Sampling

Journal of Chromatography A, 1216 (2009) 29722983
Contents lists available at ScienceDirect
Journal of Chromatography A
journal homepage: www.elsevier.com/locate/chroma
Review
Sampling and analysis of pesticides in ambient air

V. Yus a, , C. Coscoll a , W. Mellouki b , A. Pastor c , M. de la Guardia c
a
Public Health Laboratory of Valencia-CSISP, 21 Avda Catalu

na, 46020 Valencia, Spain
ICARE-CNRS, 1C Avenue de la Recherche scientique, 45071 Orleans cedex 02, France
c
Analytical Chemistry Department, University of Valencia, Edici Jeroni Mu
noz, 50 Dr. Moliner, 46100 Burjassot, Valencia, Spain
b
a r t i c l e
i n f o
Article history:
Received 22 December 2008
Received in revised form 5 February 2009
Accepted 9 February 2009
Available online 13 February 2009
Keywords:
Pesticides
Ambient air
Sampling
Analytical methods
Review
a b s t r a c t
Developments in the sampling and determination of pesticides in ambient air have been discussed and
data on the occurrence of pesticides in atmosphere have been presented. Developments in active sampling
methods were reviewed and the different materials used for trapping pesticides from gas and particulate
phases were discussed. Likewise, the use and developments of passive air samplers were reviewed. This
article pays special attention to the analysis of pesticides trapped from ambient air, and recapitulate the
procedures for extraction, clean-up and determination of these substances. Improvements in sampling
procedures, analytical methods and monitoring activities are necessary to advance the knowledge of
occurrence of currently used pesticides in atmosphere and their impact over environment and humans.
2009 Elsevier B.V. All rights reserved.
Contents
1.
2.
3.
4.
5.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Sampling of pesticides in ambient air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.
Active sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1.1.
Materials for sample collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.
Passive air sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Analytical procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Clean-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.1.
GC detection methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.2.
HPLC detection methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Occurrence of pesticides in air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions and future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1. Introduction
Pesticides such as herbicides, insecticides and fungicides, are the
most widely used chemical compounds. Its intensive use all over
the world led to ubiquitous contamination of exposed and remote
areas, not only water or soil, but also in the atmosphere. During
Corresponding author. Tel.: +34 961925865.

E-mail address: yusa vic@gva.es (V. Yus).
0021-9673/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.chroma.2009.02.019
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spray application of a pesticide a fraction of the dosage applied to

the target area could be deposited onto the adjacent non-target
areas and other fraction lost in the atmosphere. Emissions during
application can range from a few percent to 2030% [1].
Spray drift is dened as losses during application measurable
near the sprayed area (as downwind ground deposit) after sedimentation up to a few minutes after application [2]. Spray drift
depends on spray characteristics, such as volatility and viscosity
of the pesticide formulation, the equipment and application techniques, the weather conditions at the time of application (wind
V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983
speed and direction, temperature, relative humidity, atmospheric

stability at the application site), and operator skill [3] Drift losses
can be calculated using drift tables. A portion of the pesticide that
does not reach the target area consists of gas phase pesticide and
small droplets or particles (aerosols) that cannot be effectively captured by drift collectors. This is a lost that should be considered in
addition to drift.
Post-application emissions that involve volatilization from soil
and plants and wind erosion of soil particles containing sorbed
pesticides represent further signicant pesticide input into the troposphere for several days or weeks after pesticide application.
Current knowledge about pesticide volatilization was reviewed
by several authors (e.g. van den Berg et al. [1] and Bedos et al.
[4]). Volatilization is dened as the process by which a compound evaporates to the atmosphere from another environmental
compartment [5]. The dominant factors that affect volatilization
from soil are physicochemical properties of compounds (vapour
pressure, solubility, adsorption coefcient, reactivity, . . .), soil properties (water content, soil temperature, organic matter content, soil
density, pH, . . .), meteorological conditions (air temperature, wind,
air humidity) and agricultural practices (application rate, type of
formulation). Volatilization uxes from soil ranged between few
and several hundreds of ng m2 s1 [6]. Many eld measurements
performed with different techniques report that volatilization from
fallow soil could be higher than 20% of dose applied [7], and that the
majority of the losses take place within 46 days of treatment [8].
It has been shown that plant volatilization is up three times
higher than soil volatilization under similar meteorological conditions [2]. The compound characteristics (vapour pressure, Henrys
law constant) seemed closely related with de degree of volatilization. Formulation, applications characteristics and meteorological
conditions may also play an important role in the volatilization
process from plants [9].
The FOCUS Air group [2] has considered that vapour pressure
(Vp) is a key factor driving volatilization and is therefore a good trigger for screening compounds in a tiered risk assessment scheme,
and consider that substances applied to soil with Vp higher than
104 Pa (20 C), and substances applied to plants with Vp higher
than 105 Pa (20 C), has a potential to reach the air, and require a
risk assessment evaluation before authorisation.
Semi-volatile organic compounds such as pesticides present in
atmosphere are known to be simultaneously present in both the
gas and particulate phase. The distribution among these phases
(vapour/particles, or V/P partitioning) depends on the physicochemical properties of the compound considered, such as vapour
pressure and water solubility. It is also inuenced by environmental factors, especially temperature, humidity and the nature
and concentration of suspended particulate matter. The partitioning between particle and gas phase is important to determine the
environmental fate of these compounds in the air, principally the
inuence on wet and dry deposition, photochemical degradation
and atmospheric transport.
According to Bidleman [10] vapour pressure governs the partitioning of a semi-volatile substance between the gas and the
air-borne particle phases. Substances with a vapour pressure higher
than 102 Pa are predominantly observed in the vapour phase
whereas those with a vapour pressure lower than 105 Pa are almost
exclusively present in the particle adsorbed phase. The majority of
pesticides have a vapour pressure in-between the aforementioned
values and partition between these phases.
Sanusi et al. [11] reported that some organochlorine and carbamate pesticides with vapour pressures from 5.6 to 0.031 MPa
were found solely in the gas phase while some urea herbicides
and carbamate insecticides (vapour pressure: 0.0410.0003 MPa)
were found also in particulate phase up to 70%. Van Dijk et al.
[12] found that some pesticides such as deltamethrin, fenpropi-
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morph, carbofuran, chlorothalonil, 3,6-dichloro-2-methoxybenzoic

acid (dicamba), 4-chloro-2-methylphenoxy acetic acid (MCPA),
2,4-dichlorophenol (2,4-D), with vapour pressure ranging from
1.6 103 to 1.2 108 Pa were only in the particulate phase. Others
pesticides such as lindane, triuralin, chlorpyrifos and metolachlor
(vapour pressure from 0.0027 to 0.0062 Pa) appeared almost exclusively in the vapour phase. Atrazine and simazine achieved 40% of
total air concentration in particulate phase in the winter months,
whereas they were completely in the vapour phase in the MayJune
period. Recently Li et al. [13] reported that due to the highatmospheric temperature in the subtropical area of Guangzhou and
Hong Kong, China, the organochlorine pesticides (OCPs) studied
were predominantly in the gas phase in all seasons. The particle
fraction ranged between 1 and 32%. However for -endosulfan and
DDT compounds occasionally reached 75% in the winter season.
In a recent study, Scheyer et al. [14] found that the inuence of
meteorological parameters like temperature and relative humidity seems negligible for the V/P partitioning of four current-used
pesticides (CUPs) (alachlor, lindane, metalochlor and triuralin).
Additionally, the total concentration of particles does not affect the
V/P partitioning of the aforementioned four compounds.
Once a pesticide enters into the atmosphere it tends to become
well mixed and dispersed throughout the surface boundary layer.
The ability of a pesticide to travel short or long distances essentially
depends on the amount of time it resides in the atmosphere, and
this is related to pesticide properties and meteorological factors
[15].
At the local scale the dispersion last from few minutes to an hour
and it is mostly inuenced by wind speed. Consequently, pesticides
are mostly lost at local area (short-range transport) by transport
processes since the transformation and deposition processes takes
generally more time. On the other hand, at regional scale (i.e. longrange transport) vertical transport to higher layers and removal
and exchange processes such as transformation and wet and dry
deposition [10,16] are inuencing factors.
In the atmosphere, pesticides may be degraded by solar light
photolysis and chemical reactions with HO , NO3 radicals [17,18]
and ozone. Reaction with HO radicals appears to be the major loss
process for a big number of pesticides [19].
Another important loss pathway for pesticides from air is deposition [20]. Both, wet and dry deposition, depend on the distribution
of the pesticide in air. Compounds adsorbed to aerosols are mostly
found in wet deposition. Compounds mostly in the vapour phase
are divided between wet and dry deposition.
The scope of this review focuses on currently used collecting
and analytical methods for determination of pesticides in ambient
air. Additional considerations about the occurrence of pesticides
in ambient air are included. Research literature within the period
20002008 has generally been considered. The review is centred
on ambient air determination and hence, sampling and analysis
applied to indoor air has been excluded.
2. Sampling of pesticides in ambient air
Pesticides in ambient air are generally at very low concentrations, because of that, appropriate sampling and pre-concentration
techniques are necessary to achieve the sensitivity of the analytical
instruments. The most common sampling techniques for pesticides
in ambient air can be grouped into two categories: active [21] and
passive (diffusive) samplers [22,23].
2.1. Active sampling
Active samplers enable the pesticides present in gaseous and
particulate phases to be trapped by pumping air through a lter
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Fig. 1. Schematic diagram of a typical active air sampling and the analysis steps of
lters and adsorbents.
followed by a solid adsorbent. The pesticides in the particulate

