C. Postigo1, M.J. Lpez de Alda1, M. Viana 2, X. Querol 2, A. Alastuey A.2, B. Artiano3, D.

Barcel
1 Institute

of Environmental Assessment and Water Research (IDAEA), Department of Environmental Chemistry, CSIC, 08034 Barcelona, Spain
2 Institute of Environmental Assessment and Water Research (IDAEA), Department of Geosciences, CSIC, 08028 Barcelona, Spain
3 Research Center for Energy, Environment and Technology (CIEMAT), 28040, Madrid, Spain
4 Catalan Institute for Water Research (ICRA), 17003, Girona, Spain

1, 4.

4. RESULTS AND DISCUSSION

1.INTRODUCTION
The detection and quantification of the levels of drugs of abuse (cocainics, cannabinoids,
amphetaminics, etc.) in environmental water samples has been proposed as a means to
estimate drug consumption by the population (Daughton 2001) and already several analytical
methods have been reported for this purpose (Postigo et al. 2008a). This strategy provides
real-time information regarding collective drug usage in a simple, fast, economical and
anonymous way, compared to traditional methods (e.g. statistical and medical indexes and
population surveys). Presence of cocaine in airborne particles of different cities has been also
reported (Hannigan et al. 1998, Cecinato and Balducci, 2007) and concentrations may be
correlated to abuse prevalence and/or seizure amounts and may also allow identification of
drug dealing areas.
The present work describes the first analytical method specifically developed for the
multianalyte determination of several drugs of abuse in air and its application to various
samples collected in Spain. Fine grain-size airborne particles (PM2.5) were collected at two
urban background sites in Barcelona and Madrid, located in the university areas in each city.
A total of 12 and 7 samples were collected in Barcelona and Madrid, respectively, on
moving days, including weekends. High-volume (30 m3/h) samplers with PM2.5 inlets were
used, with quartz fibre filters (Schleicher & Schuell QF20) as collection substrates.

1. Drugs of abuse such as cocaine (CO), cannabis (THC), amphetamine-like

compounds (AM, MA, MDMA) or even heroin (HER) are present in aerosols at
detectable concentrations by means of the proposed methodology (significant
results above the method detection limits). Frequence of detection of the positively
identified analytes in the investigated samples and average concentrations are
shown in Table 2.
2. Cocaine was detected at both study sites, with daily concentrations ranging from
30 to 850 pg/m3. These concentrations are up to one order of magnitude higher
than those registered in Rome (5040 pg/m3, Cecinato and Balducci, 2007).
3. A major difference between the results obtained for Madrid and Barcelona refers
to heroin, which was detected in Madrid but not in Barcelona. This is probably
related to the location of the monitoring site in Madrid and also to heroin
consumption habits in this city, where heroin is preferentially smoked (De la
Fuente de Hoz et al. 2005).
4. A weekly trend was observed in Barcelona, with higher levels of most compounds
(especially cocaine) during the week-ends (including Fridays). No samples were
avilable for Madrid for the weekends, where no weekly trends were observed (see
Figure 2).
Table 2. Number of positive samples (Freq.) and average and standard deviation of the
concentrations of drugs of abuse determined in the airborne samples investigated.

2. OBJECTIVES
9 to develop an analytical method, the first described in the literature, for the determination of
17 drugs of abuse and metabolites in airborne samples
9 to investigate, for the first time, the presence of these drugs in atmospheric particulates in
Spanish urban environments
9 to obtain a preliminary picture of their spatial and temporal variability in order to interpret
consumption patterns

3. ANALYTICAL METHODOLOGY
Liquid chromatography:
- LC column: Purospher STAR
RP- 18e (1252 mm, 5 m)
- Mobile phase:
acetonitrile/water
- Flow rate : 0.3 ml/min
- Injection volume: 5 l

CO

BE

AM *

MA

FRI

MON

MDMA

a)

THC

600

Mass spectrometry:
- MS/MS: 4000 Q-Trap
(Applied Biosystems)
- Ionization: Electrospray (ESI)
- Operation mode: SRM (NI,PI)

500

400

pg/m3

Sample preparation:
- Addition of surrogate standards
- Pressurized liquid extraction
(PLE) of air sampling filters: ASE
200 (Dionex)
- Drying extract under N2
- Reconstitution of extract in 500
l methanol

300

200

Figure 1. Scheme of the analytical method: PLE extraction followed by LC-MS/MS analysis

100

Figure 1 shows an scheme of the analytical methodology developed for determination of the
target analytes in airborne particles. Sample preparation is limited to the addition of surrogate
deuterated standards to the air sampling filters and their extraction by pressurized liquid
extraction (PLE). Analysis of the extracts is performed by liquid chromatography-tandem mass
spectrometry in the selected reaction monitoring (SRM) mode, recording two SRM transitions
per compounds, thus, providing 4 identification points for each target analyte (Postigo et al.,
2008b). The performance of the method was evaluated through determination of the linearity,
sensitivity, repeatability, recovery and presence of matrix effects. Results obtained are
summed up in Table 1.

