Sampling

Journal of Chromatography A, 1216 (2009) 29722983

Contents lists available at ScienceDirect

Journal of Chromatography A

journa l homepage: www.e lsev ier .com

Review

Sampl ai

V. Yusa ara Public Healtb ICARE-CNRSc Analytical C urjassot, Valencia, Spain

a r t i c

Article history:Received 22 DReceived in reAccepted 9 FeAvailable onlin

Keywords:PesticidesAmbient airSamplingAnalytical meReview

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29722. Sampling of pesticides in ambient air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2973

2.1. Active sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29732.1.1. Materials for sample collection . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2975

2.2.3. Analy

3.1.3.2.3.3.

4. Occur5. Concl

AcknoRefer

1. Introdu

Pesticidemost widelthe world leareas, not o

CorresponE-mail add

0021-9673/$ doi:10.1016/j.cPassive air sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2975tical procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2977Extraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2977Clean-up . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2978Determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29783.3.1. GC detection methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29783.3.2. HPLC detection methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2979

rence of pesticides in air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2979usions and future trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2982wledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2982

ences . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2982

ction

s suchasherbicides, insecticides and fungicides, are they used chemical compounds. Its intensive use all overd to ubiquitous contamination of exposed and remotenly water or soil, but also in the atmosphere. During

ding author. Tel.: +34 961925865.ress: yusa [email protected] (V. Yus).

spray application of a pesticide a fraction of the dosage applied tothe target area could be deposited onto the adjacent non-targetareas and other fraction lost in the atmosphere. Emissions duringapplication can range from a few percent to 2030% [1].

Spray drift is dened as losses during application measurablenear the sprayed area (as downwind ground deposit) after sedi-mentation up to a few minutes after application [2]. Spray driftdepends on spray characteristics, such as volatility and viscosityof the pesticide formulation, the equipment and application tech-niques, the weather conditions at the time of application (wind

see front matter 2009 Elsevier B.V. All rights reserved.hroma.2009.02.019l e i n f o

ecember 2008vised form 5 February 2009bruary 2009e 13 February 2009

thods

a b s t r a c t

Developments in the sampling and determination of pesticides in ambient air have been discussed anddataon theoccurrenceof pesticides in atmospherehavebeenpresented.Developments in active samplingmethods were reviewed and the different materials used for trapping pesticides from gas and particulatephases were discussed. Likewise, the use and developments of passive air samplers were reviewed. Thisarticle pays special attention to the analysis of pesticides trapped from ambient air, and recapitulate theprocedures for extraction, clean-up and determination of these substances. Improvements in samplingprocedures, analytical methods and monitoring activities are necessary to advance the knowledge ofoccurrence of currently used pesticides in atmosphere and their impact over environment and humans.

2009 Elsevier B.V. All rights reserved./ locate /chroma

r

diacing and analysis of pesticides in ambient,, C. Coscolla, W. Melloukib, A. Pastorc, M. de la Gu

h Laboratory of Valencia-CSISP, 21 Avda Cataluna, 46020 Valencia, Spain, 1C Avenue de la Recherche scientique, 45071 Orleans cedex 02, Francehemistry Department, University of Valencia, Edici Jeroni Munoz, 50 Dr. Moliner, 46100 B

V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983 2973

speed and direction, temperature, relative humidity, atmosphericstability at the application site), and operator skill [3] Drift lossescan be calculated using drift tables. A portion of the pesticide thatdoes not reach the target area consists of gas phase pesticide andsmall dropltured by draddition to

Post-appand plantspesticides rposphere fo

Currentby several[4]). Volatipound evapcompartmefrom soil apressure, soerties (watedensity, pHair humiditformulationand severalperformedwfallow soil cmajority of

It has bhigher thantions [2]. Thlaw constantion. Formuconditionsprocess from

The FOC(Vp) is a keyger for screand conside104 Pa (20than 105 Prisk assessm

Semi-voatmospheregas and pa(vapour/parchemical prpressure anmental factand concening betweeenvironmeninuence oand atmosp

Accordintitioning ofair-bornepathan 102 Pwhereas thoexclusivelypesticides hvalues and

Sanusi ebamate peswere foundand carbamwere found[12] found

morph, carbofuran, chlorothalonil, 3,6-dichloro-2-methoxybenzoicacid (dicamba), 4-chloro-2-methylphenoxy acetic acid (MCPA),2,4-dichlorophenol (2,4-D), with vapour pressure ranging from1.6103 to1.2108 Pawereonly in theparticulatephase.Others

des sr prein thir conas the. Recheri

Kongredon ranmporece

rologms ndes (nall

rtitioe a pixedility os onrelat

he los mostlyses slly mtranschantionhe aysis aone.s forther20]. Bpestiin widedscop

alytiditioient2008bientto i

plin

ticideecauuesent

ient(dif

tive s

ive slateets or particles (aerosols) that cannot be effectively cap-ift collectors. This is a lost that should be considered indrift.lication emissions that involve volatilization from soiland wind erosion of soil particles containing sorbedepresent further signicant pesticide input into the tro-r several days or weeks after pesticide application.knowledge about pesticide volatilization was reviewedauthors (e.g. van den Berg et al. [1] and Bedos et al.lization is dened as the process by which a com-orates to the atmosphere from another environmentalnt [5]. The dominant factors that affect volatilizationre physicochemical properties of compounds (vapourlubility, adsorption coefcient, reactivity, . . .), soil prop-r content, soil temperature, organicmatter content, soil, . . .), meteorological conditions (air temperature, wind,y) and agricultural practices (application rate, type of). Volatilization uxes from soil ranged between fewhundreds of ngm2 s1 [6]. Many eld measurementsith different techniques report that volatilization from

ould be higher than 20%of dose applied [7], and that thethe losses take place within 46 days of treatment [8].een shown that plant volatilization is up three timessoil volatilization under similar meteorological condi-e compound characteristics (vapour pressure, Henryst) seemed closely related with de degree of volatiliza-lation, applications characteristics and meteorologicalmay also play an important role in the volatilization

plants [9].US Air group [2] has considered that vapour pressurefactor driving volatilization and is therefore a good trig-ening compounds in a tiered risk assessment scheme,r that substances applied to soil with Vp higher thanC), and substances applied to plants with Vp highera (20 C), has a potential to reach the air, and require aent evaluation before authorisation.

latile organic compounds such as pesticides present inare known to be simultaneously present in both the

rticulate phase. The distribution among these phasesticles, or V/P partitioning) depends on the physico-operties of the compound considered, such as vapourd water solubility. It is also inuenced by environ-ors, especially temperature, humidity and the naturetration of suspended particulate matter. The partition-n particle and gas phase is important to determine thetal fate of these compounds in the air, principally the

n wet and dry deposition, photochemical degradationheric transport.g to Bidleman [10] vapour pressure governs the par-a semi-volatile substance between the gas and therticle phases. Substanceswith a vapour pressurehighera are predominantly observed in the vapour phasesewithavapourpressure lower than105 Paarealmostpresent in the particle adsorbed phase. The majority ofave a vapour pressure in-between the aforementionedpartition between these phases.t al. [11] reported that some organochlorine and car-ticides with vapour pressures from 5.6 to 0.031MPasolely in the gas phase while some urea herbicidesate insecticides (vapour pressure: 0.0410.0003MPa)also in particulate phase up to 70%. Van Dijk et al.

that some pesticides such as deltamethrin, fenpropi-

pestici(vapousivelytotal awhereperiodatmospHongwere pfractioDDT co

In ameteoity seepesticiAdditioV/P pa

Oncwell mThe abdependthis is[15].