phase are retained in the lter, whereas those present in the gas
phase are trapped by the adsorbent (see Fig. 1). Ambient air pesticides could be sampled by using low-volume samplers (LVSs) or
high-volume samplers (HVSs).
Pesticides are present in the atmosphere at concentrations
usually ranging from 0.1 pg m3 to 10 ng m3 for each pesticide [24] Because of these low concentrations, trappers need to
be into contact with large quantity of air; consequently, pesticides in ambient air are most frequently sampled by HVSs
(capable of pumping at ows rate between 13 and 30 m3 h1 )
[25,26].
Table 1 shows data about volumetric ow rate and sampling
duration used in different monitoring studies of pesticides in atmospheric air. Filter and adsorbents used in each case, together with
an indication of pesticides sampled are also reported. The total volume sampled range between 220 and 2700 m3 with sampling times
ranging from 12 h to 7 days. It would be said that the sampling time
depends on purpose of the sampling, the sampler ow rate, and
the detection limit of the analytical method. In general, with highvolume samplers of around 30 m3 h1 , 24 h is generally enough to
detect the levels of pesticides in middle latitude atmosphere and to
avoid clogging-up the lters.
The use of high-volume sampling technique for study the gasparticle partitioning can result in some errors such as blow-on
(gaseous compounds are adsorbed on deposited particles or on lter material itself) and blow-off (volatile compounds desorbs from
the lter) [54]. The blow-on seems to be the dominant process that
can lead to an overestimation of the particulate fraction. However,
according to Sanusi et al. [11] these sampling errors appear to be
less severe than reported in literature.
Few studies have used LVSs to monitor pesticides in ambient air
(see Table 1). However, LVSs (0.033.6 m3 h1 ow rate) are mainly
used in studies related with volatilization transfer process, both
in chambers [55], and eld [68]; in spray drift studies [56,57],
greenhouse air [58,59], or occupational safety (indoor) air studies
[6062].
Different high-volume samplers are used in monitoring studies.
The major manufacturers are Tisch Environmental [63], Thermo Scientic [64] and Digitel [65]. In some cases the samplers are home
made [38].
As an alternative to high-volume samplers in order to collect
air samples for determination of semi-volatile organic compounds
(SVOCs), some authors have proposed to use diffusion denuder
systems [6668]. The most usual denuders are those with an annular design, which consists of a series of coaxial glass tubes coated
with an appropriate adsorbent through which the air ows. Vapour
phase SVOCs are removed from the air stream by diffusion onto an
adsorbent coating. Particles, which diffuse much more slowly than
gaseous molecules, are collected onto a lter downstream [69]. Others designs has been proposed including multicapillary [70,71] and
parallel plates [72].
Table 1
Examples of active sampling methods recently used for pesticides in ambient air.
Flow rate (m3 h1 )
Duration (h)
Filter type (particle phase)
Adsorbent (gas phase)
Pesticides
Ref.
12.625.8
11.015
26
15
18.5
30
4.6
42
5.829.1
1.115
12.5
8.33
10.015
20.8
34
2.3/12.5
8.33
10.015
12.048
10.4
10.015
16
16
8.33
30
34
0.35
12.018
5.59
24
23
168
12
24
24
24
24
24168
168
84
2472
24
24
24/48
84
24
24
24
24
168
168
84
24
24
1867
24
GFF, 20 cm 25 cm
GFF, 30 cm diameter
QFF, 78/516 cm2
GFF, 10.2 cm diameter
QFF, 10.5 cm diameter
QFF
QFF, 9 cm diameter
GFF
GFF, 30 cm diameter
QFF
GFF
GFF, 30 cm diameter
GFF, 10 cm diameter
QFF
QFF
GFF
GFF, 30 cm diameter
GFF
QFF, 10.2 cm diameter
GFF, 30 cm diameter
QFF
GFF, 9 cm diameter
QFF
XAD-2, 100 g, s-PUF

XAD-2, 20 g
PUF
XAD-2, 10 g, s-PUF
XAD-2, s-PUF
PUF
PUF, 827 cm3

XAD-2, 20 g
PUF
XAD-2, 25 ml, s-PUF
XAD-2, 25 ml, s-PUF
PUF (7 cm 5 cm diameter)
PUF (7.5 cm 8 cm diameter)
XAD-2
XAD-2
XAD-2, 25 ml, s-PUF
XAD-2, 20 g
XAD-2, 40 g
PUF, 7.5 cm thick 8.0 cm diameter
XAD-2, 20 g
XAD-2, 7 g + Tenax-TA, 7 g, s-PUF
XAD-2, 7 g + Tenax-TA, 7 g, s-PUF
XAD-2, 25 ml s-PUF
XAD-2, 40 g
PUF
PUF
9 multiclass pesticides
9 OCPs
23 multiclass pesticides + OCPs
OCPs
OCPs
OCPs
52 multiclass
10 herbicides
2 herbicides
OCPs
24 OCPs
OCPs
2 herbicides
20 OCPs
28 CUP
13 OP + 13 degradation products
3 fungicides
5 fungicides
OCPs
OCPs
OCPs
[27]
[11]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
Note: For details about the lters and adsorbents materials see the text.
Diffusion denuders are LVS with ow rates from 6 to 17 l min1