0
THU

FRI

MON

TUE

27-Sep-07 28-Sep-07 1-Oct-07

THU

2-Oct-07

CO

TUE

WED

18-Oct-07 19-Oct-07 29-Oct-07 6-Nov-07

BE

HER

6ACM

AM *

SAT

SUN

SUN

7-Nov-07 10-Nov-07 11-Nov-07 18-Nov-07

MA

b)

THC

900
800
700
600

pg/m3

Table 1. Quality control parameters of the analytical method

500
400
300
200
100
0
FRI

MON

WED

WED

TUE

WED

TUE

30-Nov-07

3-Dec-07

5-Dec-07

12-Dec-07

17-Jan-08

18-Jan-08

22-Jan-08

Results not confirmed by the 2nd SRM transition due to the presence of interferences

Figure 2. Levels (pg/m3) of drugs of abuse in airborne samples collected

in a) Barcelona and b) Madrid.

5. CONCLUSIONS

Amphetamine-like compounds: EPH: (R,R)(-)-pseudoephedrine + (1S,2R)(+)-ephedrine hydrochloride, AM: amphetamine,

MDMA: 3,4-methylenedioxymethamphetamine or ecstasy, MA: methamphetamine,
Cocainic compounds: BE: benzoylecgonine, CO: cocaine, CE: cocaethylene.
Lysergic compounds: O-H-LSD: 2-oxo-3-hydroxy-LSD, nor-LSD: nor-LSD + nor-iso LSD, LSD: lysergic acid diethylamide.
Opioids: 6ACM: 6-acetylmorphine, MOR: morphine, HER: heroin.
Cannabinoids: nor-THC: 11-nor-9-carboxy-THC, OH-THC: 11-hydroxy-THC, THC: 9-tetrahydrocannabinol.
IS: Internal Standard, deuterated analogue used for the corresponding analyte quantification

REFERENCES:

9 A novel analytical method has been developed for the multianalyte determination of
several drugs of abuse in air. The methodology is based on pressurized liquid
extraction of the target compounds followed by liquid chromatography-tandem mass
spectrometry.
9 Application of this methodology to various samples collected in Madrid and
Barcelona (in University areas) has revealed the presence of cocainics, cannabinoids,
amphetamine-like compounds and heroin in ambient air. The highest level recorded
has corresponded to cocaine (850 pg/m3).
9 Further research is necessary to identify possible spatial and temporal variations of
the compounds analysed in these and other cities and to compare the results obtained
with those resulting from population surveys and/or social/medical record statistics
regarding drugs of abuse usage and seizures.

Daughton, C.G. (2001) In: Daugton, C.G., Jones-Lepp T.L. (Eds) Pharmaceuticals and personal care products in the environment: Scientific and regulatory issues. ACS Symposium Series 791,
Washington DC, 116-139.
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C. Postigo, M.J. Lpez de Alda, D. Barcel (2008b) Trends Anal. Chem. 27 (11), 1053-1069.
De la Fuente de Hoz, L., Brugal Puig, M.T., Ballesta Gmez, R., Bravo Portela, M.J., Barrio Anta, G., Domingo Salvany, A., Silva do Rosario, T., Ambrs Hortensi, M. Rev. Esp. Salud Pblica
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ACKNOWLEDGMENTS:

This work has been supported by the Spanish Ministry of Science and Innovation [CGL2007-64551/HID and CGL2007-62505/CLI]), the Spanish Ministry of
Environment and Rural and Marine Affairs (010/PC08/3-04.1) and it reflects the authors view. Cristina Postigo acknowledges the European Social Fund and AGAUR (Generalitat de Catalunya,
Spain) for their economical support through the FI predoctoral grant. Special acknowledgements go to Merck (Darmstadt, Germany) for the gift of LC columns.