At tand it iare moprocesgenerarangeand exdeposi

In tphotoland ozproces

Anosition [of thefoundare div

Theand anair. Adin amb2000on amapplied

2. Sam

Pestions, btechniqinstrumin ambpassive

2.1. Ac

Actparticuuch as lindane, triuralin, chlorpyrifos and metolachlorssure from 0.0027 to 0.0062Pa) appeared almost exclu-e vapour phase. Atrazine and simazine achieved 40% ofcentration in particulate phase in the winter months,ywere completely in the vapour phase in theMayJuneently Li et al. [13] reported that due to the high-c temperature in the subtropical area of Guangzhou and, China, the organochlorine pesticides (OCPs) studiedminantly in the gas phase in all seasons. The particleged between 1 and 32%. However for -endosulfan andunds occasionally reached 75% in the winter season.nt study, Scheyer et al. [14] found that the inuence ofical parameters like temperature and relative humid-egligible for the V/P partitioning of four current-usedCUPs) (alachlor, lindane, metalochlor and triuralin).y, the total concentration of particles does not affect thening of the aforementioned four compounds.esticide enters into the atmosphere it tends to becomeand dispersed throughout the surface boundary layer.f a pesticide to travel short or long distances essentiallythe amount of time it resides in the atmosphere, anded to pesticide properties and meteorological factors

cal scale the dispersion last from fewminutes to an hourstly inuenced by wind speed. Consequently, pesticideslost at local area (short-range transport) by transportince the transformation and deposition processes takesore time. On the other hand, at regional scale (i.e. long-port) vertical transport to higher layers and removalge processes such as transformation and wet and dry[10,16] are inuencing factors.tmosphere, pesticides may be degraded by solar lightnd chemical reactions with HO, NO3 radicals [17,18]Reaction with HO radicals appears to be the major lossa big number of pesticides [19].important loss pathway for pesticides from air is depo-oth,wet anddrydeposition, dependon thedistribution

cide in air. Compounds adsorbed to aerosols are mostlyet deposition. Compounds mostly in the vapour phasebetween wet and dry deposition.e of this review focuses on currently used collecting

cal methods for determination of pesticides in ambientnal considerations about the occurrence of pesticidesair are included. Research literature within the periodhas generally been considered. The review is centredair determination and hence, sampling and analysis

ndoor air has been excluded.

g of pesticides in ambient air

s in ambient air are generally at very low concentra-se of that, appropriate sampling and pre-concentrationare necessary to achieve the sensitivity of the analyticals. Themost common sampling techniques for pesticidesair can be grouped into two categories: active [21] andfusive) samplers [22,23].

ampling

amplers enable the pesticides present in gaseous andphases to be trapped by pumping air through a lter

2974 V. Yus et al. / J. Chromatogr. A 1216 (2009) 29722983

Fig. 1. Schematic diagram of a typical active air sampling and the analysis steps oflters and adsorbents.

followed by a solid adsorbent. The pesticides in the particulatephase are retained in the lter, whereas those present in the gasphase are trapped by the adsorbent (see Fig. 1). Ambient air pes-ticides could be sampled by using low-volume samplers (LVSs) orhigh-volume samplers (HVSs).

Pesticides are present in the atmosphere at concentrationsusually ranging from 0.1pgm3 to 10ngm3 for each pesti-cide [24] Because of these low concentrations, trappers need tobe into contact with large quantity of air; consequently, pes-ticides in ambient air are most frequently sampled by HVSs(capable of pumping at ows rate between 13 and 30m3 h1)[25,26].

Table 1duration usspheric air.

an indication of pesticides sampled are also reported. The total vol-ume sampled range between220 and2700m3 with sampling timesranging from 12h to 7 days. It would be said that the sampling timedepends on purpose of the sampling, the sampler ow rate, andthe detection limit of the analytical method. In general, with high-volume samplers of around 30m3 h1, 24h is generally enough todetect the levels of pesticides in middle latitude atmosphere and toavoid clogging-up the lters.

The use of high-volume sampling technique for study the gas-particle partitioning can result in some errors such as blow-on(gaseous compounds are adsorbed on deposited particles or on l-ter material itself) and blow-off (volatile compounds desorbs fromthe lter) [54]. The blow-on seems to be the dominant process thatcan lead to an overestimation of the particulate fraction. However,according to Sanusi et al. [11] these sampling errors appear to beless severe than reported in literature.

Few studies have used LVSs to monitor pesticides in ambient air(see Table 1). However, LVSs (0.033.6m3 h1 ow rate) are mainlyused in studies related with volatilization transfer process, bothin 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.Themajormanufacturers areTischEnvironmental [63], ThermoSci-entic [64] and Digitel [65]. In some cases the samplers are homemade [38].

As an alternative to high-volume samplers in order to collectair samples for determination of semi-volatile organic compounds(SVOCs), some authors have proposed to use diffusion denudersystems [6668]. The most usual denuders are those with an annu-lar design, which consists of a series of coaxial glass tubes coatedwith an appropriate adsorbent throughwhich the air ows. Vapourphase SVOCs are removed from the air stream by diffusion onto an

ent csmoignsl pla

Table 1Examples of a

Flow rate (m3 s phas

12.625.8 s-PUF11.0152615 -PUF18.5304.6425.829.11.11512.58.3310.01520.8342.3/12.58.3310.01512.04810.410.01516168.3330340.3512.018

Note: For detashows data about volumetric ow rate and samplinged in differentmonitoring studies of pesticides in atmo-Filter and adsorbents used in each case, together with

adsorbgaseouers desparalle

ctive sampling methods recently used for pesticides in ambient air.

h1) Duration (h) Filter type (particle phase) Adsorbent (ga

5.59 GFF, 20 cm25 cm XAD-2, 100g,24 GFF, 30 cm diameter XAD-2, 20g23 QFF, 78/516 cm2 PUF168 GFF, 10.2 cm diameter XAD-2, 10g, s12 QFF, 10.5 cm diameter XAD-2, s-PUF24 QFF PUF24 QFF, 9 cm diameter

24 GFF PUF, 827 cm3

24 GFF, 30 cm diameter XAD-2, 20g24168 QFF PUF168 GFF XAD-2, 25ml, s-PUF84 GFF, 10.2 cm diameter XAD-2, 25ml, s-PUF2472 GFF, 30 cm diameter PUF (7 cm5 cm di24 GFF, 10 cm diameter PUF (7.5 cm8 cm d24 QFF XAD-224/48 QFF XAD-284 GFF XAD-2, 25ml, s-PUF24 GFF, 30 cm diameter XAD-2, 20g24 GFF XAD-2, 40g24 QFF, 10.2 cm diameter PUF, 7.5 cm thick824 GFF, 30 cm diameter XAD-2, 20g168 GFF, 10.2 cm diameter XAD-2, 7 g +Tenax-T168 GFF, 10.2 cm diameter XAD-2, 7 g +Tenax-T84 GFF, 10.2 cm diameter XAD-2, 25ml s-PUF24 GFF, 15.0 cm diameter 24 QFF XAD-2, 40g1867 GFF, 9 cm diameter PUF24 QFF PUF

ils about the lters and adsorbents materials see the text.oating. Particles, which diffuse much more slowly thanlecules, are collectedontoalterdownstream[69].Oth-has been proposed including multicapillary [70,71] andtes [72].

e) Pesticides Ref.