and sampling duration between 2 and 48 h. This sampling technique have been applied to determine concentrations in the
atmosphere or investigate gas-particle partitioning of different
SOVC such as polycyclic aromatic hydrocarbons (PAHs) [69,73,74],
polychlorinated biphenyls (PCBs) [70], OCPs [66] or carbonyl compounds [67,75]. To our knowledge, denuders have not been applied
for the determination of CUPs in ambient air.
2.1.1. Materials for sample collection
Pesticides in particulate matter are trapped using glass ber lters (GFFs) or quartz ber lters (QFFs). Its diameter varies between
9 and 30 cm, depending on the sampler used (Table 1).
Regard the absorbents used in each sampling, few materials have
been employed for collection of pesticides present in the ambient
air gas phase. Of these, the hydrophobic polymeric resin Amberlite
XAD-2 is the most employed (see Table 1). This is a hydrophobic
cross-linked polyestyrene copolymer sorbent with a large surface
area (300 m2 g1 ) that interacts with the analytes basically through
Van der Waals forces and interactions of the aromatic rings
[76].
XAD-2 is an universal adsorbent, very efcient for trapping herbicides, fungicides or insecticides. Generally 1040 g of XAD-2 resin
is employed to collect the pesticides present in gaseous phase in volumes up to 2000 m3 . It is employed alone or sandwiched between
polyurethane foam (PUF) cylinders. In this last form it has been
used to monitor different pesticide classes such as banned OCPs,
organophosphorus pesticides (OPPs) triazines and phthalimides
(see Table 1).
Although XAD-4 has not been used in many monitoring studies,
it has been employed in some works comparing the trap efciency
of different solid sorbents [57]. XAD-4 is a polymeric adsorbent
supplied as white insoluble beads. It is a nonionic cross-linked polymer which derives its adsorptive properties from its macroreticular
structure (containing both, a continuous polymer phase and a continuous pore phase), its high-surface area (800 m2 g1 ), and the
aromatic nature of its surface.
PUF is the type of foam generally used for furniture upholstery,
pillows, and mattresses. It is white and turns yellow upon exposure
to light. It is easy to use and inexpensive, and generally consists of
a polyether of a density of 0.0225 g cm3 [77].
PUF has been used in many studies mainly focused in monitoring OCPs and other priority pollutants, such as PCBs, PBDEs, etc.
This adsorbent has been tested by the US Environmental Protection Agency (EPA) for sampling 57 common pesticides (scope of the
EPA Method TO-4A) [25] including banned OCPs (aldrin, alachor or
p,p -DDT or lindane), OPPs (malathion, diazinon, dicofol) and polar
pesticides such as simazine (base-10 logarithm of octanolwater
partitioning coefcient (pKow ): 2.1), monuron (pKow : 1.46), carbaryl
(pKow : 1.85) or dicrotophos (pKow : 0.35). Using this EPA method,
LigAir [78] develops annual campaigns for monitoring up to 52 pesticides in ambient air, both banned and CUPs, including fungicides,
herbicides and insecticides.
Another sorbent employed is the porous polymer Tenax TA
[56], a resin based on 2,6-diphenylene oxide with low-surface area
(35 m2 g1 ) and low-water afnity. It has been used combined
with XAD-2 to monitor OPP or fungicides such as folpet, captan or
captafol (Table 1). However, it is a traditional sorbent for trapping
medium- to high-boiling compounds that is mainly used for collect
volatile compounds with low-volume samplers [57,79,80]. Both the
EPA for ambient air) [81] and NIOSH for indoor air [62] specify the
use of Tenax TA in their standard methods for determination of
volatile organic compounds (VOCs).
Some studies have evaluated the trapping efciency of different
solid sorbents for collecting pesticides in the gaseous phase. Dowson et al. [82] have compared the efciency of different types of
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adsorbents for trapping 27 current-used pesticides, including PUF,

XAD-2 resin, XAD-4 resin, and both resins sandwiched between
PUF. This efciency was tested by simultaneously sampling of pesticides with high-volume samplers, each one coated with one type
of adsorbent. It appears that the sandwiches PUF/XAD-2/PUF and
PUF/XAD-4/PUF are the most efcient, then the XAD-2 and XAD-4
resins, followed by PUF. The authors recommend the use of XAD-2,
because the efciency of sandwiches is only slightly greater than
XAD-2, and losses of pumping efciency occur with sandwiches.
In order to establish a procedure for sampling four fungicides
(pyrimethanil, metalaxyl-M, myclobutanil and fenhexamid) and
the insecticide malathion, Tsiropoulus et al. [58] have evaluated
the retention efciency and carried out breakthrough tests for
four solid sorbents (XAD-2, XAD-4, Supelpak-2, Florisil and C-18).
In general the retention efciency remained constant for all the
sorbents and compounds except in the case of fenhexamid on
XAD-4 and Florisil, where a decrease on trapping efciency was
observed when the amount of pesticides was increased. Retention efciency was examined by fortication of the sampling
cartridge into the front bed with different amounts of pesticides,
and ambient air was pulled through the tubes at different rates.
However, this study uses low-volume rate (12 l min1 ) and the
method was not applied for monitoring ambient air, but to monitor malation and fenhexamid in greenhouse air after application.
Supelpak-2 and Florisil were selected based on their performance
characteristics.
Before sampling new pesticides or use different sorbents, sampling efciency (ability of the sampling medium to trap analytes
of interest) or retention efciency (ability of sampling medium to
retain a compound spiked to it in liquid solution) and breakthrough
tests should be performed [25,26].
2.2. Passive air sampling
A passive air sampler (PAS) is a device that collects chemicals
from the atmosphere without the aid of a pump, and consists of
an accumulating medium that has a high-retention capacity for the
target analytes. Such samplers allow for integrative (time-averaged
concentrations, TWA) sampling in locations where active samplers
would not be practical over long periods, due to lack of electricity supply in remote locations [23]. Nevertheless, passive samplers
are able to collect only the free gaseous phase pollutants and the
duration of sampling range from few weeks to several months (see
Table 2), signicantly larger than the usual time required using
active samplers.
A range of PAS are available for sampling different chemical
species in air [83]. The majority of works that uses PAS for monitoring pesticides in ambient air are focused in sampling OCPs, joint
with others persistent organic pollutant (POPs), and the materials
utilized are mainly polyurethane foam (PUF) disks, semi-permeable
membrane devices (SPMDs), polymer-coated glass (POG) samplers,
and XAD resins. Table 2 shows an overview of recent studies concerning the monitoring of OCPs pesticides in ambient air using
PAS.
Most of the passive air sampling measures have been performed
using PUF disks (see Table 2). PUF is regularly used as a sorbent
in active high-volume sampling devices. Because of its properties
it has been also applied as a passive sampler in the form of disk.
The passive air samplers consisted of PUF disks housed in stainless
steel, domed chambers in order to reduce the inuence of wind
speed on uptake rate [96] and also to protect the PUF disks from
precipitation, direct particle deposition, and UV sunlight [85] (see
Fig. 2). Motelay et al. [84] investigate the seasonality of air concentrations for OCPs and other pollutants using PUF disks as passive
samplers. PAS were deployed for 4-month integration periods along
an urban-rural transect in Toronto. They concluded that such a
2976
Table 2
Examples of passive sampling devices employed recently for the determination of OCPs in air.
Type
Duration [sampling rate (m3 day1 )]
Uptake regime
Type of study/country
Concentrations (pg m3 )
Ref.
PUF disk
PUF disk
PUF disk
POG
PUF disk
XAD-2
XAD-2
PUF disk/SPMD
POG
PUF disks
PDMS
SPMD
4 months
6 weeks [3.4]
4 months [3.1]
7 days [3]
2 months [4.8]
1 year [1]
58 months [1]
4 months
7 days
28 days [34]
14 days [0.0025/0.017]
7 days
K
K
K
E/CL
K
K
K
K
E
K
K
K
Seasonality of air concentrations/Canada

Monitoring at continental scale/Europe
Monitoring the Laurnetian Great Lakes/Canada-USA
Vertical proling of the atmosphere/Canada
Investigation of concentrations at remote sites
Atmospheric distribution and long-range transport
Monitoring at three rural sites/Canada
Assessment of urbanrural trends/Canada
Short-term spatial variability/Europe
Impact of local points sources/Czech Republic
Control polluted area/Germany
Evaluation air quality/Spain
0.351283
<0.4390
15430
0.75730
0.67
0.07260
0.666
0.17817
01775
20120
19,5007,469,000
12
[84]
[85]
[86]
[87]
[88]
[89]
[90]
[91]
[92]
[93]
[94]
[95]
K: kinetic; E: equilibrium; CL: curvi-linear. PDMS: poly(dimethylsiloxane)-coated stir bars. For details about others acronyms of sample types see the text.
simple sampling technique can yield insightful data not available

