 32 146880 0.17 to 0.49 lg/mL below 10 (except PHE, 20) 85115 [40] [17] DI GC-MS 6 36 1 (CHY) to 15.3 (NAP) 0.0021460 4 to 9 9097 [47]
DI
GC-MS
78 to 101
[58]
DI DI DI
GC-MS GC-MS GC-MS GC-FID
2.5
60
110 ppb
below 5
95.1 83 63.2 (Nap) to 108 (BaP)
[16] [36] [55] [48]
1.3
624 0.071 to 0.153
0.3 (BAA) to 170.5 (NAP) 0.6 to 6.7
TD TD
GC-MS GC-MS
0.1
144
0.1 0.007 (ANT) to 0.026 (NAP)
3.7 (PYR) to 12.9 (NAP)
80. 5 (NAP) to 118 (BGP)
[68] [49]
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1733
(continued on next page)
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(oxy-PAHs) to sub-ng range (nitro-PAHs) in both particle and gas phase through application of a solvent-based GC-MS method. Although the absolute LOD reects the most important feature of any analytical method, it can be manipulated to a certain degree by altering the initial volume of air sampled. Hence, for comparison of LODs in a practical sense, they should be compared in terms of both absolute mass and mass concentration (e.g., ng/m3). If the available research is surveyed from this aspect, most studies were able to quantify PAHs at ng/m3 or even pg/m3 levels (Tables 6 and 7). As another important QA parameter, reproducibility expressed in terms of relative standard deviation (RSD%) can be examined across different studies. If the data on PAHs are compared from this aspect, they vary greatly across individual compounds as low as 2% in case of FLT and as high as 28% for ANT in a TD-GC-MS analysis of particle-phase PAHs in NIST SRM1649a (urban dust) [61]. Likewise, it was below 10% for all the 16 priority PAHs, except for PHN (20%) in both particle and gas phases, when analyzed by a solvent-based GC-MS method for indoor-air samples [40]. Interestingly, in vapor phase, the lowest values were 3% (PHN), while the highest was 14% (PYR) [18]; these authors used a microwave-assisted HS-SPME-GC-MS method. Wauters et al. [49] assessed the reproducibility of their TD-GC-MS analysis for 16 priority PAHs and found them in the range 3.7% (PYR) to 12.9% (NAP), with an average of 7.4%. Hence, the reproducibility of PAH analysis is generally seen to be maintained near or below the 10% level (RSD). However, on certain occasions, this TD-GC-MS method suffered from relatively poor reproducibility, especially for lighter PAHs, regardless of phase type. Although still fairly rare, some studies aimed to compare the relative performance between emerging TDbased methods and conventional solvent-based methods as a means to warrant reliability in PAH determination. Wauters et al. [49] compared their TD-GC-MS method to the classical method for quantitative analysis of the 16 priority PAHs. They found that concentrations measured using the new method were signicantly higher than those obtained using the classical method (i.e. a factor 1.23 for the high molecular weight PAHs). Moreover, those differences were extended further for lighter PAHs up to 35 times for NAP and 23 times for ACL. In another study, Van Drooge et al. [59] assessed the detectability of both conventional solvent extraction and a new TD-based method interfaced with a GC-MS system. The TD method was reported to have lower uncertainties than the conventional solvent-based extraction method, if the analysis of more reactive PAHs is made at similar concentrations (e.g., BAP); the use of TD methodology instead of the solvent-based method enabled the reduction of the analytical expanded uncertainty from 19% to
[35]
[31]
[32]
[57]
Ref.
Table 6. (continued)
Target PAHs modea
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Target mode (A = some of 16 priority PAHs designated by US EPA, B = some of 16 + some extra, C = 16 PAHs only, D = 16 PAHs + some extra, and E = All the PAHs except 16 PAHs).
Precision
Concentration (ng/m3)
(% RSD)
0.001
Sampling volume (L)
Flow rate (L/min1)
450,000 900,000 900,000
900,000 1000,000 GC-MS DI Soxhlet extraction with dichloromethane Pressurized liquid extraction with dichloromethane/Liquid chromatography purication with SPE cartridges Cool splitless injection (40320C) GC-MS 1250
Detection method
Pretreatment and sample loading
GC-MS
Extraction (Solventbased or Solvent free)
Soxhlet extraction with hexane Soxhlet extraction with hexane
DI
DI
GC-MS
600
0.01-2.60 pg (ox PAHs) and 0.03-0.07 (nitroPAHs)
LOD
Absolute mass (ng)
1484 (NitroPAHs) & 5-83 (oxPAHs)
Recovery
(%)
Table 7. Compilation of basic quality assurance (QA) data for the analysis of airborne polycyclic aromatic hydrocarbons (PAHs) in the particle phase Target PAHs Solvent-based/Solvent modea free Extraction (Solventbased or Solvent free) A Solvent free Soxhlet extraction with acetone, ether, and dichloromethane B Soxhlet extraction with dichloromethane methanol Soxhlet-extraction with dichloromethane/nhexane No DI GC-MS 6 36 0.3 (ANT) to 5.9 (NAP) 4 to 9 [47] TD DI GC-MS GC-MS 510750 172,000 to 665,000 26 mg/kg 1.27.9 104 79.3 to 103 [66] [29] Pretreatment and sample loading Detection method LOD Flow rate (L/min) Sampling volume (L) Absolute mass (ng) Concentration (ng/m3) Precision (% RSD) Recovery (%) Source
Flash chromatography with silica gel + toluene/ hexane as solvent 2 step thermal desorption TD TD DI Laser desorption ionization (LDI)
