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4th MGPR
International Symposium of
PESTICIDES IN FOOD AND THE ENVIRONMENT
in Mediterranean Countries and MGPR Annual
Meeting 2005
ORAL
PRESENTATIONS
ABSTRACTS
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-01
Oral Presentations Abstracts
Registration of Plant Protection Products and EC
Harmonisation Studies in Turkey
Canhilal R., Karaca C., Turabi M. S.
General Directorate of Protection and Control, Ankara,Turkey
Companies intending to make application for a pesticide to be
registered by a MOA, should have got a Certificate of “Plant Protection
Dealing Permission” in convenience with the 5th Article of the Regulation
for the Registration of the Plant Protection Products. Following the
preparation of the Certificate, the company is permitted to apply for a
registration together with the necessary docs in either category as follows:
Registration of a product is done in two ways:
*Registration of a product after completing trials
*Registration of a product in norm basis (Me-too registration)
Following the application is evaluated and accepted by the “Commission
for Registration and Evaluation of Plant Protection Products”, the product
is sent for physical and chemical analyses. In case of suitable to its
specification, following necessary fee is paid, Registration Certificate is
prepared by the General Directorate. Registration procedures and
regulations of EC have been evaluated and draft regulation has been
forwarded to General Secretariat of EC for investigation. For some articles
which are different from current system and take time for applying into
practice, transition time will be needed to combine with the European
Union Regulation as new participated countries to Europen Union.
Keywords : Plant protection products, registration, EU harmonisation
1
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-02
Oral Presentations Abstracts
Novel Approaches to Improved Performance of GC/MS
Analysis of Pesticide Residues
Hajslová J., Ticha J.
Institute of Chemical Technology, Technicka 3, 16628, Prague, Czech
Republic
Gas chromatographic (GC) separation of sample extract
components followed by mass spectrometric (MS) identification
/quantification of target analytes still represents the main approach in
analysis of non-polar and/or moderately polar modern pesticides residues
of which may occur in various matrices including foodstuffs. Quadrupole is
probably the most popular MS analyser; however, to obtain sufficiently low
detection limits (LODs) required for residues regulation purpose, selected
ion monitoring (SIM) function has to be used. When using ion trap mass
analyser in (ultra)trace analysis, its operation in MS/MS mode is necessary
to obtain high detection selectivity hence improved signal-to-noise ratio
needed for achieving low LODs. Unfortunately, utilization of these sensitive
detection MSD settings, full spectral information is not available anymore,
what may - under certain circumstances - result in failing to fulfil
requirements specified in European Commission Guidelines [Off. J. Eur.
Commun. L221 (2002) 8-36] for confirmation of analytes identity. This
should be based on detection of at least four characteristic ions matching
the relative abundance criteria. The most serious problem as regards the
confirmation of apparent residues is encountered in analysis of complex
matrices, specifically in case of pesticides yielding low and hence
unspecific m/z value ions which might be obscured by co-elutions.
Improved selectivity of detection process as well as compatibility with fast
chromatography (compression of elution bands resulting in decrease of
LODs) is offered by the recently introduced mass analysers based on time-
of-flight (TOF) technology. This novel technique allows overcoming most of
the above drawbacks limiting full exploitation of mass spectrometry
potential in residue analysis. There are several challenging features
provided by the time-of-flight MS technique coupled to gas
chromatography (GC/TOF-MS). Depending on the type of instrument,
acquisition speed as high as 500 spectra/sec can be achieved by TOF.
While such „fast“ TOF MS instruments enable only a unit mass resolution
(typically about 1400 FWHM) its value for those systems employing high-
resolution TOF analysers may be as high as 7000 FWHM and even more.
Another unique feature of TOF-MS systems resulting from high mass-
analyser efficiency is continuous acquisition of full mass spectra even at
very low concentration levels. In addition, due to the absence of spectral
2
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
skew, utilization of a special computer software (deconvolution function)
Oral Presentations Abstracts
allows resolution of partially overlapped peaks in collected spectra hence
identification/confirmation of compounds by library search. In our
presentation the potential of both high resolution TOF-MS (GCT
Micromass, UK) and fast TOF-MS (Pegasus 4D, USA) in pesticide residue
analysis will be documented, performance characteristics achievable by
these sophisticated instruments will be compared with those obtained by
conventional MS scanning techniques. Besides improvement of detection
parameters, unique solution of separation problem (critical pairs that
cannot be resolved by deconvolution) that is enabled by utilization of
comprehensive two-dimensional gas chromatography (GCxGC) will be
discussed. The potential of GCxGC coupled to fast TOF-MS to identify
/quantify 70 modern pesticides at 0.01 mg/kg and lower levels in extracts
prepared from baby food by various sample handling approaches
(including QuEChERS) will be demonstrated.
Acknowledgement: This project was partly funded by NATO SfP-977983
project. Kind support provided by Dr. J. Zrostliková, Leco Instrumente
Plzen, CZ, is highly appreciated.
3
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-03
Oral Presentations Abstracts
The Strengths of Liquid Chromatography-Tandem Mass
Spectrometry (LC-MS/MS) in Residue Analysis
Zimmer D., Billian P., Schöning, R.
Bayer CropScience AG, Residues, Operator and Consumer Safety, Alfred-
Nobel-Str. 50, D-40789 Monheim, Germany
Introduction LC-MS/MS with electrospray ionization (ESI) and
atmospheric pressure chemical ionization (APCI) is the state-of-the-art
analytical technique for rapid and highly selective quantitation allowing for
high sample throughput and pg/mL sensitivity on a routine use basis.
Triple quadrupole based LC-MS/MS instruments commonly available from
different vendors for more than 10 years have proven to be robust and
reliable equipment in the modern pesticide residue analytical laboratory.