until the moment of the study.
Semi-permeable membrane devices (SPMDs) comprise a lowdensity polyethylene (LDPE) bag, 7090 m wall thickness, lled
with triolein (1,2,3-tris-cis-9-octadecenoyl glycerol). Standard
devices are 106 cm long, 2.54 cm wide, and contain 1 ml of triolein [97]. The operation of a SPMD as passive sampler is based
on the diffusion of compounds through the polymeric membrane
bag and their accumulation in the lipophilic solvent (see Fig. 2).
SPMDs have been used mainly for sampling a variety of non-polar
and moderately polar organic contaminants from water [22,98].
However, some authors have used them for sampling pollutants
in ambient air [99,100]. Harner et al. [91] used SPMD housed in
protective chambers for sampling POPs, including some OCPs. The
samplers were deployed at six sites for 4 months of sampling duration. Results demonstrated the feasibility of using such devices to
determine air concentrations of considered pesticides and to assess
their spatial distribution.
POG samplers are created by applying a thin polymeric stationary phase (ethylene vinyl acetate-EVA-) to a solid glass surface.
The characterisation and principles of POG sampling have been
described by Harner et al. [101]. Farrar et al. [87] reported the rst
application of PGO samplers for process-based study of OCPs pesticides in ambient air. The same authors have used POG samplers to
investigate short-term spatial variability of POPs including lindane
and HCB [92]. The passive air samplers were deployed at 38 sites
across 19 European countries with an exposure time of 7 days.
As we have shown above, XAD-2 is routinely used as a sampling medium in active samplers. Wania et al. [90] developed and
calibrated a PAS based on the sorption of gaseous pollutants to the
sampling resin XAD-2. The sampler consists of a stainless steel mesh
cylinder, lled with XAD-2 resin and suspended in a steel can with
an open bottom. They concluded that XAD-2-based passive sampler

is suitable to derive time-weighted, semi-quantitative information
on concentrations of vapour-phase POPs, including OCPs pesticides,
in the atmosphere over times scales of month to years. Shen et al.
[89] deployed the same XAD-2 resin passive sampler over 40 stations across North America in order to evaluate the distribution and
long-range transport of OCPs. The samplers were deployed for an
entire year to yield one annually averaged concentration in each
station.
A major challenge in understanding data obtained from PAS is to
estimate the air concentration from the concentrations found in the
sampler, which can allow comparison between passive samplers
deployed at various locations and times.
Gas phase compounds partition into the PAS during the uptake
can achieve the equilibrium if the exposure time is long enough.
In general, there are three different phases for chemical uptake
in a PAS. The uptake is initially linear with time, followed by a
curvilinear region, and nally a constant phase when equilibrium
is established between air and PAS [102].
The capacity and time to reach equilibrium can be varied
by the choice of sampler type, storage medium and size. Moreover, the total capacity of the sampler at equilibrium also differs
between compounds. Chemicals with high-equilibrium partition
coefcients will take longer to reach equilibrium than others with
low-partition coefcients. The equilibrium concentration depends
on the PAS-air partition coefcient (KPAS-A ), which is well correlated
to the octanolair partition coefcient, KOA [91].
Sampling can therefore be conducted using two principal air
phase strategies: the kinetic (linear) or the equilibrium sampling
mode. The relationship between the amount of pollutants absorbed
by the PASs and their concentrations in air can be obtained by mathematical models. These calculations can be governed by linear or
Fig. 2. Schematic diagram of typical passive air samplers: (a) design of a PUF passive air sampler [88]; (b) design of a SPMD [22].
2977
Table 3
Overview methods proposed for the analysis of pesticides in ambient air.
Pesticides
Extraction
9 OCPs
Soxhlet, 16 h
Soxhlet, 12 h, n-Hx:DCM
Soxhlet, 8 h, acetone
Ultrasonic, 30 min, n-Hx
Soxhlet, 12 h, DCM:PE
Soxhlet, 24 h, PE:DCM
Soxhlet 24 h, n-Hx:acetone
Soxhlet, 16 h, DCM
Soxhlet, 12 h, Hx:DCM
Soxhlet, 16 h, DEE + Hx
Shoxlet, 16 h, acetone
Soxhlet 12 h, n-Hx:DCM
Soxhlet 16 h, PE
Soxhlet 24 h, PE
Soxhlet 24 h, acetone:Hx
Soxhlet, 18 h, PE
Inmersion in DCM
Soxhlet, 24 h, PE
Soxhlet, 24 h, n-Hx:DEE
Soxhlet, 12 h, DCM:Hx
Soxhlet, 24 h, Hx:acetone
PLE, Hx-DCM-EE
Soxhlet, 12 h, Hx:DCM
PLE, EtAc
PLE, EtAc
PLE, acetone
Soxhlet 24 h, PE
40 multiclass pesticides (OCPs, OPPs, neutral herbicides)

22 OCPs
OCPs
OCPs
10 multiclass herbicides
2 herbicides
17 OCPs
24 OCPs
44 OCPs
14 OCPs
19 OCPs
4OCPs
OCPs
20 OCPs
10 OPPs + 14 OPPs DP
3 fungicides
5 herbicides
OCPs
Clean-up
Determination
LOD (pg m3 )
Ref.
GCMS
GC-ECD; HPLC-UV
0.7089
HPLC, silica
[27]
[11]
[28]
Silica gel; Florisil

Alumina
Alumina
Alumina
L-L partitioning; Florisil
Silica
Alumina/Florisil
Florisil
No clean-up
Alumina
Florisil + alumina
Silica gel
Alumina
Silica gel
Alumina
Florisil
Silica
No clean-up
C18
C18
Florisil
No clean-up
Silica
GC-ECD
GC-ECD; GCMS
GC-ECD
GCNI-MS
GC-ECD; GCMS
GCMS
GC-ECD; HPLC-UV
GCMS; HPLC-UV
GCMS; GCMS/MS
GC-ECD; GCMS
GC-ECD
GCECNI-MS
GCMS
GC-ECD
GCMS
GCNI-MS
GCNI-MS
HPLC-UV
GCMS/MS
GCEI-MS
GCEI-MS
GCMS/MS
LCMS/MS
GCNI-MS
GCMS
LCMS/MS
GC-ECD; GCNI-MS
1.473
4.020
0.0020.13
0.0050.1
0.1
1
50.25
40
5.08.0
0.114
0.249
0.71.3
1.226
0.010.48
7013,800
2.51250
0.71110
0.41.6
2.51250
0.210
0.83.8
40
6.532.8
0.1
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[85]
[40]
[86]
[87]
[88]
[41]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[52]
Hx: hexane; DCM: dichloromethane; EtAc: Ethyl acetate; PE: Light petroleum. DP: degradation products.
equilibrium models, after establishing the corresponding experimental parameters (e.g. KPAS-A or sampling rate (m3 day1 ) for each
compound studied). During the kinetic period the sampling rate
remains linear at values ranging from 1 to 4.8 m3 day1 (Table 2)
for the different sampler types and OCPs. The experimental parameters can be established by eld calibration experiments [101,103] or
using permeation reference compounds (PRCs) also named depuration compounds [88,104].
Currently PAS can allow estimations of air concentrations within
a factor of 23 of the true air concentrations [105]. For many situations, this may be an acceptable level of accuracy. Nevertheless,
further improvements may be possible, although PAS will probably
always be less reliable than active methods.
3. Analytical procedures
A complete method for pesticide analysis in ambient air, as in
other matrices, includes additionally to the sampling step, a sample preparation procedure and a pesticide determination method.
Table 3 gives a summary of analytical methods proposed for identication and quantication of pesticides in ambient air. The steps
involved are extraction, clean-up, and determination.
3.1. Extraction
Extraction aims to remove as much as possible of the pesticides
from the sampling material. So it is a fundamental aspect in the
analytical process. After sampling, lters and cartridges could be
extracted separately or together, depending if the work attempts to
measure the partitioning of the pesticides between gas and particulate phase or not.
Current methodology involves liquidsolid extraction (LSE) of
pesticides trapped in lters and cartridges, and is carried out by
using and appropriate organic solvent. Lammel et al. [28] extracted
some persistent OCPs regulated under the global POP convention
[106], from particulate matter trapped in lters with n-hexane