GC-MS
1250
720,000
81
[37]
GC-MS
38.3 and 1250 6900 and 720,000
0.084.0
No No Soxhlet extracted with dichloromethane No
GC-MS GC-MS GC-MS TOF-MS
$38.3
0.010.05 0.010.05 0.00259 320980 0.01
8 to 16 (analytical uncertainty) 3.84 to 14.76 2 to 28 (Anth)
[59]
more than 95 more than 95 78 to 101
[61] [61] [61] [61]
2.7
C Dichloromethane with ultrasonication Hexane:methylene chloride with sonication Dichloromethanemethanol with ultrasonication Soxhlet extraction with hexane and cyclohexane Acetonitrile with utltrasonication Acetonitrile with utltrasonication Ultrasonic agitation in dichloromethane DI DI DI GC-MS GC-FID GC-MS 4 34 146880 88 0.17 to 0.49 lg/mL below 10 85115 (except Phe, 20) [36] [40] [17]
GC-MS DI DI DI GC-FID GC-MS GC-MS
100
86400
100
48000
0.001 (DBA) to 0.74 (NAP) 1.6 (CHY) to 6.2 (ICP) 0.12 (FLR) to 0.45 (ANT) 0.003 (ACL) to 0.508 (PHE)
84.5 (NAP) to [55] 133.1 (BAP) [39] 44 (NAP) to 121 (DBA) 7388 [39] [25]
Trends
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Table 7. (continued) Target PAHs modea Solvent-based/Solvent free Extraction (Solventbased or Solvent free) Pretreatment and sample loading Detection method LOD Flow rate (L/min) 600 1 Sampling volume (L) 900,000 240480 Absolute mass (ng) Concentration (ng/m3) 0.001 4.2 to 16 (Coefcient of variation) 8090 0.00259 450,000 900,000 $1612,000 3224,000 78 to 101 Precision (% RSD) Recovery (%) Source
D Soxhlet extraction with hexane Soxhlet extraction with dichloromethane Microwave assisted methanol-acetone Soxhlet extracted with dichloromethane Soxhlet extraction with hexane Dichloromethane with ultrasonication E Supercritical uid extraction Soxhlet extraction with dichloromethane Pressurized liquid extraction with dichloromethane/Liquid chromatography purication with SPE cartridges
a
DI DI
GC-MS GC-MS
[32] [38]
DI DI DI DI
HRGC-MS/MS GC-MS GC-MS GC-MS
$666
960,000
[40] [58] [31]
$1120
50.77 to 99.70
[30]
Direct injection (DI) Cool splitless injection (40320C)
GC-ECD and MS GC-MS GC-MS
1000
1,440,000 900,000 1000,000
[33] [35] 0.012.60 pg (ox PAHs) and 0.030.07 (nitroPAHs) 1484 (NitroPAHs) & 5-83 (oxPAHs) [57]
1250
Target mode (A = some of 16 priority PAHs designated by US EPA, B = some of 16 + some extra, C = 16 PAHs only, D = 16 PAHs + some extra, and E = All the PAHs except 16 PAHs).
Trends
8% [59]. Based on the initial results of TD methods, it appears that TD can be a superior choice for certain PAHs; however, acquiring good recovery of all the major individual PAHs is still a challenge, as it is sensitive to the physicochemical properties of individual PAHs. In fact, quality control (QC) parameters have been considered in the European standard method for benzo[a]pyrene analysis [56]. Indeed, to highlight the difculty of these measurements, it is worth noting that the target relative expanded uncertainty for these measurements is 50% of which only about one tenth is attributable to the air sampling. Furthermore, this document states that, even if laboratories are highly procient at an individual analysis technique, it is still possible to nd signicant between-laboratory variability between expert laboratories using the same or different methods. This may contribute to the overall uncertainty of the method. Full uncertainty budgets for the GC-MS analysis of PAHs and similar organic compounds are available [71]. The key QC parameters highlighted in the European reference method EN 15549 are: (1) Reagent-blank checks (of solutions and collection media) to ensure blank levels remain acceptably low. (2) Calibration-drift check. Following calibration with a standard of known composition to establish the sensitivity of the analyzer, it is recommended that a representative calibration standard is remeasured every 10 samples to check for drift in the analyzer response. If necessary, a drift correction may be performed. (3) Measurement of QC solutions on a regular basis and plotting the results on a QC chart to ensure that the methods remains under control, and to take corrective action, if necessary. (4) Assessing the performance of the method by regularly measuring reference materials (e.g., NIST SRM 1649b or the newly released European Union reference material ERM-CZ100) (5) Correction of the reduced extract volume by means of a known quantity of added internal standard (usually a deuterated PAH). This accounts for the volume of the extract following rotary evaporation or similar techniques being unlikely to be exactly the same every time. Ratioing of the analytical response to the response obtained from the internal standard corrects for this. (6) Use of surrogate standards to correct for losses during extraction and sample preparation (as described earlier). (7) Regular participation in interlaboratory comparison to assess competency and external quality assessment by relevant accreditation bodies (e.g., UKAS in the UK).