Objectives To demonstrate the strengths of LC-MS/MS in the
determination of residues of polar to unpolar compounds in complex
matrices of plant and animal origin and make comparisons with data
obtained using traditional methods such as. GC/ECD, GC/MS. Standard
LC columns with mostly reversed-phase material, mobile phases
containing methanol or acetonitrile, water and acetic or formic acid or
ammonium formate, and triple quadrupole MS/MS-instruments were used.
Due to the high selectivity and sensitivity of LC-MS/MS method
development is faster than previous traditional techniques. In many cases
time consuming clean-up steps are not neededand diluted raw extracts are
injected. LOQs of 0.01 mg/kg are typically achieved. Matrix effects, e.g. ion
suppression by co-eluting endogeneous components are reduced by
dilution of injection solutions or use of APCI instead of ESI. Internal
standards with structure and ionization capabilities similar to the analytes
compensate for matrix effects and are of benefit to further reduce method
development and run time . Favoured internal standards are stable
isotopically labeled analytes. The examples demonstrate that LC-MS/MS
has become a reliable, selective and sensitive residue analytical
methodology for data generation and enforcement.
Keywords : Liquid chromatography, tandem mass spectrometry,
residues, pesticides
4
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-04
Oral Presentations Abstracts
Using Automated Deconvolution Reporting Software to
Find Targets in Complex Matrices
Sandy C.
Life Sciences and Chemical Analysis Group, Agilent Technologies UK Ltd,
Eskdale Road, Winnersh Triangle, Wokingham Berkshire, UK RG41 5DZ
The multi-residue analysis if pesticides in foodstuffs by gas-
chromatography mass spectrometry is a very demanding analytical process.
The rate limiting step is often not the sample clean-up and preparation or the
sample analysis, but the reviewing and validation of the often complex
analytical data. This interactive data review process puts great pressure on the
analyst since complex matrix interferences inevitably result in either missing
the presence of target analytes completely or the reporting of many false
positive hits. These false positive hits must be individually reviewed and
processed by an experienced analyst – a very labour intensive process that
could lead to errors simply due to the large amount of interactive data
processing required.
This presentation discusses a fully automated approach to the multi-residue
analysis of pesticides in food extract samples using the Agilent Mass Selective
Detector – Deconvolution Reporting Software (MSD-DRS). MSD-DRS is an
application for target compound analysis which combines results from the
Agilent GC-MSD ChemStation, the NIST Automated Mass spectral
Deconvolution and Identification Software (AMDIS 32) and the NIST 2005
Mass Spectral Search Program (NIST05) into one easy-to-read report.
Target compounds are initially identified and quantified based on target and
qualifier ions. The total ion chromatogram is then processed by AMDIS 32 and
the deconvoluted full mass spectra searched against an application specific
mass spectral database – matrix interferences are usually eliminated and peak
integration is not used. The use of Retention Time Locking (RTL) enables
AMDIS to accept or reject hits based upon the locked retention time of the
target analytes. Targets identified by AMDIS 32 are then further searched
against the NIST05 MS database. Final report generation combines results
from the three techniques described above. Results are compared and sorted
both by locked retention time and by CAS number. A printed report is
generated together with a file in html format.
Latest developments with the DRS software, in conjunction with the latest
revision of AMDIS, enable fully automated graphics reporting of targets and
the analysis of data generated in Selected Ion Monitoring (SIM) mode.
‘Real World’ data will be shown demonstrating the quality of data produced by
the MSD-DRS software and the significant time savings compared to manual
data review.
5
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-05
Oral Presentations Abstracts
Fast GC-MS in Pesticide Residues Analysis
Matisová E., Kirchner M., Hercegová A., Dömötörová M.,
Hrouzková S.
Dept. Anal. Chem., Faculty of Chemical and Food Technology, SLovak
University of Technology, Radlinského 9, Bratislava 812 37, Slovak
Republic
There is a number of ways to take advantage of the improved speed
of analysis by faster GC, as the increased laboratory throughput resulting
in the reduced cost per analysis and the required time to get results. Many
more replicate analyses are performed in the same time that it would take
to perform a single conventional GC (this can be associated with better
analytical precision) [1]. For the ultra-trace analysis of pesticide residues
the sample preparation methods are very important. We have evaluated,
optimized and validated various approaches to sample preparation step for
baby food analysis. Contribution of various factors was estimated by
measuring their influence on recoveries, LOQs and repeatability of
measurements [2,3]. In spite of increasing selectivity through MS detection
(once the method of sample preparation has been selected) maximization
of selectivity through separation utilizing fast GC is important due to matrix
interferences and matrix phenomena that are the burden of
chromatographic system for pesticide residues analysis in non-fatty food
samples.The lower the required MRLs, as in baby food (10μg.kg-1), the
higher separation efficiency is required and reachable with narrow-bore
capillary columns. The search on the possibilities and limitations of
quadrupole mass spectrometric detector in fast GC with narrow-bore
capillary columns and the ruggedness with real sample measurement was
performed. Several ways to reduction of matrix effects that have a great
negative impact on the performance of chromatographic system were
practiced. Input control of raw material for the baby food production and
tracing the fate of pesticides during the technological processing and
wastes was performed utilizing optimized sample preparation technique
combined with PTV injection-fast GC-MS.
Acknowledgement: The authors acknowledge support of this research by
NATO project No. SfP 977 983 and Slovak Grant Agency VEGA No.