using ultrasonic extraction during 30 min. Shen et al. [89] using a
method rst described by Wania et al. [90], extracted organochlorine pesticides from a XAD-2 PAS transferring the XAD-2 material
to an elution column and passing through it 250 ml of methanol
followed by 350 ml of dichloromethane.
For extracting OCPs trapped in a POG passive air sampler with
a coating of ethylene vinyl acetate (EVA), Farrar et al. [87] just dissolved the EVA coating by immersion in 35 ml of dichloromethane
(DCM).
However, Soxhlet is the rst choice when pesticides are to
be extracted from lters and cartridges used in active air samplers, because it has the advantage of being simple and low-cost
method, and it has been adopted in some standardized analytical methodologies for determining pesticides in ambient air
[107,108]. Soxhlet extraction is performed with different solvents
used alone, such as acetone, DCM, or as solvent mixtures such as
hexaneDCM, DCMlight petroleum (PE), cyclohexaneacetone or
hexaneacetone (see Table 3). This classical extraction technique
has the disadvantage of being both, time (from 6 to 24 h) and solvent
(250700 ml), consuming.
This aforementioned drawbacks together with the long-heating
periods in the Soxhlet ask that are prone to broke the structural
integrity of polar thermally labile pesticides applied in modern
agricultural (N-methylcarbamates, sulfonyl urea, and chlorophenoxy acid herbicides), are leading to use alternative procedures as
pressurized liquid extraction (PLE) [109].
It is widely recognized that PLE (Dionex trade name ASE, for
accelerated solvent extraction), gives recoveries comparable to
those obtained with Soxhlet and other techniques in use. PLE utilizes organic solvents under elevated temperature (50200 C) and
pressures (10002000 psi) to extract organic pollutants from environmental matrices [110,111].
PLE increases the speed of the extraction process with lowsolvent consumption, and can be automated. The main parameters
2978
for method optimization are solvent, temperature and time. Pressure, between the operating values, is not considered a critical
experimental parameter [112]. Despite of that, PLE has been
scarcely used for the extraction of pesticides on traps from air
samples.
Recently some authors have been used PLE to extract OCPs
from air samples. Yang et al. [45] have extracted loaded QFF and
PUF plugs individually, using a mixture of hexaneDCMdiethyl
ether (7:1:2, v/v), at 100 C during 15 min (four times). Recoveries ranged from 62 to 100%. Raina et al. [47] extracted 10 OPPs
and 14 OPPs degradation products from a glass bber lter and
PUF/XAD-2/Tenax/PUF sorbent cartridge. They used ethyl acetate
as solvent, at 100 C during 30 min. No degradation of OPPs pesticides was observed and the recoveries ranged from 70 to 100%,
with relative standard deviations from 1 to 21%, except for phorate
oxon and malathion monocarboxylic acid that were not sufciently
extracted by PLE with ethyl acetate, because were strongly held to
the sorbent material. Likewise, the same extracting method was
used by Baliley et al. [48] to extract the fungicides captan, captanol
an folped. Surrogate recoveries (diazino d10 ) were 85105%, and a
second extraction with acetone showed no presence of pesticides
in the extracts.
Applying statistical design of experiments (DoE) [113], Coscoll
et al. [50] optimized PLE parameters for the determination of nine
currently used pesticides from ne airborne particulate matter (PM
2.5). No signicant differences between acetone, ethyl acetate and
acetonitrile, used as solvents, were found, with recoveries ranging
from 72 to 110%. However, extracts with acetone present less matrix
effect. A central composite design (CCD) was chosen to study the
relative inuence of temperature, pressure on the recovery of pesticides by PFE. The optimised conditions were 50 C, 1750 psi, and
a static time of 1 min.
It is well known that microwave-assisted extraction (MAE)
allows reduction of both, extraction time and organic solvent
consumption, and increases sample throughput in the extraction
of different pollutants from environmental matrices [114116].
Applications of MAE for extracting pesticides from soils [117,118],
sediments [119] and foods [120122] have been proposed. However, to our knowledge, no works has been published related with
the extraction of pesticides from air traps.
Prior to the sampling, the traps need to be cleaned. The more
usual cleaning method is Soxhlet, with the same solvents used for
extraction. Sanusi et al. [34] pre-extracted the glass bber lter
and the XAD-2 resin with Soxhlet for 24 h using n-hexaneDCM
(85:15), and then dried in it a 60 C oven and stored in polyethylene bags and bottles, respectively. Peck et al. [44] pre-cleaned the
XAD-2 resin with 24-h Soxhlet extraction with methanol, acetone,
dichloromethane, hexane and 50:50 hexaneacetone. The XAD-2
resin was put into stainless steel sampling in the laboratory. The
resin lled cartridges were stored in aluminium canisters sealed
with Teon tap and sealed plastic bags during transport to and from
the sampling locations.
As pre-clean procedures some authors used PLE with different
solvent mixtures. For PUF plugs pre-cleaning, Yang et al. [45] used
a mixture solvent of hexaneDCMethyl ether (7:1:2), and the PLE
was operated at a temperature of 100 C, 15 min. The extraction
procedure was repeated six times using fresh solvent each time. The
PUF plugs were dried overnight in a vacuum desiccator and stored in
solvent-rinsed glass jars with Teon lined lids before use. QFFs were
baked at 450 C for 8 h to remove organic contaminants. Similar PLE
pre-cleaning procedure for QFF were followed by Sofuoglu et al.
[30], who baked overnight the lters previously wrapped loosely
with aluminium foil, in a mufe furnace at 450 C. Also Bailey et
al. [48] used PLE for PUF, XAD-2 and Tenax TA cleaning, but they
utilize a rst extraction with ethyl acetate, and a second one with
acetone.
3.2. Clean-up
Air samples can contain a signicant amount of other components. During the extraction step many interfering (mainly
organic) components are co-extracted together with target analytes
and may interfere in their identication and quantisation. Therefore, a clean-up step performed after concentration is generally
required.
The column based-SPE has become the most common cleanup approach for the purication of pesticide residues from air
samples (Table 3). The most frequent sorbents include normal
phase sorbents [123] such as Florisil (synthetic magnesium silicate), alumina, silica gel, or a combination of them (alumina/silica
or alumina/Florisil). In these polar sorbents, only extracts in a
non-polar solvent, typically hexane or isooctane, are percolated
through the sorbent after conditioning. Step elution with solvent
of increasing polarity allows a fractionation on the basis of polar
difference.
Alumine was employed for the clean-up of lters and PUF air
sample extracts for the determination of OCPs [39]. The extract
was obtained from Soxhlet extraction with PE and concentrated by
rotary evaporation, blown down with a gentle stream of nitrogen
and exchanged into isooctane. Clean-up was made on a column
of 1 g of neutral alumina (Al2 O3 ). The column was pre-eluted
with 10 ml dichloromethane followed by 10 ml PE. Extracts were
applied in 1 ml isooctane and the column was eluted with 15 ml
(5% DCM/PE). The eluate was concentrated by nitrogen blow-down
and solvent-exchanged into isooctane before analysis.
Polar sorbents perform good clean-up for most apolar pesticides
such as organochlorine and some organophosphorus compounds,
but are less suitable for clean-up of analytes covering a wide polarity
range.
Reversed-phase C18 silica has been used for clean-up of more
polar pesticides such as OPP herbicides and OPP degradation products [47] and some fungicides [48]. Extracts in methanol were
loaded onto the preconditioned C18 cartridge and eluted with 5 ml
of ethylacetate. However, no macroporous polymeric sorbents [76]
such as LiChrolut EN, Oasis HLB, Bond Elut PPL, Isolute ENV+ have
been used, probably because of the low number of polar pesticides
monitored in atmosphere.
Gel permeation chromatography (GPC) or size exclusion chromatography separates compounds on the basis of their size [124].
GPC is best suited for removing materials like waxes and fats. Jaward
et al. [85] have been used GPC with Biobeads SX3, in a two-step
clean-up procedure to detect OCPs and other persistent organics
pollutants (POPs), after an alumina-silica chromatographic column
for purication of extracts from PUF passive sampler.
In some cases, mainly when using very selective detectors such
as GCMS/MS [46] and LCMS/MS [50], no previous clean-up was
necessary. However, it is essential to study the matrix effect [125]
(signal enhancement or suppression) before to decide not to perform a clean-up step, ruggedness and instrumental maintenance.
3.3. Determination
Over the past decades, approaches to detect trace levels of pesticides have changed signicantly, moving away from the use of
GC with classical detectors to GCMS because of the sensitivity and
selectivity offered by the MS detector. Likewise, the increasingly use
of polar and sometimes thermal-labile compounds, mainly herbicides, has promoted the use of LCMS based methods.
3.3.1. GC detection methods
Until now, pesticide residues in air are mainly analysed by gas
chromatography (GC). Volatility and thermal stability are required
for amenable-GC pesticides.
The detection methods most widely used are electron-capture