9 multiclass pesticides [27]11 multiclass pesticides [11]9 OCPs [28]40 multiclass pesticides [29]23 multiclass pesticides +OCPs [30]OCPs [31]OCPs [32]OCPs [33]11 multiclass pesticides [34]52 multiclass [35]10 herbicides [36]2 herbicides [37]

ameter) OCPs [38]iameter) 24 OCPs [39]

OCPs [40]15 multiclass pesticides [41]2 herbicides [42]27 multiclass pesticides [43]51 multiclass pesticides [44]

.0 cm diameter 20 OCPs [45]28 CUP [46]

A, 7 g, s-PUF 13 OP+13 degradation products [47]A, 7 g, s-PUF 3 fungicides [48]

5 fungicides [49]9 multiclass pesticides [50]OCPs [51]OCPs [52]OCPs [53]


Diffusion denuders are LVS with ow rates from 6 to 17 lmin1

and sampling duration between 2 and 48h. This sampling tech-nique have been applied to determine concentrations in theatmosphere or investigate gas-particle partitioning of differentSOVC suchpolychlorinpounds [67,for the dete

2.1.1. MaterPesticide

ters (GFFs) o9 and 30 cm

Regard tbeen emploair gas phasXAD-2 is thcross-linkedarea (300mVan der Wa[76].

XAD-2 isbicides, funis employedumes up topolyurethanused to moorganophos(see Table 1

Althoughit has beenof differentsupplied asmerwhich dstructure (ctinuous poraromatic na

PUF is thpillows, andto light. It isa polyether

PUF hasing OCPs anThis adsorbtion AgencyEPA Methodp,p-DDT orpesticides spartitioning(pKow: 1.85LigAir [78] dticides in amherbicides a

Another[56], a resin(35m2 g1)with XAD-2captafol (Tamedium- tovolatile comEPA for ambuse of Tenavolatile org

Some stusolid sorbenson et al. [8

adsorbents for trapping 27 current-used pesticides, including PUF,XAD-2 resin, XAD-4 resin, and both resins sandwiched betweenPUF. This efciency was tested by simultaneously sampling of pes-ticides with high-volume samplers, each one coated with one type

rbenD-4folloe the, andrderethaectictentilid seralts ananded wfciege inbiener, td walatioak-2teristore sfcierest)a comould

ssive

assivhe atmul

analytratinotply ie ton of), si

sampanges in apestithersd areraneD re

g the

st of tUF d

ve hibeenssiveomeon uitatioMots forrs. Pan-ras polycyclic aromatic hydrocarbons (PAHs) [69,73,74],ated biphenyls (PCBs) [70], OCPs [66] or carbonyl com-75]. To our knowledge, denuders have not been appliedrmination of CUPs in ambient air.

ials for sample collections in particulate matter are trapped using glass ber l-r quartz ber lters (QFFs). Its diameter varies between, depending on the sampler used (Table 1).heabsorbentsused ineach sampling, fewmaterialshaveyed for collection of pesticides present in the ambiente. Of these, the hydrophobic polymeric resin Amberlitee most employed (see Table 1). This is a hydrophobicpolyestyrene copolymer sorbent with a large surface

2 g1) that interacts with the analytes basically throughals forces and interactions of the aromatic rings

an universal adsorbent, very efcient for trapping her-gicides or insecticides. Generally 1040g of XAD-2 resintocollect thepesticidespresent ingaseousphase invol-2000m3. It is employed alone or sandwiched betweene foam (PUF) cylinders. In this last form it has beennitor different pesticide classes such as banned OCPs,phorus pesticides (OPPs) triazines and phthalimides).XAD-4 has not been used in many monitoring studies,

employed in some works comparing the trap efciencysolid sorbents [57]. XAD-4 is a polymeric adsorbent

white insoluble beads. It is a nonionic cross-linkedpoly-erives its adsorptive properties from itsmacroreticular

ontaining both, a continuous polymer phase and a con-e phase), its high-surface area (800m2 g1), and theture of its surface.e type of foam generally used for furniture upholstery,mattresses. It is white and turns yellow upon exposureeasy to use and inexpensive, and generally consists ofof a density of 0.0225g cm3 [77].been used in many studies mainly focused in monitor-d other priority pollutants, such as PCBs, PBDEs, etc.ent has been tested by the US Environmental Protec-(EPA) for sampling 57 common pesticides (scope of theTO-4A) [25] including banned OCPs (aldrin, alachor orlindane), OPPs (malathion, diazinon, dicofol) and polaruch as simazine (base-10 logarithm of octanolwatercoefcient (pKow): 2.1),monuron (pKow: 1.46), carbaryl

) or dicrotophos (pKow: 0.35). Using this EPA method,evelops annual campaigns formonitoring up to 52 pes-bient air, both banned and CUPs, including fungicides,nd insecticides.sorbent employed is the porous polymer Tenax TAbased on 2,6-diphenylene oxide with low-surface areaand low-water afnity. It has been used combinedto monitor OPP or fungicides such as folpet, captan orble 1). However, it is a traditional sorbent for trappinghigh-boiling compounds that is mainly used for collectpoundswith low-volume samplers [57,79,80]. Both theient air) [81] and NIOSH for indoor air [62] specify thex TA in their standard methods for determination ofanic compounds (VOCs).dies have evaluated the trapping efciency of differentts for collecting pesticides in the gaseous phase. Dow-2] have compared the efciency of different types of

of adsoPUF/XAresins,becausXAD-2

In o(pyrimthe insthe refour soIn gensorbenXAD-4observtion ecartridand amHowevmethoitor maSupelpcharac

Befpling eof interetaintests sh

2.2. Pa

A pfrom tan accutargetconcenwouldity supare ablduratioTable 2active

A rspecietoringwith outilizememband XAcerninPAS.

Mousing Pin actiit hasThe pasteel, dspeedprecipFig. 2).trationsamplean urbt. It appears that the sandwiches PUF/XAD-2/PUF and/PUF are the most efcient, then the XAD-2 and XAD-4wed by PUF. The authors recommend the use of XAD-2,efciency of sandwiches is only slightly greater thanlosses of pumping efciency occur with sandwiches.to establish a procedure for sampling four fungicides

nil, metalaxyl-M, myclobutanil and fenhexamid) andide malathion, Tsiropoulus et al. [58] have evaluatedon efciency and carried out breakthrough tests fororbents (XAD-2, XAD-4, Supelpak-2, Florisil and C-18).the retention efciency remained constant for all thed compounds except in the case of fenhexamid onFlorisil, where a decrease on trapping efciency washen the amount of pesticides was increased. Reten-ncy was examined by fortication of the samplingto the front bed with different amounts of pesticides,t air was pulled through the tubes at different rates.

his study uses low-volume rate (12 lmin1) and thes not applied for monitoring ambient air, but to mon-n and fenhexamid in greenhouse air after application.and Florisil were selected based on their performanceics.ampling new pesticides or use different sorbents, sam-ncy (ability of the sampling medium to trap analytesor retention efciency (ability of sampling medium topound spiked to it in liquid solution) and breakthroughbe performed [25,26].

air sampling

e air sampler (PAS) is a device that collects chemicalsmosphere without the aid of a pump, and consists ofating medium that has a high-retention capacity for thetes. Such samplers allow for integrative (time-averagedons, TWA) sampling in locations where active samplersbe practical over long periods, due to lack of electric-n remote locations [23]. Nevertheless, passive samplerscollect only the free gaseous phase pollutants and thesampling range from few weeks to several months (seegnicantly larger than the usual time required usinglers.of PAS are available for sampling different chemicalir [83]. The majority of works that uses PAS for moni-cides in ambient air are focused in sampling OCPs, jointpersistent organic pollutant (POPs), and the materialsmainlypolyurethane foam(PUF)disks, semi-permeabledevices (SPMDs), polymer-coated glass (POG) samplers,sins. Table 2 shows an overview of recent studies con-monitoring of OCPs pesticides in ambient air using

he passive air samplingmeasures have been performedisks (see Table 2). PUF is regularly used as a sorbent

gh-volume sampling devices. Because of its propertiesalso applied as a passive sampler in the form of disk.air samplers consisted of PUF disks housed in stainlessd chambers in order to reduce the inuence of windptake rate [96] and also to protect the PUF disks fromn, direct particle deposition, and UV sunlight [85] (seeelay et al. [84] investigate the seasonality of air concen-OCPs and other pollutants using PUF disks as passive

ASweredeployed for 4-month integrationperiods alongural transect in Toronto. They concluded that such a


Table 2Examples 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 (pgm3) Ref.