1/2463/05. [1] Matisova E., Dömötörová M., J. Chromatogr. A, 1000 (2003)
199-221 [2] Hercegová A., Dömötörová M., Matisová E., Kirchner M.,
Otrekal R., Štefuca V. J. Chromatogr. A, 2005 (in print) [3] Kirchner M.,
Matisová E., Otrekal R., de Zeeuw J., J. Chromatogr. A, 2005 (in print)
Keywords : Fast GC, fast GC-MS, pesticide residues, baby food
6
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-06
Oral Presentations Abstracts
New Strategies for Sampling Pesticides in Air: Active and
Passive Methods
Tuduri L., Harner T., Waite D.T., Montury M.
Equipe Périgourdine de Chimie Appliquée, LPTC-Université Bordeaux 1.
BP 1043. 24001 Périgueux cedex, France
Pesticides are by nature toxic molecules so it is desireable that they
stay in their place of application and/or degrade. Before being registered
for sale on the market, they are evaluated by government agencies. They
must be efficient and as selective as possible. Toxicity and eco-toxicity are
also studied. Potential for transport is investigated. Volatilization is also of
interest and is evaluated through the use of Henry’s constant the vapor
pressure of the considered molecule. It is now well known that pesticides
can enter the atmospheric compartment during application (spray-drift),
evaporation or wind erosion. Usually, to assess the presence of pesticides
in the atmosphere, air samples are pumped through a filter (Quartz,
Teflon…) to trap the particle phase followed by an adsorbent
(polyurethane foam, XAD resin, chromosorb, tenax…) tube for vapor
phase molecules using high or low volume pump. Sampling times may
vary from a few hours up to one week. Adsorbents are then solvent
extracted. Extracts are evaporated and usually solvent-exchanged prior to
chromatographic analysis. To address some of the drawbacks of these
techniques, namely solvent use, multi-step sampling preparation, need of
electric power, lack of flexibility in the sampling time, new techniques are
developed. In this work, three alternative techniques will be discussed.
Advantages and drawbacks of Solid Phase Microextraction (SPME),
adsorbent tubes followed by thermal desorption and polyurethane foam
disk passive sampler (PUF-D), as well as applications will be presented.
Keywords : Pesticides, atmosphere, SPME, PUF disks, adsorbent
tubes
7
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-07
Oral Presentations Abstracts
Environmental Risk Assessment of the Used Pesticides
in Turkey
Delen N., Durmuşoğlu E.
Ege University, Agricultural Faculty, Department of Plant Protection 35100
Bornova, İzmir, Turkey
All of the pesticides are toxic chemicals. For this reason, intensive
and uncontrolled pesticide usage can cause different environmental
problems. Hazardous pesticides are used for protecting the crops in most
of the developed and especially developing countries. For this reason, we
would like to give some examples on the possible environmental risks of
these chemicals from Turkey. Total amount of pesticide usage as active
ingredient (a.i.) in Turkey was about 8.396 tons in 1979 and 13.144 tons in
2004. While consumption of the European Union countries (according to
the mean of the 1993-1995) varies from 1,2 to 13,8 kg a.i/ha, consumption
in Turkey varies between 0,5 to 0,7 kg. a.i/ha according to years. These
digits show us that, pesticide consumption of Turkey is still rather low. But,
if the most intensively used 5 insecticides, fungicides or herbicides were
examined, it can be seen that the usage of these chemicals was more than
half of the used pesticides in 2004. Moreover, these most intensive used
pesticides have some human health and environmental hazard risks. On
the other hand, 66,64% of the consumed insecticides, nematicides and
fumigants in 2004 were high acut toxic chemicals, and some of them have
long half lives. Their residues can contaminate air or/and the surface and
ground waters. According to 2004 consumption, 23,23% and 34,87% of
the used pesticides have pollution risk to waters and air respectively. But
usage of the environmentally friendly and low risk pesticides increased in
2004 as to 2002. Some fungicides which are containing heavy metals for
example mancozeb, metiram and propineb (containing zinc and/or
mangan) and copper salts can be important soil pollutants. These
chemicals, especially copper salts can be applied through the drip
irrigation systems in greenhouses. This application can effect the soil
fertility. For solving these problems, the pesticides must be selected very
carefully in the registration according to their environmental risks.
Moreover, chemical programs must be revised and environmentally
friendly and low risk pesticides take place instead of the high risk
pesticides. The pesticides should never be used without control or official
advises.
Keywords : Risk assessment, Pesticide usage, Environment, Turkey
8
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-08
Oral Presentations Abstracts
Strategies and Technologies to Reduce Pollution of
Natural Resources with Pesticides
Özkan H. E.
Food Agricultural and Biological Engineering Dept. Ohoi State University
Columbus, OH 43210, USA
Achieving satisfactory results with pesticides largely depends on
how efficiently the pesticide is applied. One major source of inefficiency in
application of pesticides is loss of spray droplets during their transport from
the nozzle to the intended target. Loss of spray from the intended target to
another site is defined as spray drift which is a serious problem negatively
affecting human health and the environment. Data from several States in
the United States indicate that around 75% of all the complaints
associated with misapplication of pesticides brought to the attention of
officials are related to spray drift. This situation may get even worse as the
area planted with genetically modified crops increases. Spray drift occurs
wherever liquid sprays are applied. Although complete elimination of spray
drift is impossible, problems can be reduced to a minimum if chemicals are
applied with the proper equipment under favorable weather conditions.
Increased awareness of environmental quality and better understanding of
the causes of spray drift can help operators make sounder judgments for
safer, more efficient applications. This paper discusses the major factors
affecting spray drift, and provides recommendations for its reduction.
These recommendations include: simple changes in the way existing
conventional sprayers are operated; use of drift retardant chemicals;
establishment of buffer zones; and using new application equipment
specifically designed to reduce spray drift. Recent technological
developments include new Low-Drift nozzles, air-assisted sprayers,
shielded spray booms, and electrostatic atomizers. Working principles and
effectiveness of these techniques in drift reduction will be discussed in this
paper.