detection (ECD), nitrogen-phosphorus detection (NPD) and mass
spectrometry (MS).
GC-ECD was commonly used for the analysis of OCPs. Many
works related with air monitoring for POPs, that includes some
OCPs (aldrin, cis and trans-chlordane, DDT and transformation
products, dieldrin, endrin, heptachlor, HCB, mirex) still are using
this very sensitive and selective detector (Table 3). Columns
employed are non-polar or semi-polar, 5% phenyl/95% polydimethylsiloxane (DB-5, Optima-5), mostly of 30 m 0.32 mm
ID 0.25 m lm thickness, or 60 m 0.25 mm ID, 0.10 m. They
utilize helium as carrier gas and the splitless injection mode.
Because of uncertainty of the identication with GC-ECD, some
authors carried out a conrmation of pesticides by GCMS (see
Table 3). GCMS is increasingly replacing traditional detectors in the
determination of pesticide residues in air, and is nowadays the analytical technique most widely used. GCMS is a necessary approach
in the analysis of pesticides in air for its capacity to provide quantitative and conrmatory results, and for its high sensitivity.
The MS analyser most frequently used is quadrupole, mainly
working in selected ion monitoring (SIM) mode, which provided
a higher sensitivity than full scan mode. In multiresidue analysis
by GCMS, electron ionization (EI) in positive mode, is most commonly used. Peck et al. [44] have analysed 51 CUPs in ambient air by
GCMS, using a quadrupole analyzer in SIM mode, with EI+. A 30-m
5% phenyl methylsiloxane capillary column was utilized (HP-5MS;
0.25 mm ID, 0.25 m lm thickness). All analytes were identied by
retention time and with two characteristics ions, and the internal
standard method was used for quantication. The analytes present
retention times ranging from 23.86 to 85.22 min.
The GCMS technique has been also used with negative chemical
ionization (NCI), mainly for analysis of OCPs (see Table 3). Chemical ionization (CI) is a softer ionization approach that tends to give
lower LOQ depending on the pesticide, but is not widely applicable in multiclass pesticide methods and does not provide as much
structural information about the analyte as EI.
Some polar pesticides cannot be analysed directly by GC (no
amenable-GC pesticides). However, different polar pesticides have
been also determined by GCMS, both in EI and NCI ionization
mode, after a prior derivatization step. Waite et al. [36] have
analysed 10 polar herbicides, including aryloxyalkanoic acids (2,4D, MCPA), triazines (atrazine) and thiocarbamates (triallate), by
GCMS after methylation with ethereal diazomethane. The same
derivatizing agent has been used in a previous work [49] to analyse
ve polar herbicides such as triuralin, dicamba, diclofop, MCPA
and triuralin.
Scheyer et al. [43,46] have used pentauorobenzylbromide
(PFBBr) to derivatice urea herbicides (diuron, isoproturon, chlorotoluron) and aryloxyalkanoic acids (2,4-D, MCPP, MCPA).
Some authors, looking for a best sensitivity and highest specicity, have used GC coupled to mass spectrometry in tandem
(MS/MS) using ion trap (IT) instruments [126]. Scheyer et al. [43]
have developed a multiresidue method using GCIT-MS/MS for
the analysis of 27 multiclass pesticides, some of them requiring
a derivatization step (ureas). Owing to the high specicity, the
method does not require a clean-up step.
Precise optimization of MS/MS parameters is needed in order
to maximize the signal for each pesticide. Usually the rst step is
the selection of the parent ions from each pesticide study of the
fragmentation (full scan spectra) of each analyte. Precursor ions are
then isolated in the ion trap and fragmented by collision-induced
dissociation (CID) [127] and the two most abundant product ions
for each congener are selected. Different parameters can potentially
affect the fragmentation by CID and the analytical response of the
ITMS system, depending on the instrument used. The optimization
can be made by software, by the approach of changing-one-factor-
2979
at-a-time (COST), or using DoE [116] Methods for multiresidue

determination of pesticides by GCMS/MS have been widely set up
in other matrices such as vegetables, soils or sediments, using both
IT [128], and triple quadrupole detectors (QqQ) [129]. Until now,
this last detector has not been used in the analysis of pesticides
in air.
3.3.2. HPLC detection methods
High-performance liquid chromatography (HPLC) has been used
for the analysis of non amenable-GC pesticides, i.e. those polar
compounds or with low-thermal stability such as urea herbicides,
carbamates, triazines or phenoxy acids [60], or those requiring
derivatization to improve volatility or chromatography performance when GCMS methods are used. Sanusi et al. [11,34] have
fractionated the extracted pesticides from XAD-2 resin and lters,
and analysed two out of three fractions by HPLC-UV, which includes
phosalane, mecoprop, atrazine, diuron, isoproturon, carbofuran and
carbaryl. They used a reverse phase column C18 (30 cm 3.9 mm ID,
4 m lm thickness), with a binary solvent (methanolacetonitrile,
80:20) as mobile phase.
Baraud et al. [41] developed a multiresidue method for the
determination of 16 polar pesticides in atmosphere, belonging
to 9 chemical families, using HPLC-UV. After extraction with
Soxhlet using n-hexane:diethyl ether (90:10, v/v) for 24 h, and
evaporation, the deposit was dissolved in 2 ml of mobile phase
(acetonitrile:water:acetic acid, 30:59:2, v/v). The limits of detection
ranged from 0.7 to 13.8 ng m3 .
Some authors have described the benets that HPLC coupled to
MS/MS present in terms of wider scope, increased sensitivity and
better selectivity [130] for pesticide analysis. For this reason in other
elds such as food safety, the development of multiresidue pesticide
residue methods by LCMS/MS has become essential in order to
achieve higher sensitivity and specicity and conrmatory procedures [130134]. However, few methods have been developed and
validated for multiresidue analysis of pesticides in environmental
air samples.
Raina et al. [47] have developed a LCMS/MS method for determination of 24 OPPs and their degradation products in air samples,
using electrospray ionization in the positive mode (ESI+). They
reported that APCI ionization mode gave poorer sensitivity for
these molecules than ESI+. For most compounds two characteristics
transitions with best sensibility for each compound were selected,
choosing the most intense for quantitative analysis (SRM1) and the
second transition (SRM2), along with the ratio SRM1/SRM2 for conrmation of the compound. The method detection limits ranging
typically from 0.2 to 10 pg m3 with typical air volumes of 2700 m3 .
In a recent work, Coscoll et al. [50] developed a LCESI-MS/MS
method for analysis of nine currently and extensively used pesticides in citric, fruits and grapes, in ne airborne particulate matter
(PM 2.5). Acetone was selected as the most appropriate solvent for
extraction with PLE. All compounds presented matrix effect mainly
ion suppression. In order to compensate the matrix effect, a calibration strategy based on using matrix-matched standard calibration
was used [134].
Signal suppression or enhancement as a result of matrix effect
can severely compromise quantitative analysis of pesticides at trace
levels by LCMS/MS. Matrix effect must be evaluated and discussed
in the context of method development before studying its performance characteristics and appropriate strategies for compensation
should be carried out, improving sampling preparation or selecting
an appropriate calibration strategy [125].
4. Occurrence of pesticides in air
In recent years, several monitoring studies have been reported
pesticide concentrations in remote, rural and urban zones of
2980
Table 4
Concentrations of pesticides in ambient air.
Compound
Class
Regulatory EU
Range (ng m3 )
Site
Ref.
2,4-D
DDTs
Acetochlor
Aclonifen
Alachlor
Aldrin
Ametryn
Atraton
Atrazine
Azinfos-methyl
Azinfos-methyl oxon
Bitertanol
Bromoxynil
Butachlor
Butylate
Captan
Carbaryl
Carbendazim
Carbofuran
Carboxin
Chlordane, transChloroneb
Chlorothalonil
Chlorpyrifos
Chlorpyrifos ethyl
Chlorpyrifos oxon
Chlorthal
cis-Chlordane
cis-Nonachlor
Cycloate
Cyprodinil
DEA
Deltamethrin
DEP
DIA
Diazinon
Diazinon oxon
Dicamba
Dichlobenil
Dichlorvos
Dieldrin
Diufenican
Dimethoate
Dimethomorphe
Disulfoton
Diuron
Endosulfan I
Endosulfan sulfate
Endosulfan, Endosulfan, Endrin
Endrin, KetoEpoxyconazole
EPTC
Ethaluralin
Ethofumesate
Ethoprop
Etridiazole
Fenpropidin
Fenpropimorph
Fluazifop-P-butyl
Folpet
Fonofos
HCB
HCH, HCH, HCH, Heptachlor
Heptaclhorepoxy
Hexythiazox
Imazalil
IMP
Isofenfos
Isomalation
Isoproturon
Linron
Aryloxyalkanoic acid (H)