PUF disk 4 months K Seasonality of air concentrations/Canada 0.351283 [84]PUF disk 6 weeks [3.4] K Monitoring at continental scale/Europe


Table 3Overview methods proposed for the analysis of pesticides in ambient air.

Pesticides Extraction Clean-up Determination LOD (pgm3) Ref.

9 multiclass pesticides Soxhlet, 16h GCMS 0.7089 [27]11 multiclass p LC, sil9 OCPs

40 multiclass p ca gel23 multiclass p mina22 OCPs minaOCPs minaOCPs partit11 multiclass p ca54 multiclass p mina10 multiclass h2 herbicides risil17 OCPs clean24 OCPs mina44 OCPs risil +14 OCPs ca gel19 OCPs mina4OCPs ca gelOCPs mina15 multiclass p27 multiclass p51 multiclass p risil20 OCPs ca28 multiclass p clean10 OPPs +14 O3 fungicides5 herbicides risil9 multiclass pe cleanOCPs ca

Hx: hexane; D oduct

equilibriummental paracompoundremains linfor thediffeters can be eusing permration comp

Currentla factor of 2uations, thifurther impalways be le

3. Analytic

A complother matriple preparaTable 3 givetication aninvolved are

3.1. Extract

Extractiofrom the saanalytical pextracted semeasure thulate phase

Currentpesticides tusing and asome persis

fromltras

d rssticilutio

ed byextrng ofesticides Soxhlet, 12h, n-Hx:DCM HPSoxhlet, 8 h, acetoneUltrasonic, 30min, n-Hx

esticides (OCPs, OPPs, neutral herbicides) Soxhlet, 12h, acetone Siliesticides Soxhlet, 12h, DCM:PE Alu

Soxhlet, 24h, PE:DCM AluSoxhlet 24h, n-Hx:acetone AluSoxhlet, 16h, DCM L-L

esticides Soxhlet, 12h, Hx:DCM Siliesticides Soxhlet, 16h, DEE+Hx Aluerbicides Soxhlet, 8 h, acetone

Shoxlet, 16h, acetone FloSoxhlet 12h, n-Hx:DCM NoSoxhlet 16h, PE AluSoxhlet 24h, PE FloSoxhlet 24h, acetone:Hx SiliSoxhlet, 18h, PE AluInmersion in DCM SiliSoxhlet, 24h, PE Alu

esticides Soxhlet, 24h, n-Hx:DEE esticides Soxhlet, 12h, DCM:Hx esticides Soxhlet, 24h, Hx:acetone Flo

PLE, Hx-DCM-EE Siliesticides Soxhlet, 12h, Hx:DCM NoPPs DP PLE, EtAc C18

PLE, EtAc C18Soxhlet, 12h, acetone Flo

sticides PLE, acetone NoSoxhlet 24h, PE Sili

CM: dichloromethane; EtAc: Ethyl acetate; PE: Light petroleum. DP: degradation pr

models, after establishing the corresponding experi-meters (e.g. KPAS-A or sampling rate (m3 day1) for eachstudied). During the kinetic period the sampling rateear at values ranging from 1 to 4.8m3 day1 (Table 2)rent sampler typesandOCPs. Theexperimentalparame-stablished by eld calibration experiments [101,103] oreation reference compounds (PRCs) also named depu-ounds [88,104].

[106],using umethorine peto an efollow

Fora coatiy PAS can allowestimations of air concentrationswithin3 of the true air concentrations [105]. For many sit-s may be an acceptable level of accuracy. Nevertheless,rovements may be possible, although PAS will probablyss reliable than active methods.

al procedures

ete method for pesticide analysis in ambient air, as inces, includes additionally to the sampling step, a sam-tion procedure and a pesticide determination method.s a summary of analytical methods proposed for iden-d quantication of pesticides in ambient air. The stepsextraction, clean-up, and determination.

ion

n aims to remove as much as possible of the pesticidesmpling material. So it is a fundamental aspect in therocess. After sampling, lters and cartridges could beparately or together, depending if the work attempts toe partitioning of the pesticides between gas and partic-or not.methodology involves liquidsolid extraction (LSE) ofrapped in lters and cartridges, and is carried out byppropriate organic solvent. Lammel et al. [28] extractedtent OCPs regulated under the global POP convention

solved the E(DCM).

Howevebe extracteplers, becaumethod, anlytical met[107,108]. Sused alone,hexaneDChexaneacehas thedisa(250700m

This aforperiods in tintegrity ofagriculturalnoxy acid hpressurized

It is widacceleratedthose obtailizes organipressures (1ronmental

PLE incrsolvent conica GC-ECD; HPLC-UV [11][28]

GC-ECD 1.473; Florisil GC-ECD; GCMS 4.020 [29]

GC-ECD [30]GCNI-MS 0.0020.13 [31]GC-ECD; GCMS 0.0050.1 [32]

ioning; Florisil GCMS 0.1 [33]GC-ECD; HPLC-UV [34]

/Florisil GCMS; HPLC-UV 1 [35]GCMS; GCMS/MS 50.25 [36]GC-ECD; GCMS 40 [37]

-up GC-ECD 5.08.0 [38]GCECNI-MS 0.114 [39]

alumina GCMS 0.249 [85]GC-ECD [40]GCMS 0.71.3 [86]GCNI-MS 1.226 [87]GCNI-MS 0.010.48 [88]HPLC-UV 7013,800 [41]GCMS/MS 2.51250 [43]GCEI-MS 0.71110 [44]GCEI-MS 0.41.6 [45]

-up GCMS/MS 2.51250 [46]LCMS/MS 0.210 [47]GCNI-MS 0.83.8 [48]GCMS 40 [49]

-up LCMS/MS 6.532.8 [50]GC-ECD; GCNI-MS 0.1 [52]

s.

particulate matter trapped in lters with n-hexaneonic extraction during 30min. Shen et al. [89] using at described by Wania et al. [90], extracted organochlo-des from a XAD-2 PAS transferring the XAD-2 materialn column and passing through it 250ml of methanol350ml of dichloromethane.

acting OCPs trapped in a POG passive air sampler withethylene vinyl acetate (EVA), Farrar et al. [87] just dis-

VA coating by immersion in 35ml of dichloromethane

r, Soxhlet is the rst choice when pesticides are tod from lters and cartridges used in active air sam-se it has the advantage of being simple and low-costd it has been adopted in some standardized ana-

hodologies for determining pesticides in ambient airoxhlet extraction is performed with different solventssuch as acetone, DCM, or as solvent mixtures such asM, DCMlight petroleum (PE), cyclohexaneacetone ortone (see Table 3). This classical extraction techniquedvantageof beingboth, time (from6 to24h) and solventl), consuming.ementioned drawbacks together with the long-heatinghe Soxhlet ask that are prone to broke the structuralpolar thermally labile pesticides applied in modern(N-methylcarbamates, sulfonyl urea, and chlorophe-

erbicides), are leading to use alternative procedures asliquid extraction (PLE) [109].ely recognized that PLE (Dionex trade name ASE, forsolvent extraction), gives recoveries comparable to

ned with Soxhlet and other techniques in use. PLE uti-c solvents under elevated temperature (50200 C) and0002000psi) to extract organic pollutants from envi-

matrices [110,111].eases the speed of the extraction process with low-sumption, and can be automated. The main parameters


for method optimization are solvent, temperature and time. Pres-sure, between the operating values, is not considered a criticalexperimental parameter [112]. Despite of that, PLE has beenscarcely used for the extraction of pesticides on traps from airsamples.