Keywords : Pesticides, sprayers, spray drift
9
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-09
Oral Presentations Abstracts
Behaviour of Pestcides: Trends of Research in Morocco
Dahchour A.
Institut Agronomique et Vétérinaire Hassan II. BP 6202 Rabat-Instituts,
Morocco
Research in pesticide in Morocco has been closely associated to the
improvement of the agriculture. Starting from the sixties, an important
agricultural program, supervised at regional level, was launched including
new crops and techniques and more interestingly the irrigation of 1 million
ha. Consumption of pesticide has exceeded 9000 tons. Negative impact of
pesticides on the health and environment is controlled at different level
starting from the implementation of “homologation” act and the control of
residue in locally marketed and exported commodities. Data related to the
behaviour of pesticides were limited and based on test performed under
conditions different of those prevailing locally. The emergence of new
universities and the creation of specialized laboratories offer opportunities
to assess the impact of these substances. Most of published studies were
performed in agronomic institute and deal especially with efficacy.
However, the new standards applied to water and soil quality open the way
to the involvement of different teams in his topic. Research on residue
seems to be less attractive than other topics due probably to the cost of
equipment and consumable required. Generally, data related to partition,
mobility and dissipation in the soil aimed to classification of the affinity
toward the soils used. Kinetic approaches and new formulation were
attempted. Financial support remains the most constraining problem.
Government actions are very limited and could not cover all aspects. This
could be reinforced by the new reform introduced at the university and the
involvement of national laboratories as partner.
Keywords : Behaviour, pesticide, research, Morocco
10
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-10
Oral Presentations Abstracts
Study of Disappearance Mechanism of Fenamidone with
Model Systems
De Melo Abreu S., Garcia A. J., Caboni P., Cabras P., Alves A.,
Garau V. L.
Dipartimento di Tossicologia, Università di Cagliari, Via Ospedale, 72,
09124 Cagliari, Italy
Fenamidone is a recent fungicide applied to vine, belongings the
imidazolinones family and is part of the Quinone outside Inhibitors (QoI)
fungicide group. In this work, the disappearance mechanism of this
pesticide was studied. The model systems for photodegradation,
codistillation, evaporation and thermodegradation were studied according
a previous work of our research group. All experiments were carried out
also in the presence of grape epicuticular wax and using the commercial
formulation. Residues of Fenamidone were determined by a gas
chromatographic with mass spectrometry detector (GC-MS) analysis (SIM
mode). Limit of detection of the method was 0.05 mg/kg and limit of
quantification was 0.1 mg/kg. Good linearity was achieved in the range
from 0.05 to 1.00 mg/kg, with a coefficient of determination (R2) of 0.9995.
Keywords : Fenamidone, model systems, GC-MS
11
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-11
Oral Presentations Abstracts
The Effects of Storage and Processing on Residue Levels
of Some Organophosphorus Pesticide Residues
in Wheat, Flour, Bran, Cookies, Semolina and Spaghetti
Şenöz B., Uygun Ü., Öztürk S., Köksel H., Atlı A.
Department of Food Engineering, Hacettepe University, Beytepe, Ankara,
Turkey
In this presentation, a part of ongoing studies carried out in
collaboration of Ministry of Agriculture and Hacettepe University on the
effects of storage, milling and processing on residue levels of
organophosphorus pesticide residues in postharvest-treated wheat and its
products were investigated. Pesticide-free wheat was placed into sealed
metal containers and treated with the pesticides (malathion, fenitrothion,
chlorpyrifos methyl and pirimiphos methyl for durum wheat; malathion and
chlorpyrifos methyl for common wheat) according to the raw material
legislation of Turkey. Malathion, chlorpyrifos and pirimiphos methyl
emulsions were sprayed onto the wall of storage vessels. The residues of
the insecticides were determined in wheat at one-week intervals for the
first month and one-month intervals during five months of storage.
Residues of the pesticides were also detected in bran, flour, cookies,
semolina and spaghetti obtained from treated wheat at intervals of about a
month. A multiresidue analysis was performed using GC equipped with an
NPD. The confirmation was performed by GC-MS. During the storage, the
residue levels of pesticides declined in both raw and processed materials.
Although the residue levels in wheat were approximately between 2-6
mg/kg at the end of storage, there was no detectable residue in the
spaghetti produced from this wheat. The residues in wheat, except
malathion, were higher than the maximum residue levels given in Turkish
Food Codex. The residue levels in the cookies with bran were higher than
that of the cookies without bran, as expected. Further investigations are
required to elucidate the effects of processing on pesticide residue levels
in foods.
Keywords : Organophosphorus pesticides, wheat, spaghetti, cookies,
semolina.
12
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-12
Oral Presentations Abstracts
Evaluation and Control of Pesticide Residues in Food:
Limitations and Trends
Valverde A.
Pesticide Residues Research Group, University of Almería, 04071
Almería, Spain
The complexity and main limitations of the procedures currently
established to regulate, fix and control pesticides Maximum Residue Limits
(MRLs) are due to the fact that to apply these procedures it is necessary to
take into account very diverse aspects and experimental results -of
toxicological, agricultural, chemical-analytical (and even legislative and
socio-economic) nature- which, in many cases, are difficult to combine. In
this presentation, some critical points of these procedures are presented
and analyzed, which are, directly or indirectly, related to the availability of
adequate analytical tools to perform an efficient control of the MRLs.
Special attention is paid to aspects like the residue definition, the scope
and quality of the control laboratories and monitoring programs, or the
introduction of new pesticides into the routine control. This presentation
concludes with a clear defence of the generalization of the "in-house"
control and the normalised systems of agricultural production, and a timid
proposal for the possible introduction of a "P for Pesticides" number guide
similar to the "E for Additives".