Organochlorine (I)
Chloroacetamide (H)
Diphenyl ether (H)
Chloroacetamide (H)
Organochlorine (I)
Triazine (H)
(H)
Triazine (H)
Organophosphorus (I)
Metabolite
Triazole (F)
Hydroxybenzonitrile (H)
Chloroacetamide (H)
Thiocarbamate (H)
Phthalimide (F)
Carbamate (I)
Benzimidazole (F)
Carbamate, N-methyl (I)
Oxathiin (F)
Organochlorine (I)
(F)
Chloronitrile (F)
Organophosphorous (I)
Organophosphorous (I)
Metabolite
Benzenedicarboxylic acid (H)
Organochlorine (I)
In
Out
Out
Pending
Out
Out
Out
0.028637
ND0.293
ND53.5
ND4.2
ND8.5
ND0.466
Rural
[29,36,41]
[38]
[44]
[35]
[29,35,36,44]
[30,31,38,45]
[44]
[44]
[29,3436,44,46]
[27,48]
[48]
[50]
[29]
[44]
[44]
[35,48]
[34]
[50]
[34]
[44]
[30]
[44]
[27,35]
[30,44]
[35]
[47]
[44]
[32,38,39,45]
[39]
[44]
[35]
[44]
[41]
[41]
[44]
[35,41,44]
[41]
[29]
[35]
[44]
[30,31,3840]
[35,46]
[41]
[35]
[44]
[34,46]
[30,39]
[30,31]
[27,35,38]
[27,38]
[30,38]
[30]
[35]
[44]
[29,36]
[35]
[44]
[44]
[35]
[35]
[27]
[35,48]
[44]
[34]
[30,34,38,39,45]
[30,32,45]
[30,31,34,38,46]
[30,32,39]
[39,45]
[50]
[50]
[47]
[44]
[47]
[34,41]
[41]
Thiocarbamate (H)
Anilinopyrimidine (F)
Metabolite
Pyrethroid (I)
Metabolite
Metabolite
Metabolite
Auxine (H)
Benzonitrile (H)
Organochlorine
Pyridinecarboxamide (H)
Cinnamic acid (F)
Urea (H)
Organochlorine (I)
Metabolite
Organochlorine (I)
Organochlorine (I)
Organochlorine (I)
Organochlorine (I)
Triazole (F)
Thiocarbamate (H)
Dinitroaniline (H)
Benzofuran (H)
Aromatic hydrocarbon (F)
Morpholine (F)
Morpholine (F)
Aryloxyphenoxypropionate (H)
Phthalimide (F)
Organochlorine (F)
Organochlorine (I)
Organochlorine (I)
Organochlorine (I)
Organochlorine (I)
Metabolite
(A)
Imidazole (F)
Metabolite
Metabolite
Urea (H)
Urea (H)
Out
Out
Out
In
Out
Out
In
Out
In
Out
Out
In
In
Pending
Out
Out
In
In
Out
Out
In
Out
Out
Out
In
In
Out
In
Out
Out
Out
Out
In
Out
Out
In
In
Out
In
In
In
Out
Out
Out
Out
Out
Out
Out
In
Out
In
In
ND2
ND8.5
ND16.5
ND0.0061
ND0.155
0.00860.791
ND0.15
ND5.3
ND22.8
ND0.696
ND0.572
ND8.1
ND0.24
0.0130.894
ND2.4
ND458
ND2.9
ND97.8
0.1960.189
ND0.033
ND0.25
ND0.004
ND0.74
ND3.3
ND1.3
ND4770
ND0.102
ND612.4
ND0.696
0.0190.615
ND0.74
ND2.3
0.0020.136
ND0.462
0.00130.019
ND0.1
ND1.4
ND12.8
0.0031.373
0.0011.271
ND81.3
ND7.2
0.0050.891
0.0060.082
ND0.4
ND0.85
ND0.453
ND1.2
ND1.2
ND0.23
ND3.5
ND13.2
ND0.07
ND82.2
ND0.099
0.0811.62
0.0043.853
ND0.631
0.0010.666
0.00080.156
ND0.072
ND0.434
ND0.637
ND0.226
ND0.54
ND0.0036
ND19
ND5.1
Rural
Rural
Rural, urban
Rural, urban
Rural
Rural
Rural, remote
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural, remote
Rural
Rural, remote
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Urban
Rural
Rural
Rural
Rural
Rural, urban
Rural
Rural
Rural
Rural
Rural
Urban
Rural
Rural, urban
Urban
Rural
Urban
Rural
Remote, rural, urban
Rural
Rural
Rural, urban
Rural, urban
Rural, urban
Rural
Urban
Rural
Rural
Rural
Rural
Rural
Rural, urban
Urban, rural
Rural
Rural, urban
Rural
Remote, rural
Rural
Rural
Urban, rural, remote
Rural, urban
Rural
Rural
Rural
Rural
Rural
Rural
Remote, rural, urban
Urban
2981
Table 4 (Continued)
Compound
Class
Regulatory EU
Range (ng m3 )
Site
Ref.
Malathion
Malathion oxon
MCPA
MCPP
Metalaxil
Metazachlor
Methamidofos
Methidathion
Methoxychlor
Metobromuron
Metolachlor
Metribuzin
Metsulfuron methyl
Mirex
Molinate
Napropamide
Omethoate
Oxychlordane
Oxyuorfen
Parathion-methyl
Pebulate
Pendimethalin
Phorate
Phosalone
Primicarb
Prometon
Propachlor
Propargite
Propazine
Propyzamide
Pyriproxyfen
Simazine
Simetryn
Spiroxamine
TCP
Tetrachlorvinphos
Thiabendazole
Tolyluanid
Toxaphene
Triadimefon
Triallate
Tricyclazole
Triuralin
Vernolate
Vinclozolin
Metabolite
Acylalanine (F)
Chloroacetamide (H)
Organochlorine (I)
Urea (H)
Chloroacetamide (H)
Triazinone (H)
Triazinylsulfonylurea (H)
Organochlorine (I)
Thiocarbamate (H)
Alkanamide (H)
Metabolite
Organochlorine
Diphenyl ether (H)
Thiocarbamate (H)
Dinitroaniline (H)
Carbamate (I)
Triazine (H)
Chloroacetamide (H)
(A)
Triazine (H)
Benzamide (H)
Juvenile hormon mimic (I)
Triazine (H)
Methylthiotriazine (H)
Morpholine (F)
Metaolite
Benzimidazole (F)
Sulphamide (F)
Organochlorine (I)
Triazole (F)
Thiocarbamate (H)
Reductase (F)
Dinitroaniline (H)
Thiocarbamate (H)
Dicarboximide (F)
Out
ND4450
0.00290.611
ND4.96
ND5130
ND1
ND0.8
ND10.5
ND0.3
0.0430.99
ND3.1
ND27.5
ND0.96
ND11
0.00660.255
ND0.015
ND0.025
0.00090.0027
ND0.00022
ND3
ND6
ND12
ND117.3
ND91.2
ND3.670
ND5.1
ND4.3
ND1.7
ND45.6
ND0.12
ND0.33
ND0.155
ND0.4
ND0.09
ND12.1
0.0260.131
ND0.61
ND1.371
ND86.4
0.3190.771
ND2.9
ND15.3
ND0.17
ND40.7
ND0.19
ND0.2
Urban
Rural
Rural
Rural
Rural
Urban, rural
Rural
Urban
Rural
Rural
Urban, rural
Rural
Urban
Urban
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural, remote
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Rural
Urban, rural
Rural
Rural
Rural
Rural
Urban, rural, remote
Rural
Urban, rural
[35,41]
[47]
[29,36]
[41]
[27,29]
[35]
[27]
[35]
[30]
[27]
[35,44]
[27]
[41]
[29]
[44]
[44]
[47]
[31]
[35]
[44]
[44]
[35]
[44]
[34]
[27]
[44]
[35,44]
[35]
[44]
[44]
[50]
[44]
[44]
[35]
[47]
[44]
[50]
[35]
[39]
[35]
[29,36,44]
[44]
[29,3436,44,46]
[44]
[35]
In
In
Out
Pending
Out
Out
Out
Out
Out
In
Out
In
Out
Out
Out
Out
Out
In
Out
Out
In
Out
Out
Out
In
Out
Out
In
Out
In
In
Out
Out
Pending
Out
Out
Out
Out
H: herbicide, F: fungicide, I: insecticide; ND: non-detected.
different countries. Table 4 identies about a hundred pesticides