Recentlyfrom air saPUF plugsether (7:1:2ies rangedand 14 OPPPUF/XAD-2as solvent,ticides waswith relativoxon and mextracted bthe sorbentused by Balan folped. Ssecond extrin the extra

Applyinget al. [50] ocurrently us2.5). No sigacetonitrilefrom72 to 1effect. A cerelative inticides by Pa static tim

It is weallows reduconsumptioof differentApplicationsedimentsever, to ourthe extracti

Prior tousual cleanextraction.and the XA(85:15), andlene bags anXAD-2 resindichloromeresin was presin lledwith Teonthe samplin

As pre-csolvent mixa mixture swas operatprocedurewPUFplugswsolvent-rinsbaked at 45pre-cleanin[30], who bwith alumial. [48] useutilize a rsacetone.

3.2. Clean-up

Air samples can contain a signicant amount of other com-ponents. During the extraction step many interfering (mainly

c) comay inclead.coluroacs (Tsorblumminalar sh theeasinnce.mineext

taineevapchanof n0mld inM/PElventar sors orgless

ersedestic7] aontolacets LiCsed,redpermraphybest s85] hp prnts (icaomeMS/Mary. Henhclea

eterm

r thehavh clavity or andas p

C deil noatogrenabsome authors have been used PLE to extract OCPsmples. Yang et al. [45] have extracted loaded QFF andindividually, using a mixture of hexaneDCMdiethyl, v/v), at 100 C during 15min (four times). Recover-from 62 to 100%. Raina et al. [47] extracted 10 OPPss degradation products from a glass bber lter and/Tenax/PUF sorbent cartridge. They used ethyl acetateat 100 C during 30min. No degradation of OPPs pes-observed and the recoveries ranged from 70 to 100%,e standard deviations from 1 to 21%, except for phoratealathion monocarboxylic acid that were not sufcientlyy PLE with ethyl acetate, because were strongly held tomaterial. Likewise, the same extracting method was

iley et al. [48] to extract the fungicides captan, captanolurrogate recoveries (diazino d10) were 85105%, and aaction with acetone showed no presence of pesticidescts.statistical design of experiments (DoE) [113], Coscoll

ptimized PLE parameters for the determination of nineed pesticides fromne airborne particulatematter (PMnicant differences between acetone, ethyl acetate and, used as solvents, were found, with recoveries ranging10%.However, extractswith acetone present lessmatrixntral composite design (CCD) was chosen to study theuence of temperature, pressure on the recovery of pes-FE. The optimised conditions were 50 C, 1750psi, ande of 1min.ll known that microwave-assisted extraction (MAE)ction of both, extraction time and organic solventn, and increases sample throughput in the extractionpollutants from environmental matrices [114116].

s of MAE for extracting pesticides from soils [117,118],[119] and foods [120122] have been proposed. How-knowledge, no works has been published related withon of pesticides from air traps.the sampling, the traps need to be cleaned. The moreing method is Soxhlet, with the same solvents used forSanusi et al. [34] pre-extracted the glass bber lterD-2 resin with Soxhlet for 24h using n-hexaneDCMthen dried in it a 60 C oven and stored in polyethy-d bottles, respectively. Peck et al. [44] pre-cleaned thewith 24-h Soxhlet extraction with methanol, acetone,

thane, hexane and 50:50 hexaneacetone. The XAD-2ut into stainless steel sampling in the laboratory. Thecartridges were stored in aluminium canisters sealedtap and sealed plastic bags during transport to and fromg locations.lean procedures some authors used PLE with differenttures. For PUF plugs pre-cleaning, Yang et al. [45] usedolvent of hexaneDCMethyl ether (7:1:2), and the PLEed at a temperature of 100 C, 15min. The extractionas repeated six timesusing fresh solvent each time. Theeredriedovernight inavacuumdesiccator andstored inedglass jarswith Teon lined lids before use. QFFswere0 C for 8h to remove organic contaminants. Similar PLEg procedure for QFF were followed by Sofuoglu et al.aked overnight the lters previously wrapped looselynium foil, in a mufe furnace at 450 C. Also Bailey etd PLE for PUF, XAD-2 and Tenax TA cleaning, but theyt extraction with ethyl acetate, and a second one with

organiand mfore, arequire

Theup appsamplephasecate), aor alunon-pothrougof incrdiffere

Alusamplewas obrotaryand exof 1 gwith 1applie(5% DCand so

Polsuch abutarerange.

Revpolar pucts [4loadedof ethysuch abeen umonito

GelmatogGPC iset al. [clean-upollutafor pur

In sas GCnecess(signalform a

3.3. D

OveticidesGC witselectiof polacides, h

3.3.1. GUnt

chromfor amponents are co-extracted togetherwith target analytesterfere in their identication and quantisation. There-n-up step performed after concentration is generally

mn based-SPE has become the most common clean-h for the purication of pesticide residues from airable 3). The most frequent sorbents include normalents [123] such as Florisil (synthetic magnesium sili-ina, silica gel, or a combination of them (alumina/silica/Florisil). In these polar sorbents, only extracts in aolvent, typically hexane or isooctane, are percolatedsorbent after conditioning. Step elution with solvent

g polarity allows a fractionation on the basis of polar

was employed for the clean-up of lters and PUF airracts for the determination of OCPs [39]. The extractd from Soxhlet extraction with PE and concentrated byoration, blown down with a gentle stream of nitrogenged into isooctane. Clean-up was made on a columneutral alumina (Al2O3). The column was pre-eluteddichloromethane followed by 10ml PE. Extracts were1ml isooctane and the column was eluted with 15ml). The eluate was concentrated by nitrogen blow-down-exchanged into isooctane before analysis.bents performgood clean-up formost apolar pesticidesanochlorine and some organophosphorus compounds,suitable for clean-upofanalytes coveringawidepolarity

-phase C18 silica has been used for clean-up of moreides such as OPP herbicides and OPP degradation prod-nd some fungicides [48]. Extracts in methanol werethe preconditioned C18 cartridge and eluted with 5mlate. However, no macroporous polymeric sorbents [76]hrolut EN, Oasis HLB, Bond Elut PPL, Isolute ENV+ haveprobably because of the low number of polar pesticidesin atmosphere.eation chromatography (GPC) or size exclusion chro-separates compounds on the basis of their size [124].uited for removingmaterials likewaxes and fats. Jawardave been used GPC with Biobeads SX3, in a two-stepocedure to detect OCPs and other persistent organicsPOPs), after an alumina-silica chromatographic columntion of extracts from PUF passive sampler.cases, mainly when using very selective detectors suchS [46] and LCMS/MS [50], no previous clean-up wasowever, it is essential to study the matrix effect [125]

ancement or suppression) before to decide not to per-n-up step, ruggedness and instrumental maintenance.

ination

past decades, approaches to detect trace levels of pes-e changed signicantly, moving away from the use ofssical detectors to GCMS because of the sensitivity andfferedby theMSdetector. Likewise, the increasinglyusesometimes thermal-labile compounds, mainly herbi-

romoted the use of LCMS based methods.

tection methodsw, pesticide residues in air are mainly analysed by gasaphy (GC). Volatility and thermal stability are requiredle-GC pesticides.


The detection methods most widely used are electron-capturedetection (ECD), nitrogen-phosphorus detection (NPD) and massspectrometry (MS).