Keywords : Pesticide Residues, Foods, Evaluation, Control
13
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-13
Oral Presentations Abstracts
Recent Trends in the EU Policy on Pesticide Residues
Lentza-Rizos C.
NAGREF, 1, Sof Venizelou str, 141 23 Lycovrissi, Greece
The first European legal act on pesticide residues was Council
Directive 76/895/ EEC. The aim of this initiative was to ensure free
movement of products throughout the Community. Following adoption of
Council Directives 86/362/ EEC, 86/363/ EEC, and 90/642/EEC these old
MRLs are gradually being reviewed. Provisions for residue monitoring by
check sampling to ensure compliance of food products with MRLs were
also introduced. In the year 1991 Council Directive 91/414/EEC
concerning the placing on the market of plant protection products was
published. The programme of work of the residue Directives is now aligned
with that of 91/414/ EEC Directive.In February 2005 Regulation (EC) No
396/2005 was published. This reflects the new trend in the EU for MRLs
fixing and for pesticide residue monitoring, namely: --MRLs established
with the previous Directives will be re-assessed taking into account: § the
scientific and technical knowledge currently available § the possible
presence of pesticide residues arising from sources other than plant
protection uses and their known cumulative and synergistic affects, when
the methods to assess such effects are available § the results of an
assessment of any potential risks to consumers with a high intake and high
vulnerability, and where appropriate, to animals For not yet harmonized
commodity/pesticide combinations and for active substances not yet
included in Annex I of 91/414/EEC Directive temporary EU MRLs will be
fixed for a limited period of validity. -- The aim of pesticide residue
monitoring will mainly focus on consumer exposure assessment than
enforcement of MRLs and control of GAP. This will result to increased
demands for number of samples analysed, number of pesticides sought
and limits of quantification achieved.
Keywords : Pesticides, residues, EU
14
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-14
Oral Presentations Abstracts
The New MRL Regulation 396/2005. An Agrochemical
Industry Point of View: The New Era in Europe can be
Successful.
Sgouri V.P.
16 rue Jean-Marie Leclair,69009 Lyon, France
The new Maximum Residue Levels Regulation 396/2005 was
published in Europe on March 16th,2005 and is expected to be in full
application in October 2006.
This new piece of legislation is intended to enforce the common protection
of consumers accross Europe but also to raise trade barriers.
Novelties introduced are the existence of European Maximum Residue
Levels only, applicable in all 25 Member States, a single procedure to
evaluate and set MRLs, the link of the MRL setting procedure to the
European registration procedure and its simplification and transparency.
European MRLs are either temporary or final, after evaluation of the
inclusion of the active substance into annex I of 91/414, international
organisations involved with world wide consumer protection are consulted
and there is a declared will, to be transparent and to consider the concerns
of all the Food chain stakeholders, from the farmer to the consumer.
Still, there is a way to go throught the evaluation of the existing, National
MRLs, to define the Temporary European ones. So, an important workload
will be faced during the next months by EFSA, Member States and the
Commission, that leaves questions about the realistic deadlines compared
to existing capacities. The list of the commodities and the extrapolation
rules are revisited and the results must be there soon. A big challenge for
Europe and a very important period for the Authorities as well as for the
Industry that should lead to public acceptance of safe plant protection
poducts use.
Keywords : MRL regulation,396/2005, EFSA, Europe
15
4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-15
Oral Presentations Abstracts
Monitoring of Pesticide Residues in Selected Fruits and
Vegetables
Hormatallah ,A., Ait-Oubahou A., Salghi R., Goumari M.
IAV HassanII CHA. Pesticides Laboratory BP 18/S Agadir Morocco
Several exported horticultural crops are high value cash crops for
farmers and constitute an import source of hard currency for Morocco. The
country produces annually over 7 million tons of fresh fruits and
vegetables. Souss Massa valley located in the south- west near the city of
Agadir is by far the main producing and exporting area of primers (early
maturing products). Most of the production is geared to export mainly to
European markets. Intensive cultivation of horticultural crops under plastic
greenhouse over the years resulted in high infestation of soils and an
increase in the number of pests and pathogens associated with these
crops. To control these pests and diseases, growers are frequently
spraying pesticides which in turn may increase the risks of pesticide
residues in consumed parts. From 188 samples of the most common
vegetables (tomatoes, peppers, cucumbers, zucchini, green beans, melon
and eggplant) collected between October 2004 and April 2005 from
several packinghouses and analyzed using GC multiresidues method for
compounds of organophosphorus, organochlorides, synthetic pyrethroids,
conazoles, dicarboximides. Dithiocarbamates and benzimidazoles were
determined by Spectrophotometric method. Each method was validated by
the percentage of recovery, accuracy, reproducibility, detection and
quantification limit. The results showed that pesticides residues were not
detected from 18.1% of the sample, detectable but below the European
MRLs from 61.1% and at levels little bit higher than recommended MRLs
from 20.8%. All the detected compounds are registered to be used on
vegetable crops. The presentation will discuss the frequency of each
compound depending on the fruit type and harvesting season.
Keywords:Pesticide Residues, MRLs, tomatoes, peppers, cucumbers,
zucchini, green beans, melon, eggplant, Souss Massa Valley.
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-16
Oral Presentations Abstracts
Results from the AOAC Collaborative Study on the
QuEChERS Method and New Developments
Lehotay S.J.