7. Summary and concluding remarks Considering the potential health impact of airborne PAHs, an accurate assessment of their concentration levels in target environmental settings is crucial to establish their proper management, to assess abatement strategies and to develop future policy options. As the physicochemical properties of PAHs vary between lighter and heavier compounds, they are fractionated differentially between gas phase (lighter with high volatility) and particle phase (relatively heavy PAHs). As such, a suite of PAHs can exhibit noticeable differences in concentration levels in line with their molecular weights. For this reason, it has often been a challenge to develop precise techniques to measure their distribution in a particular environment. In line with technological advancement in analytical methodologies, we can quantify airborne PAHs, along with other harmful air contaminants, at trace level quantities (at or below ng/m3). As is the case for the most common organic contaminants (e.g., VOCs), GCbased methods are by far the most reliable for the analysis of airborne PAHs with a selected preconcentration (or treatment) method. However, due to their semi-volatile nature, high molecular weight, and different reactivities across gas or particle phase, the PAHs cannot be analyzed without establishing proper analytical protocols for their nal determination with robust QA procedures. This involves the collection of gas-phase PAHs on sorbents (e.g., PUF) or particle-phase PAHs on some lter materials (GFF or QFF) preferably in different size fractions (i.e. PM10 or PM2.5) relevant to exposure mechanisms (e.g., inhalation). To this end, sufciently large volumes of air are required to pass through highvolume samplers to collect enough material to analyze with t-for-purpose uncertainty. After collecting PAHs on sorbent or lter, extraction is normally accomplished with a number of organic solvents with Soxhlet or ultrasonication treatments. These conventional solvent-based methods have been successfully used to retrieve a wide range of PAHs [16 priority PAHs + other PAHs + their derivatives (e.g., nitro and oxy)] from various environmental settings. However, the extraction efciencies are often highly uncertain, and those values presented are rarely comparable across different studies and different methods. The most noticeable variation in recovery rates of PAHs is observed most commonly for lighter ones or PAHs with high volatility (e.g., NAP). Figs. 1 and 2 present common combinations of sampling and analysis strategies employed by previous researchers for PAHs in particle phase and gas phase, respectively. Due to the complexities involved in the multi-step procedure of sample preparation (for PAHs), the use of toxic organic solvents, and eventually the probable
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chances of analyte loss, there have been a number of efforts to develop solvent-free analysis of PAHs. These solvent-free methods rely on the collection of the airborne PAHs on sorbent or lter materials for subsequent release by the thermal desorption. Although these methods are still in development, initial results have shown a number of advantages (e.g., improved recovery and reduced analytical uncertainty) over conventional methods, especially for lighter PAHs (e.g., NAP and ACL). Moreover, these methods do not require the high sample volume (or sampling time), that is a prerequisite for conventional methods. For the nal determination of these airborne PAHs in gas and particle phases, GC-MS has been most commonly selected. When we compared the LODs of PAH analysis across different studies, the GC-MS method was reliable to determine the concentrations of PAHs and their derivatives at the sub-ng level (in absolute terms), irrespective of the sample-preparation method. Although the LODs of all individual PAHs varied to a certain degree across different studies, most of these studies were able to quantify airborne PAHs at sufciently low concentrations (e.g., pg/m3 level in remote rural, coastal, or pristine areas). However, they have also shown many discrepancies in terms of recovery or reproducibility, depending mainly on the nature of the individual PAHs in association with possible bias in their collection and/ or sample-preparation steps. In recent years, many efforts have been made to test the compatibility between conventional solvent-based methods and emerging TD-based methods. These comparisons have often shown the superiority of TD-based methods [e.g., reduced analytical uncertainty, improved recovery, requirement for smaller sample volumes (or shorter times), and no use of toxic organic solvents]. However, these methods are conned to a relatively narrow window of target PAHs relative to the conventional ones. Hence, future research should warrant evaluation of suitable sorbent materials with such considerations as: expansion of the method to cover more target PAHs and enhanced breakthrough capacity. Moreover, one also needs to establish some effective measures to check the accuracy of results between conventional solvent-based methods and emerging solvent-free methods. This would probably help us understand the atmospheric behavior of these toxic substances in a more meaningful way and offer a stronger basis to establish strategies for their management.
References
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Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