GC-ECD was commonly used for the analysis of OCPs. Manyworks relatOCPs (aldriproducts, dthis very semployeddimethylsilID0.25mutilize heliu

Becauseauthors carTable3).GCdeterminatlytical technin the analytitative and

The MSworking ina higher seby GCMS,monly usedGCMS, usi5% phenyl m0.25mm IDretention tistandard mretention ti

TheGCionization (cal ionizatiolower LOQble in multistructural in

Some poamenable-Gbeen also dmode, afteanalysed 10D, MCPA),GCMS aftederivatizingve polar hand triura

Scheyer(PFBBr) to dtoluron) an

Some aucity, have(MS/MS) ushave develothe analysia derivatizamethod doe

Precise oto maximizthe selectiofragmentatthen isolatedissociationfor each conaffect the frITMS systemcan be mad

at-a-time (COST), or using DoE [116] Methods for multiresiduedetermination of pesticides by GCMS/MS have been widely set upin other matrices such as vegetables, soils or sediments, using bothIT [128], and triple quadrupole detectors (QqQ) [129]. Until now,

st de

HPLCh-peana

undsatesizatiwhe

natedalyseane,yl. Thlm thas maudinathemt usiationitrilfrome aupre

selecuchame

e hig130ed foples

na eton ofelectd tholec

ionsng thtranon oly froreced forn citr5). Acion wpresrateged [1al suerelyy LCcontecharbe cropr

urre

ecende ced with air monitoring for POPs, that includes somen, cis and trans-chlordane, DDT and transformationieldrin, endrin, heptachlor, HCB, mirex) still are usingensitive and selective detector (Table 3). Columnsare non-polar or semi-polar, 5% phenyl/95% poly-oxane (DB-5, Optima-5), mostly of 30m0.32mm

lm thickness, or 60m0.25mm ID, 0.10m. Theym as carrier gas and the splitless injection mode.of uncertainty of the identication with GC-ECD, someried out a conrmation of pesticides by GCMS (seeMS is increasingly replacing traditionaldetectors in theion of pesticide residues in air, and is nowadays the ana-iquemostwidely used. GCMS is a necessary approachsis of pesticides in air for its capacity to provide quan-conrmatory results, and for its high sensitivity.analyser most frequently used is quadrupole, mainlyselected ion monitoring (SIM) mode, which providednsitivity than full scan mode. In multiresidue analysiselectron ionization (EI) in positive mode, is most com-. Peck et al. [44] have analysed 51 CUPs in ambient air byng a quadrupole analyzer in SIMmode, with EI+. A 30-methylsiloxane capillary column was utilized (HP-5MS;

, 0.25mlm thickness). All analyteswere identied byme and with two characteristics ions, and the internalethod was used for quantication. The analytes presentmes ranging from 23.86 to 85.22min.MS techniquehasbeenalsousedwithnegative chemicalNCI), mainly for analysis of OCPs (see Table 3). Chemi-n (CI) is a softer ionization approach that tends to givedepending on the pesticide, but is not widely applica-class pesticide methods and does not provide as muchformation about the analyte as EI.lar pesticides cannot be analysed directly by GC (noC pesticides). However, different polar pesticides haveetermined by GCMS, both in EI and NCI ionization

r a prior derivatization step. Waite et al. [36] havepolar herbicides, including aryloxyalkanoic acids (2,4-

triazines (atrazine) and thiocarbamates (triallate), byr methylation with ethereal diazomethane. The sameagent has been used in a previous work [49] to analyseerbicides such as triuralin, dicamba, diclofop, MCPAlin.et al. [43,46] have used pentauorobenzylbromideerivatice urea herbicides (diuron, isoproturon, chloro-

d aryloxyalkanoic acids (2,4-D, MCPP, MCPA).thors, looking for a best sensitivity and highest speci-used GC coupled to mass spectrometry in tandeming ion trap (IT) instruments [126]. Scheyer et al. [43]ped a multiresidue method using GCIT-MS/MS for

s of 27 multiclass pesticides, some of them requiringtion step (ureas). Owing to the high specicity, thes not require a clean-up step.ptimization of MS/MS parameters is needed in ordere the signal for each pesticide. Usually the rst step isn of the parent ions from each pesticide study of theion (full scan spectra) of each analyte. Precursor ions ared in the ion trap and fragmented by collision-induced(CID) [127] and the two most abundant product ions

gener are selected. Different parameters canpotentiallyagmentation by CID and the analytical response of the, depending on the instrument used. The optimization

e by software, by the approach of changing-one-factor-

this lain air.

3.3.2.Hig

for thecompocarbamderivatmancefractioand anphosalcarbar4m80:20)

Bardetermto 9 cSoxhleevapor(acetonranged

SomMS/MSbetterelds sresidueachievdures [validatair sam

Raiminatiusingreportethesemtransitchoosisecondrmatitypical

In amethocides i(PM 2.extraction suption stwas us

Signcan sevlevels bin themanceshouldan app

4. Occ

In rpesticitector has not been used in the analysis of pesticides

detection methodsrformance liquid chromatography (HPLC) has beenusedlysis of non amenable-GC pesticides, i.e. those polaror with low-thermal stability such as urea herbicides,, triazines or phenoxy acids [60], or those requiringon to improve volatility or chromatography perfor-n GCMS methods are used. Sanusi et al. [11,34] havethe extracted pesticides from XAD-2 resin and lters,

d twoout of three fractions byHPLC-UV,which includesmecoprop, atrazine, diuron, isoproturon, carbofuranandey used a reverse phase columnC18 (30 cm3.9mm ID,ickness), with a binary solvent (methanolacetonitrile,obile phase.et al. [41] developed a multiresidue method for theion of 16 polar pesticides in atmosphere, belongingical families, using HPLC-UV. After extraction withng n-hexane:diethyl ether (90:10, v/v) for 24h, and, the deposit was dissolved in 2ml of mobile phasee:water:acetic acid, 30:59:2, v/v). The limits of detection

0.7 to 13.8ngm3.thors have described the benets that HPLC coupled tosent in terms of wider scope, increased sensitivity andtivity [130] forpesticideanalysis. For this reason inothers foodsafety, thedevelopmentofmultiresiduepesticidethods by LCMS/MS has become essential in order toher sensitivity and specicity and conrmatory proce-134]. However, few methods have been developed andr multiresidue analysis of pesticides in environmental.al. [47] have developed a LCMS/MS method for deter-24 OPPs and their degradation products in air samples,rospray ionization in the positive mode (ESI+). Theyat APCI ionization mode gave poorer sensitivity forules than ESI+. Formost compounds two characteristicswith best sensibility for each compound were selected,e most intense for quantitative analysis (SRM1) and thesition (SRM2), alongwith the ratio SRM1/SRM2 for con-f the compound. The method detection limits rangingm0.2 to 10pgm3 with typical air volumes of 2700m3.nt work, Coscoll et al. [50] developed a LCESI-MS/MSanalysis of nine currently and extensively used pesti-ic, fruits and grapes, in ne airborne particulate matteretone was selected as the most appropriate solvent forith PLE. All compounds presented matrix effect mainly

sion. In order to compensate thematrix effect, a calibra-y based on using matrix-matched standard calibration34].ppression or enhancement as a result of matrix effectcompromise quantitative analysis of pesticides at trace

MS/MS.Matrix effectmust be evaluated and discussedxt of method development before studying its perfor-acteristics and appropriate strategies for compensationarried out, improving sampling preparation or selectingiate calibration strategy [125].

nce of pesticides in air

t years, several monitoring studies have been reportedoncentrations in remote, rural and urban zones of


Table 4Concentrations of pesticides in ambient air.

Compound Class Regulatory EU Range (ngm3) Site Ref.