that have been determined in ambient air in studies developed in
recent years using active sampling, mainly high-volume samplers.
Also, their regulatory status in the European Union (EU) [135] are
reported.
It could be said that pesticides listed in Table 4 is not comprehensive of the actual atmospheric contamination, since the compounds
found are those that were sought for, although several compounds
such as oxydemeton-S-methyl, oxadiazon, uazinam, udioxonil,
imidacloprid, methidation or methiocarb [35,50], which were analysed but not detected.
In general, the reported values are the sum of pesticides present
in gas and particulate phases, although some studies reported the
distribution between gas and particles. Concentrations of pesticides
in ambient air ranged from few pg per m3 to many ng per m3 .
Taking into account the compounds listed in Table 4, near 50%
of the substances detected in ambient air are herbicides, mostly
aryloxyalkanoic acids, chloroacetamides, thiocarbamates and triazines. More than half of these herbicides detected are nowadays
forbidden according to the EU regulations.
Regarding insecticides, only 5 (primicarb, chlorpiryfos,
dimethoate, ethoprop and deltamethrin) out of 35 insecticides detected could now be used for plant treatments in Europe.
Table 4 also shows 21 fungicides belonging to different chemical

classes such as morpholines (fenpropidin, fenpropimorph, spiroxamide) benzimidazole (carbendazim, thiabendazole) or ftalamides
(captan, folpet). Nine of these fungicides are today forbidden in all
countries of the EU. Consequently, it can be said that the occurrence
in air of the majority of the currently used pesticides in air are
poorly investigated.
Some authors have shown that atmospheric concentrations of
CUPs are correlated to the proximity of sampling to sources areas
and that the occurrence usually is linked with local use [136] However, Peck et al. [44] showed that the amount of pesticide used in
an area of USA is only slightly correlated to the detection frequency
and not correlated to average concentrations. These means that the
presence of a pesticide in the air is dependent on its use, but other
factors, such as V/P distribution, wet and dry deposition, transport
and atmospheric degradation, are also important. Nevertheless, the
overall concentration at a regional scale is expected to be higher
during the period when a given pesticide is applied over large areas
[137].
Locally high concentrations of pesticides in air are very seasonal
and are correlated to local use patterns. The highest concentrations
in air usually occur in the spring and summer months coinciding with application times and warmer temperatures. However, for
2982
some CUPs that are detected, it is not always clear if their concentration and frequency in air is associated with local use and/or
long-range transport (LRT) from other sources [137].
Pesticides have also been detected at low levels during periods
after use, but the determination of their sources has proven to be
difcult. These off-season occurrences could be due to volatilization
and wind erosion or the result of long-range transport from other
areas. White et al. [27] found that the herbicide metribuzin was
detected in an overnight sample more than 2 months after its application on the farms elds. They attribute this fact to the relative
persistence of metribuzin in soil (half-life is 106 days) and, therefore, the possibility of post-application volatilization of metribuzin
from soil even 2 months after application.
5. Conclusions and future trends

During the past decade different studies related with pesticides
in ambient air have been developed, mainly focused in emission of
pesticides to the air during application, volatilization from plants
and soil, monitoring ambient air in remote, rural and urban areas
and development of sampling and analytical methods. However,
further studies are necessaries to improve the sampling procedures and the analytical methods, and wider monitoring studies
are required to achieve a better knowledge of the occurrence and
fate of currently used pesticides in ambient air.
There is a lack of consistency in sampling methodologies. New
sorbents should be selected in order to increase the scope of the
trapped pesticides and to make the HVS suitable to sample new
currently used pesticides. Also, studies related with the retention
capacity of the different materials need to be developed for a wider
range of pesticides, principally for those that are used in greater
quantities.
Presently used analytical methods generally involve Soxhlet
extraction that requires big solvent volumes and is time consuming.
Therefore, efforts should be made to develop sample preparation
techniques based on modern extraction techniques such as ASE
or microwave in order to avoid these aforementioned drawbacks.
These techniques have provided good results in multiresidue analysis of pesticides in other matrices such as food, soil or sediments.
So, they will also be used in ambient air.
Sample preparation is the limiting step of the analysis of pesticides in air. Even using powerful detection techniques such
as LCMS/MS, some clean-up is still necessary since otherwise
interferences or matrix effect can occur. Further studies toward
simplication of sample preparation, including automation and
integration of sample preparation and instrumental analysis are
necessaries to improve performance of faster procedures.
Analytical methodologies employed must be capable of residue
measurements at very low levels, and must provide unambiguous evidence to conrm the identity of any residue detected.
Consequently, MS is a necessary tool in the modern analysis of
pesticides in air, coupled to GC or HPLC. Likewise, the number of
non GC-amenable compounds because of their poor volatility or
thermal instability has grown considerably in the last years; consequently, HPLC coupled to MS, in tandem mode, should be an
essential approach in the multiresidue analysis of pesticide in air.
Also further developments involving techniques such as TOF-MS
could be necessaries in order to apply non-target analysis in monitoring pesticides and their degradation compounds in ambient
air.
Many of the active substances studied are now banned pesticides
and only a small percentage can be considered CUPs. Additional
monitoring studies and wider sampling networks are necessaries
to reach a better knowledge of the occurrence, fate, and impacts of
the currently used pesticides.
Acknowledgements
This work has been nanced by the Generalitat Valenciana through the project DEPESVAL (GV/2007/257), and by the
Ministerio de Ciencia e Innovacion through the projects CTQ200805719/BQU and ECOPEST, CGL 2007-65223/CLI. The authors are
grateful to LigAir (Orleans, France) for the information provided.
VY wants to thank Conselleria de Sanitat for the grant received to
realize this study.
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Journal of Chromatography A, 1216 (2009) 29722983

Contents lists available at ScienceDirect

Sampling and analysis of pesticides in ambient air

Public Health Laboratory of Valencia-CSISP, 21 Avda Catalu

Corresponding author. Tel.: +34 961925865.

spray application of a pesticide a fraction of the dosage applied to

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

speed and direction, temperature, relative humidity, atmospheric

morph, carbofuran, chlorothalonil, 3,6-dichloro-2-methoxybenzoic

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

followed by a solid adsorbent. The pesticides in the particulate

Filter type (particle phase)

Adsorbent (gas phase)

XAD-2, 100 g, s-PUF

PUF, 827 cm3

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

Diffusion denuders are LVS with ow rates from 6 to 17 l min1

adsorbents for trapping 27 current-used pesticides, including PUF,

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

Duration [sampling rate (m3 day1 )]

Seasonality of air concentrations/Canada

simple sampling technique can yield insightful data not available

an open bottom. They concluded that XAD-2-based passive sampler

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

40 multiclass pesticides (OCPs, OPPs, neutral herbicides)

Silica gel; Florisil

[106], from particulate matter trapped in lters with n-hexane

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

The detection methods most widely used are electron-capture

at-a-time (COST), or using DoE [116] Methods for multiresidue

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Aryloxyalkanoic acid (H)

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H: herbicide, F: fungicide, I: insecticide; ND: non-detected.

different countries. Table 4 identies about a hundred pesticides

Table 4 also shows 21 fungicides belonging to different chemical

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

5. Conclusions and future trends

[17] A. Le Person, A. Mellouki, A. Munoz,

[18] V. Feigenbrugel, A. Leprson, S. Lecalvea, A. Mellouku, A. Munoz,

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

[120] E. Fuentes, M.E. Bez, A. Quinones,

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