A review of techniques for the determination of polycyclic aromatic hydrocarbons in air

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Benzo(a)anthracene Chrysene Benzo(a)pyrene

BAA CHY BAP

C18H12 C18H12 C20H12

56-55-3 218-01-9 50-32-8

228 228 252

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

[63] [23,59,61] [20]

(A) Some of 16 PAHs

(B) Some of 16 PAHs + extra

(C) 16 priority PAHs only

(D) 16 priority PAHs +extra

(E) All extra

(C) 16 priority PAHs only

(E) All extra

GFF + solvent desorption [29 ], QFF + TD [59]

QFF [36, 39], PTFE [17], GFF [25] + solvent desorption

GFF [31, 32, and 58] + solvent desorption

Teflon coated GFF [35], GFF + solvent desorpti on [33]

QFF + solvent desorption [39]

GFF + solvent desorption [33]

GFF + solvent desorption [29]

GFF + solvent desorption [55]

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

GFF + solvent desorption [29]

Lab and others

QFF + solvent desorption [37]

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

(A) Some of 16 PAHs

(B) Some of 16 PAHs + extra

(C) 16 priority PAHs only

(D) 16 priority PAHs +extra

(E) All extra

(C)16 priority PAHs only

Carbopack [15] and PUF [29] + solvent desorption

PUF and XAD + solvent desorption [47, 58]

XAD and PUF + solvent desorption [17, 36]

PUF + solvent desorption [ 31, 32]

PUF + solvent desorption [25]

PUF/XAD -2/PUF + solvent desorption [48]

PUF + solvent desorption [29]

PUF + solvent desorption [55]

Lab and others

PDMS traps +TD [62]

PDMS alone & Mixed (PDMS +Tenax bed) + TD [49, 68]

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Target PAHs modea

[58] [29,36,40,55]b [31,32] [25,57]

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Trends in Analytical Chemistry, Vol. 30, No. 11, 2011

Period 19941995 19941995 19941995

Detection method GC-MS GC-MS GC-MS

Ref. [29] [29] [29]

Rome (Italy) Augsburg (Germany) Wiesbaden (Germany) USA

20022003 20022005 20062007

GC-MS GC-TOFMS GC-MS TOF-MS