2,4-D Aryloxyalkanoic acid (H) In 0.028637 Rural [29,36,41]DDTs Organochlorine (I) Out ND0.293 [38]Acetochlor Chloroacetamide (H) Out ND53.5 Rural [44]Aclonifen Diphenyl ether (H) Pending ND4.2 Rural [35]Alachlor Chloroacetamide (H) Out ND8.5 Rural, urban [29,35,36,44]Aldrin Organochlorine (I) Out ND0.466 Rural, urban [30,31,38,45]Ametryn Triazine (H) Out Rural [44]Atraton (H) ND2 Rural [44]Atrazine Triazine (H) Out ND8.5 Rural, remote [29,3436,44,46]Azinfos-methyl Organophosphorus (I) Out ND16.5 Rural [27,48]Azinfos-methyl oxon Metabolite ND0.0061 Rural [48]Bitertanol Triazole (F) Out ND0.155 Rural [50]Bromoxynil Hydroxybenzonitrile (H) In 0.00860.791 Rural [29]Butachlor Chloroacetamide (H) Out ND0.15 Rural [44]Butylate Thiocarbamate (H) Out ND5.3 Rural [44]Captan Phthalimide (F) In ND22.8 Rural [35,48]Carbaryl Carbamate (I) Out ND0.696 Rural, remote [34]Carbendazim Benzimidazole (F) In ND0.572 Rural [50]Carbofuran Carbamate, N-methyl (I) Out ND8.1 Rural, remote [34]Carboxin Oxathiin (F) Out ND0.24 Rural [44]Chlordane, trans- Organochlorine (I) 0.0130.894 Rural [30]Chloroneb (F) ND2.4 Rural [44]Chlorothalonil Chloronitrile (F) In ND458 Rural [27,35]Chlorpyrifos Organophosphorous (I) In ND2.9 Rural [30,44]Chlorpyrifos ethyl Organophosphorous (I) ND97.8 Rural [35]Chlorpyrifos oxon Metabolite 0.1960.189 Rural [47]Chlorthal Benzenedicarboxylic acid (H) Pending ND0.033 Rural [44]cis-Chlordane Organochlorine (I) Out ND0.25 Urban [32,38,39,45]cis-Nonachlor ND0.004 Rural [39]Cycloate Thiocarbamate (H) Out ND0.74 Rural [44]Cyprodinil Anilinopyrimidine (F) In ND3.3 Rural [35]DEA Metabolite ND1.3 Rural [44]Deltamethrin Pyrethroid (I) In ND4770 Rural, urban [41]DEP Metabolite Out ND0.102 Rural [41]DIA Metabolite Rural [44]Diazinon Organophosphorus (I) Out ND612.4 Rural [35,41,44]Diazinon oxon Metabolite ND0.696 Rural [41]Dicamba Auxine (H) In 0.0190.615 Rural [29]Dichlobenil Benzonitrile (H) Out ND0.74 Urban [35]Dichlorvos Organophosphorus (I) Out ND2.3 Rural [44]Dieldrin Organochlorine Out 0.0020.136 Rural, urban [30,31,3840]Diufenican Pyridinecarboxamide (H) In ND0.462 Urban [35,46]Dimethoate Organophosphorus (I) In 0.00130.019 Rural [41]Dimethomorphe Cinnamic acid (F) ND0.1 Urban [35]Disulfoton Organophosphorus (I) Out ND1.4 Rural [44]Diuron Urea (H) In ND12.8 Remote, rural, urban [34,46]Endosulfan I Organochlorine (I) Out 0.0031.373 Rural [30,39]Endosulfan sulfate Metabolite 0.0011.271 Rural [30,31]Endosulfan, - Organochlorine (I) Out ND81.3 Rural, urban [27,35,38]Endosulfan, - Organochlorine (I) Out ND7.2 Rural, urban [27,38]Endrin Organochlorine (I) Out 0.0050.891 Rural, urban [30,38]Endrin, Keto- Organochlorine (I) 0.0060.082 Rural [30]Epoxyconazole Triazole (F) In ND0.4 Urban [35]EPTC Thiocarbamate (H) Out ND0.85 Rural [44]Ethaluralin Dinitroaniline (H) Out ND0.453 Rural [29,36]Ethofumesate Benzofuran (H) In ND1.2 Rural [35]Ethoprop Organophosphorus (I) In ND1.2 Rural [44]Etridiazole Aromatic hydrocarbon (F) Out ND0.23 Rural [44]Fenpropidin Morpholine (F) In ND3.5 Rural, urban [35]Fenpropimorph Morpholine (F) In ND13.2 Urban, rural [35]Fluazifop-P-butyl Aryloxyphenoxypropionate (H) ND0.07 Rural [27]Folpet Phthalimide (F) In ND82.2 Rural, urban [35,48]Fonofos Organophosphorus (I) Out ND0.099 Rural [44]HCB Organochlorine (F) Out 0.0811.62 Remote, rural [34]HCH, - Organochlorine (I) Out 0.0043.853 Rural [30,34,38,39,45]HCH, - Organochlorine (I) Out ND0.631 Rural [30,32,45]HCH, - Organochlorine (I) Out 0.0010.666 Urban, rural, remote [30,31,34,38,46]Heptachlor Organochlorine (I) Out 0.00080.156 Rural, urban [30,32,39]Heptaclhorepoxy Metabolite ND0.072 Rural [39,45]Hexythiazox (A) Out ND0.434 Rural [50]Imazalil Imidazole (F) In ND0.637 Rural [50]IMP Metabolite ND0.226 Rural [47]Isofenfos Organophosphorus (I) Out ND0.54 Rural [44]Isomalation Metabolite ND0.0036 Rural [47]Isoproturon Urea (H) In ND19 Remote, rural, urban [34,41]Linron Urea (H) In ND5.1 Urban [41]


Table 4 (Continued)

Compound Class Regulatory EU Range (ngm3) Site Ref.

Malathion Organophosphorus (I) Out ND4450 Urban [35,41]Malathion oxon Metabolite 0.00290.611 Rural [47]MCPA D4.9MCPP D513Metalaxil D1Metazachlor D0.8Methamidofos D10.Methidathion D0.3Methoxychlor .0430Metobromuro D3.1Metolachlor D27.Metribuzin D0.9Metsulfuron m D11Mirex .0066Molinate D0.0Napropamide D0.0Omethoate .0009Oxychlordane D0.0Oxyuorfen D3Parathion-met D6Pebulate D12Pendimethalin D117Phorate D91.Phosalone D3.6Primicarb D5.1Prometon D4.3Propachlor D1.7Propargite D45Propazine D0.1Propyzamide D0.3PyriproxyfenSimazineSimetrynSpiroxamineTCPTetrachlorvinpThiabendazoleTolyluanidToxapheneTriadimefonTriallateTricyclazoleTriuralinVernolateVinclozolin

H: herbicide, F

different cothat have brecent yearAlso, their rreported.

It couldbsive of the afound are thsuch as oxyimidaclopriysed but no

In generin gas and pdistributionin ambient

Taking inof the subsaryloxyalkaazines. Morforbidden a

Regardindimethoatecides detecAryloxyalkanoic acid (H) In NAryloxyalkanoic acid (H) In NAcylalanine (F) Out NChloroacetamide (H) Pending NOrganophosphorus (I) Out NOrganophosphorus (I) Out NOrganochlorine (I) Out 0

n Urea (H) Out NChloroacetamide (H) Out NTriazinone (H) In N

ethyl Triazinylsulfonylurea (H) NOrganochlorine (I) Out 0Thiocarbamate (H) In NAlkanamide (H) Out NMetabolite Out 0Organochlorine NDiphenyl ether (H) Out N

hyl Organophosphorus (I) Out NThiocarbamate (H) Out NDinitroaniline (H) In NOrganophosphorus (I) Out NOrganophosphorus (I) Out NCarbamate (I) In NTriazine (H) NChloroacetamide (H) Out N(A) Out NTriazine (H) Out NBenzamide (H) In N

Juvenile hormon mimic (I) Out ND0.1Triazine (H) Out ND0.4Methylthiotriazine (H) ND0.0Morpholine (F) In ND12.1Metaolite 0.0260

hos Organophosphorus (I) Out ND0.6Benzimidazole (F) In ND1.3Sulphamide (F) In ND86Organochlorine (I) Out 0.3190Triazole (F) Out ND2.9Thiocarbamate (H) Pending ND15.Reductase (F) Out ND0.1Dinitroaniline (H) Out ND40Thiocarbamate (H) Out ND0.1Dicarboximide (F) Out ND0.2