USDA ARS; 600 East Mermaid Lane; Wyndmoor, PA 19038; USA
The “quick, easy, cheap, effective, rugged, and safe” (QuEChERS)
method is a highly streamlined approach to analyze pesticide residues in
food, which was introduced by Anastassiades et al., J. AOAC Int. 86, 412-
431 (2003). Three subsequent studies were published in J. AOAC Int. 88
595-638 (2005) that made the following accomplishments:
1) extended the method to LC/MS-MS as well as GC/MS and validated the
method for hundreds of pesticides in many fruits and vegetables;
2) modified the method to employ buffering which improved results pH-
sensitive pesticides (e.g. captan, pymetrozine, chlorothalonil,
dichlofluanid); and
3) demonstrated that the method also works well for many pesticides in
fatty foods (<15% fat).
In another development, the buffered QuEChERS method was evaluated
in a Collaborative Study involving 13 laboratories in 7 countries. The inter-
laboratory trial entailed the analysis of 20 fortified pesticides at 3 levels
between 10-1,000 ng/g, plus 7 incurred residues, in 3 matrices (grape,
lettuce, and orange). Statistical review of the results showed that the
method gave satisfactory results with Horwitz ratios <1 for nearly all
pesticides in the different matrices. In other developments, the QuEChERS
method has been adapted successfully for the analysis of acrylamide in a
variety of processed food matrices, and the method was evaluated for
relatively dry matrices, such as soybean, animal feed, and nuts. The
QuEChERS method has demonstrated its performance to meet a number
of challenges in the pesticide analysis arena, and is growing in its
usefulness to provide similar benefits in other analytical applications.
Keywords : QuEChERS, validation, pesticide residues, analysis
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-17
Oral Presentations Abstracts
Proficiency Tests for Pesticides Residues Analysis
Testqual Experience
Fernandez-Alba A.R., Medina P.
TestQual. University of Almeria. 04120 Almeria, Spain
The common use of pesticides in food and their monitoring is a
worldwide practice, where an analytical control in various matrices is a
must for chemical analysis. As a consequence of the socioeconomic
interest on laboratories result, it is clear that a robust quality assurance
methodology is necessary to have enough confidence on them. From the
different system to evaluate accuracy results, the Proficiency Tests have
demonstrated their capability and prevalence on others. Therefore,
organizing Proficiency Test it becomes a necessity to assess a control
over the analytical practice. There general scheme is as follows:
ORGANIZATION
Results Samples Report
Lab Lab Lab Lab Lab
11 2 3 4 5
TestQual is a provider of proficiency test in pesticide residues born as a
spin-off enterprise of the Spanish University of Almeria. It has a lot of
experience on organising Proficiency Test close related to the European
Proficiency Test.
Based on this experience uses a fix standard deviation (fit-for-purpose,
FFP) to calculate a relative standard deviation. This is applied to z-score
calculation to obtain each laboratory performance for each pesticide
present in the sample sent.
So the z-score value comes up from calculating the following formula:
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
Oral Presentations Abstracts
z = (x-X) / σ
Where:
x is the result reported by the participant laboratory for a pesticide
present in the sample
X is the assigned value or true concentration taking the median
value
σ is the target standard deviation (using the median and FFP value)
So in this presentation it will be explain in more detail the experience using
true cases and coming up with the obtained results. Explanation on
sample treatment will also be mentioned.
References
- Guidelines for the Requirements for the Competence of Providers
of Proficiency Testing Schemes. ILAC-G13:2000
- Proficiency testing by interlaboratory comparison. Developing and
operation of proficiency testing schemes. UNE 66543-1
- Thompson M. and Wood R. International Harmonized Protocol for
Proficiency Testing of (Chemical) Analytical Laboratories. J.
AOACInt. 1993; 76 (4): 926-940
Keywords : Proficiency tests, pesticide residues
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-18
Oral Presentations Abstracts
Assessment of the Performance of Pesticide Testing
Şenyuva H. Z. , Gilbert J.
TUBITAK-ATAL Konya Yolu No.67 Beşevler, Ankara
Pesticide residue testing of water and foodstuffs is carried out
worldwide more extensively than any other contaminant in the food chain.
Residue data is used in exposure assessment by safety and heath
authorities, and regulatory limits are imposed at EU and US borders for
control of standards for imported foods. Regulatory limits have
progressively decreased and for example for baby food limits of 0.01
mg/Kg for individual pesticides are enforced in the EU which imposes
demanding analytical requirements on laboratories undertaking quality
assurance and testing for enforcement purposes. To harmonise testing at
EU level, control laboratories are required to use validated methods, to be
accredited to ISO17025 and to demonstrate satisfactory performance in
regular participation in proficiency testing. To assess whether laboratories
are in fact meeting these demanding standards recent data from a number
of FAPAS proficiency testing for pesticides will be critically examined and
compared. Trends in performance of laboratories will be identified looking
for patterns in performance based on food matrix, levels and types of
pesticides and correlating where possible with specificity and sensitivity of
chosen methods.
Keywords : Pesticide, proficiency testing, FAPAS, ISO17025
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-19
Oral Presentations Abstracts
Uncertainty Sources in Pesticide Residue Analysis
Ömeroğlu Yolci. P., Boyacıoğlu D., Ambrus A, Karaali A.
