© Benaki Phytopathological Institute
Vlastaras
et al.
68
R.T. of metribuzin, as in our case. The Kovats
RI of the other metabolite is much small-
er than the Kovats RI of metribuzin, which
makes metribuzin-diketo (M.W.=184) and
metribuzin-desamino-diketo (M.W.=169) as
smaller compounds to have earlier R.T. At
the time of the study, no reference materi-
al was available in our laboratory to confirm
the presence of any metabolite. Therefore,
the identification of any degradation prod-
uct or metabolite was not possible and this
investigation was used to partly explain the
low recovery of the certain compound. The
spectra presented in Figure 4(b) are in full
scan mode and in accordance with the com-
mercial available library of Dr Ehrenstofer,
which is a special collection of pesticides
and pollutants.
In conclusion, the peak with R.T.=13.17
min in the GC-MS system, shown in Figure
4(b), may have been a metabolite, a degra-
dation product or a pollution of the system
or matrix. However, in the framework of the
present study, it was difficult to determine
its identity. Further studies dedicated to the
identification of this compound are required.
Conclusions
Themethodof analysis proposedby thepres-
ent study is fast, easy and effective. By using
44 representative analytes, the method ap-
plied for the determination of more that 180
pesticides by gas chromatography with elec-
tron capture (ECD) and nitrogen phosphorus
(NPD) detectors was validated. Neverthe-
less, several difficulties occurred with certain
problematic molecules (dichlorvos, metibuz-
in) or specific chemical subgroups (polar or-
ganophosphorus pesticides). In addition,
the matrix effect played an important role in
the sensitivity of the analytes. For example,
in the case of demeton-s-methyl, propicon-
azole and penconazole, the signal to noise
ratio was higher in tomatoes than in grapes.
Although the validation of the method by
choosing representative analytes is of low
cost, effective and easy technique for testing
if a method is suitable for the determination
of a wider range of pesticides, it is not ade-
quate. According to the European
Commis-
sion (3),
for checking the methods perfor-
mance for all the analytes in its scope, each
laboratory should have a rolling programme
to include all other analytes at least every 12
months, but preferably every 6 months
.
Literature cited
Barceló, D., Hennion, M.C. 1997.
1.
Trace determina-
tion of pesticides and their degradation products
in water
, Elsevier, Amsterdam, 542 p.
Worthing, C.R. 1987.
2.
The Pesticide Manual.
12th
edition, British Crop Protection Council, 1344 p.
European Commission 2007.
3.
Method valida-
tion and Quality control procedures for pesticide
residues analysis in food and feed,
Document
No. SANCO/2007/3131. Available from: www.
ec.europa.eu/food/plant/protection/resourc-
es/ qualcontrol_en.pdf.
Council Directive 91/414/EEC. Concerning the
4.
placing of plant protection products on the
market.
Official Journal of European Community
L 230, 19.8.1991, p. 6
Working group “Development and improve-
5.
ment of Residue-analytical methods”. 1996.
An-
alytical Methods for Pesticide Residues in Food-
stuffs. Part I: Multiresidue methods,
6th Edition,
Ministry of Public Health, Welfare and Sport,
The Netherlands, p. 1-21.
Hellenic
6.
Accreditation System S.A. 2007.
Κατευθυ-
ντήρια Οδηγία για την Επικύρωση Μεθόδων Προ-
σδιορισμού Υπολειμμάτων Φυτοπροστατευτικών
Προϊόντων
nonismoi_eggrafa/f_mnimonia/mnimonio_fy-
toprostateytikon.doc (accessed on 29/12/2008).
Interactive PhysProp Database, url, available
7.
at:
(accessed on 29/12/2008).
Jarczyk, H.J. 1983a.
8.
Pflanzenschutz-nachrichten
Bayer
, 36/1983,1: 63-72.
Jarczyk, H.J. 1983b.
9.
Pflanzenschutz-nachrichten
Bayer
, 36/1983,1: 84-94.
Lehotay, S. 2007. Pesticide Residues in Foods
10.
by Acetonitrile Extraction and Partitioning with
Magnesium Sulfate.
Journal of AOAC Internation-
al
90: 485-520.
NIST/EPA/NIH Mass Spectral Library, Data Ver-
11.
sion: NIST 06 (Software Version 2.0 d).
Wells, D., Terence, G.B., Langner, E. 1986. Vapour
12.
pressure of permethrin.
Pesticide Science,
Vol. 17
(5): 473-476.
Received: 4 January 2010; Accepted: 17 June 2010
1...,28,29,30,31,32,33,34,35,36,37 39,40,41,42,43,44,45,46,47,48,...59