: fungicide, I: insecticide; ND: non-detected.

untries. Table 4 identies about a hundred pesticideseen determined in ambient air in studies developed ins using active sampling, mainly high-volume samplers.egulatory status in the European Union (EU) [135] are

e said that pesticides listed inTable 4 is not comprehen-ctual atmospheric contamination, since the compoundsose that were sought for, although several compoundsdemeton-S-methyl, oxadiazon, uazinam, udioxonil,d,methidation ormethiocarb [35,50], whichwere anal-t detected.al, the reported values are the sum of pesticides presentarticulate phases, although some studies reported thebetweengas andparticles. Concentrationsofpesticidesair ranged from few pg per m3 to many ng per m3.to account the compounds listed in Table 4, near 50%

tances detected in ambient air are herbicides, mostlynoic acids, chloroacetamides, thiocarbamates and tri-e than half of these herbicides detected are nowadaysccording to the EU regulations.g insecticides, only 5 (primicarb, chlorpiryfos,, ethoprop and deltamethrin) out of 35 insecti-ted could now be used for plant treatments in Europe.

Table 4 alsoclasses suchamide) ben(captan, folcountries oin air of thpoorly inve

Some auCUPs are coand that theever, Peck ean area of Uand not corpresence offactors, sucand atmospoverall conduring the p[137].

Locally hand are corrin air usuaing with ap6 Rural [29,36]0 Rural [41]

Rural [27,29]Urban, rural [35]

5 Rural [27]Urban [35]

.99 Rural [30]Rural [27]

5 Urban, rural [35,44]6 Rural [27]

Urban [41]0.255 Urban [29]15 Rural [44]25 Rural [44]0.0027 Rural [47]0022 Rural [31]

Rural [35]Rural [44]Rural [44]

.3 Rural [35]2 Rural [44]70 Rural, remote [34]

Rural [27]Rural [44]Rural [35,44]

.6 Rural [35]2 Rural [44]3 Rural [44]

55 Rural [50]

Rural [44]9 Rural [44]

Rural [35].131 Rural [47]1 Rural [44]71 Rural [50].4 Urban, rural [35].771 Rural [39]

Rural [35]3 Rural [29,36,44]7 Rural [44].7 Urban, rural, remote [29,3436,44,46]9 Rural [44]

Urban, rural [35]

shows 21 fungicides belonging to different chemicalas morpholines (fenpropidin, fenpropimorph, spirox-

zimidazole (carbendazim, thiabendazole) or ftalamidespet). Nine of these fungicides are today forbidden in allf the EU. Consequently, it can be said that the occurrencee majority of the currently used pesticides in air arestigated.thors have shown that atmospheric concentrations ofrrelated to the proximity of sampling to sources areasoccurrence usually is linked with local use [136] How-t al. [44] showed that the amount of pesticide used inSA is only slightly correlated to the detection frequencyrelated to average concentrations. These means that thea pesticide in the air is dependent on its use, but other

h as V/P distribution, wet and dry deposition, transportheric degradation, are also important. Nevertheless, thecentration at a regional scale is expected to be highereriod when a given pesticide is applied over large areas

igh concentrations of pesticides in air are very seasonalelated to local use patterns. The highest concentrationslly occur in the spring and summer months coincid-plication times and warmer temperatures. However, for


some CUPs that are detected, it is not always clear if their con-centration and frequency in air is associated with local use and/orlong-range transport (LRT) from other sources [137].

Pesticides have also been detected at low levels during periodsafter use, but the determination of their sources has proven to bedifcult. Thand wind eareas. Whitdetected incation on thpersistencefore, the pofrom soil ev

5. Conclus

During tin ambientpesticides tand soil, mand develofurther studures and tare requiredfate of curre

There issorbents shtrapped pecurrently ucapacity ofrange of pequantities.

Presentlextraction tTherefore, etechniquesor microwaThese technysis of pestSo, they wil

Sampleticides inas LCMS/Minterferencesimplicatiintegrationnecessaries

Analyticmeasuremeous evidenConsequentpesticides inon GC-amthermal inssequently,essential apAlso furthecould be neitoring pesair.

Manyofand only amonitoringto reach a bthe current

Acknowledgements

This work has been nanced by the Generalitat Valen-ciana through the project DEPESVAL (GV/2007/257), and by theMinisterio d

BQUl tonts tothis

nces

van d. SmeCUS Went, EGil, CBedosVoutsBedosllier, EFerrarP. Rice. Leisti. TechF. BidlSanu

.F.G. VLi, G. Z(200Schey. Addutchatater A.A.H.AemosLe PeemosFeigevironAtkinil Poll.A.H. APesticviron. Tadeess, BA. Este(200

Namieem. 3Bedosmpen

ormalns la

enis, 2M. Wh006) 1. LammvironYao, Llzerf,Sofuo

on. 35Gioiamos.. Xua,MHarra. Sanu3.ntamrt n

.T. WaemosJ. CessSchey17.. AlegrBurhlBarau003) 1eseoff-seasonoccurrences couldbedue tovolatilizationrosion or the result of long-range transport from othere et al. [27] found that the herbicide metribuzin wasan overnight samplemore than 2months after its appli-e farms elds. They attribute this fact to the relativeof metribuzin in soil (half-life is 106 days) and, there-ssibility of post-application volatilization of metribuzinen 2 months after application.

ions and future trends

he past decade different studies related with pesticidesair have been developed, mainly focused in emission ofo the air during application, volatilization from plantsonitoring ambient air in remote, rural and urban areaspment of sampling and analytical methods. However,dies are necessaries to improve the sampling proce-he analytical methods, and wider monitoring studiesto achieve a better knowledge of the occurrence and

ntly used pesticides in ambient air.a lack of consistency in sampling methodologies. Newould be selected in order to increase the scope of thesticides and to make the HVS suitable to sample newsed pesticides. Also, studies related with the retentionthe different materials need to be developed for a widersticides, principally for those that are used in greater

y used analytical methods generally involve Soxhlethat requires big solvent volumes and is time consuming.fforts should be made to develop sample preparationbased on modern extraction techniques such as ASEve in order to avoid these aforementioned drawbacks.iques have provided good results in multiresidue anal-icides in other matrices such as food, soil or sediments.l also be used in ambient air.preparation is the limiting step of the analysis of pes-air. Even using powerful detection techniques suchS, some clean-up is still necessary since otherwises or matrix effect can occur. Further studies toward

on of sample preparation, including automation andof sample preparation and instrumental analysis areto improve performance of faster procedures.al methodologies employed must be capable of residuents at very low levels, and must provide unambigu-ce to conrm the identity of any residue detected.ly, MS is a necessary tool in the modern analysis ofn air, coupled to GC or HPLC. Likewise, the number ofenable compounds because of their poor volatility ortability has grown considerably in the last years; con-HPLC coupled to MS, in tandem mode, should be anproach in the multiresidue analysis of pesticide in air.r developments involving techniques such as TOF-MScessaries in order to apply non-target analysis in mon-ticides and their degradation compounds in ambient

theactive substances studiedarenowbannedpesticidessmall percentage can be considered CUPs. Additionalstudies and wider sampling networks are necessariesetter knowledge of the occurrence, fate, and impacts ofly used pesticides.

05719/gratefuVY warealize

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Sampling and analysis of pesticides in ambient airIntroductionSampling of pesticides in ambient airActive samplingMaterials for sample collection

Passive air sampling

Analytical proceduresExtractionClean-upDeterminationGC detection methodsHPLC detection methods

Occurrence of pesticides in airConclusions and future trendsAcknowledgementsReferences

Documents

Sampling