Kalite Sistem Laboratories Group Münir Nurettin Selçuk Cad. No:28 81300
Kalamış, İstanbul, Türkiye
It is a requirement under ISO/IEC 17025 that laboratories determine
and make available the uncertainty associated with each analytical method
and result. The uncertainty of measurements is comprised of many
components, arising from activities involved with the sample. The activities
taking place in pesticide residue analysis may be divided into two groups;
field/external operations (sampling) and laboratory operations (sample
preparation, sample processing and analysis). Packing, shipping, storage,
and laboratory preparation of samples may have significant influence on
the residues detected, but their contribution to the uncertainty cannot be
quantified based on the current information. The objectives of this
presentation to review the currently available information on the major
sources of uncertainty in pesticide residue data and to summarize the
methods of the estimation of uncertainty of individual steps in pesticide
residues. The uneven distribution of pesticide residues in the treated
objects leads to an inevitable variability of sampling which may significantly
influence the combined uncertainty of the analytical results. The relative
uncertainty of 28% can be used as typical sampling uncertainty of small
and medium size crops with minimum sample size of 10. The test portion
is unlikely to be representative if the processed laboratory sample is not
well-mixed. Therefore the sample processing procedure shall be included
in the validation of the analytical method, and its uncertainty shall also be
estimated. Losses of pesticide residues have been shown to occur during
processing of fruit and vegetables. Depending on the pesticide and sample
matrix involved, the effects may result in complete or partial decomposition
of pesticide residues. Testing the stability of residues has to be included in
the possible sources of uncertainty. The average relative uncertainty of the
analytical phase alone is about 17-25% in the usual 0.01-10 mg/kg
concentration range. The major contributor to this error can be the GLC or
HPLC analysis due to the matrix effect of the sample extract. The
uncertainty estimation of routine instrumental analysis indicated that the
GLC analysis may amount to the 75-95% of the CVA at the lowest
calibrated level.
Keywords : Pesticide, uncertainty
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-20
Oral Presentations Abstracts
Uncertainty of Sample Processing of Cucumber
Commodity
Tiryaki O., Baysoyu D.
Turkish Atomic Energy Authority, Ankara Nuclear Agriculture and Animal
Sciences Research Center, Nuclear Agriculture Department, Istanbul
Road 30.km, 06983, Saray, Ankara, Turkey.
The evaluation of uncertainty requires the analyst to look closely at
all possible sources of uncertainty. One of them is sample processing,
which may be source of substantial systematic and random errors. It is
general requirements of method validation and internal quality control of a
laboratory. Sample processing is the procedure used to make the
analytical sample acceptably homogenous with respect to the analyte
distribution. Inhomogeneity of analytical sample will result in
underestimates of the residue levels with implications for both MRL
compliance monitoring and consumer risk assessment. The use of
radiolabelled compound gives a great advantage in residue analysis
because it allows one to quickly quantify the analyte directly in the extract,
without clean-up. By eliminating the effects of the rest of the analytical
procedure, the precision of the final results is significantly improved and
the uncertainty of sample processing may be kept at <2%. When the
processed sample is statistically homogenous the efficiency of sample
processing is characterized by typical sampling constant (Ks), and the
uncertainty of sample processing (CVSP) within the tested analytical
portion mass (W) range, is calculated from Ks = W x CVsp2 In this study,
14C-Chlorpyrifos was applied to the cucumber as a surface treatment for
the estimation of the uncertainty of sample processing. Then the material
was comminuted by using Waring Blender. Seven replicate analytical
portions of 5g and 50g were withdrawn from homogenized sample and
extracted with ethyl acetate by using 25G Ultra Turrax. After the
centrifugation, extracts were assayed in Liquid Scintillation Analyzer.
Keywords : Uncertainty of sample processing, sampling constant,
radiotracer technique
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-21
Oral Presentations Abstracts
IPM In Turkey: Implementations, Achievements,
Problems, Solutions.
Aydemir M., Yaşarakıncı N., Kaya Ü.
Plant Protection Research Institute, Bornova, İzmir, Turkey
History of IPM (Integrated pest management) in Turkey can be
extended to early 1900’s, which is a predatory insect, Rodolia cardinalis,
was released in citrus orchards against Icerya purchasi. The research
project on cotton pest is the beginning of IPM researches in Turkey in
1970, and followed by apple, hazelnut researches in 1972. In 1992, the
strategies and the politics are determined as IPM in plant protection
department of Agriculturel and Rural Affairs Ministry. The IPM starategy,
tactics, methods, national IPM instruction were prepared for each
economically important crops in Turkey. Currently, IPM implementation
project has been carried out on 15 crops in nationalwide as, protected
vegetables, potato, corn, cotton, sunflower, and apple, cherry, olive,
hazelnut and pistachio since 1994. The IPM Central Commission were
established to coordinate IPM programs in Nationwide. This commission
consists of 9 members, 2 from General Directorate for Agricultural
Research, 1 from the General Directorate of Preventation and Control, 2
from the Plant Protection Departments of the universities and 4 among the
IPM National Coordinators. The Plant Protection and Agricultural Research
Institutes are the regional coordinator for each crops in their region, trained
extension technicians. Extension technician carried out the IPM together
with the growers. It is basic for the Turkish Agricultural Chambers Union
(TZOB) and the other farmer unions to join actively both with their budget
and man power to the IPM programs as the IPM projects are prepared for
the farmers and must be applied by them. The general policy and
strategies in IPM are determined as:
1.Plant protection research projects must be considered as nationwide and
crop based IPM projects aimed to solve the plant protection problems,
2. IPM projects are being planned and carried on taking the crops and / or
crop groups together.
3. It is basic to establish a National IPM Network for each IPM project.
4.To carry on the IPM projects with the coordination of the research
institutes, universities, agricultural province and district directorates, farmer
unions, cooperatives and the farmers, is essential.
5. It is aimed to increase the number of the IPM projects that will be carried
on with the coordination and the collaboration of the other research
institutes attached to the General Directorate of Agricultural Research,
universities, TÜBİTAK and the Ministry of Environment and the
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4th MGPR International Symposium of Pesticides in Food and the Environment in
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international institutes such as the World Bank , UNDP, FAO, EU, NATO,
GTZ and the other countries.
Oral Presentations Abstracts
6.An attempt has been started and continuing progressively as dense
programs, on the training and introduction of IPM. The implementation
results, achievements, problems and solutions will be given in the paper
and discussed.
Keywords : IPM, Turkey
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-22
Oral Presentations Abstracts
Determination and Residues of Botanical Pesticides in
Organic Food
Angioni A., Cabras P.
Via Ospedale 72 agliari, Sardinia, ITALY
The label of synthetic pesticides formulations reports the amount in
active ingredients (a.i.), as well the label of botanical pesticides
formulations reports the amount of one a.i.. However, botanical pesticides
are plants extracts and the supposed a.i. is only a component of a complex
mixture of molecules, structurally similar and with potential insecticide
activity. For this reason the knowledge of the a.i. alone do not allow the
correct interpretation of the efficacy and toxicity of these formulations.
Nowadays, in Europe the plant extracts registered are those from
Azadiractha indica (a.i. azadiracthin), Derris, Lonchocarpus, Thephrosia
(rotenone) Chrysantemum cinerariaefolium (pyrethrins), while among the
not registered there is a good interest on Ryana speciosa extracts
(ryanodine). The analyses of the formulations of these extracts have
shown that the supposed a.i. is not always the main compound. Infact,
neem oil contains azadiractin A and B,salanin, nimbin and their desacetyl
derivatives, the extracts from Derris consist of rotenone, deguelin,
tephrosin, and b-rotenolone. Ryania extracts showed ryanodine and
dehydroryanodine, the extracts of pyrethrum are a mixture of six main
compounds. Our research group has studied the analytical methods for the
determination of the residues of the main components found in the
extracts. Furthermore has carried out field trials to determine the residues
of these compounds on fruits and vegetables.
Keywords : Botanical pesticides, plant extracts composition
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-23
Oral Presentations Abstracts
Antimicrobial Activity of Polyphenols from Edible Fruits
Fattouch S., Coroneo V., Caboni P., Angioni A., Dessi S., Cabras P.
INSAT, Zone Urbaine Nord, Tunis, Tunisia
Recently, remarkable advancements have been made in the science
of “safe” or “eco-friendly” pesticides. Research has been researching non-
toxic and biologically derived pesticides known as biopesticides. These
bio-chemicals are biodegradable and cause specific biological effects
rather than by inducing chemical poisoning. Biopesticides fall into three
major classes:
(i) microbial pesticides (e.g., a bacterium, fungus, virus or protozoan),
(ii) transgenic Plant-Incorporated-Protectants (PIPs) producing pesticidal
substances and
(iii) naturally occurring biochemical substances that control pests by non-
toxic mechanisms.
Around 250 effective ingredients have been registered as bio-pesticides in
the U.S. since 2003, and there are approximately 1200 products made by
such ingredients. Many studies have presented data that show a variety of
antimicrobial activities of the naturally occurring phenolics from olives, tea
and wine. It has been reported that tea catechins, for example, have
activity against various foodborne pathogenic bacteria. However, there is
very little information about the antimicrobial capacity of phenolics present
in edible fruits. In the present work, we describe the use of phenolic
extracts of apple, pear and quince common fruits as antimicrobial agents.
Pulp and peel polyphenolic extracts were firstly analysed for total
phenolics by the Folin-Ciocalteau method. The total phenolic content was
expressed as catechol equivalents in milligrams per gram of fresh material.
Then, the phenolic composition of the extracts was separated and
identified by HPLC-DAD-MS using a gradient programme of different
solvents. Antimicrobial activity of the crude phenolic extracts or HPLC-
collected fractions was measured against a collection of Gram-positive and
Gram-negative bacterial species. Two methods were used: the agar
diffusion assay and the measurement of bacterial growth in liquid culture.
Our results showed that different bacterial species exhibit different
sensitivities towards phenolics. These properties can be utilized in
functional food development and in food preservative purpose.
Keywords : Biopesticide, Polyphenols, edible fruits, Antimicrobial,
LC-MS
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4th MGPR International Symposium of Pesticides in Food and the Environment in
Mediterranean Countries
O-24
Oral Presentations Abstracts
Effect of Adjuvant on Pesticide Residue on Tomatoes
Aksu P., Kahyaoğlu M., Hışıl Y.
Ankara Zir. Müc. Mrk. Arş. Ens. Gayret Mah. Fatih Sultan Mehmet Bulvarı
No.66 Yenimahalle / Ankara 06172 / Türkiye
A pesticide adjuvant is defined as a substance added to the spray
tank, separate from the pesticide formulation (plant protection product) or it
can be directly included to the plant protection product as an ingredient.
Adjuvant was used to increase effectiveness of pesticides since 1950s, so
it reduces high dose applications to low dose. Several thousand adjuvants
of widely varying quality are sold throughout the world. In some countries,
registration is required for using an agricultural adjuvant. However, in other
countries like in Turkey adjuvant was widely used without any registration
requirement. Although adjuvant was most cost effective and easiest way to
reduce agrochemical rates, minimize unwanted side effects and improve
pest control, there was not any published study about the influence of
adjuvant on pesticide residue on crops. In order to obtain the effect of
adjuvant on pesticide residue, a field application has been carried out. First
of all, an adjuvant and a pesticide have selected according to technical
advice and amount of use on tomatoes. Application has carried out at two
different doses, one dose was given in “Technical Instructions on Plant
Protection in Turkey” and the other was doubled up dose. Samples are
taken at first day until pre-harvest interval. To investigate the amounts of
pesticide residue, samples were extracted and analyzed by using Gas
Chromatography and Gas Chromatography/Mass Spectrometer
equipments.
Keywords : Adjuvant, pesticide residue, tomatoe, GC, GC-MS
27
