WP2.2/ACTION: Innovative control of pesticides in air and standardization
of analytical methods (Draft 2_30/10/08)
Description
Pesticides are designed to influence fundamental processes in living organisms and thus
may have the potential to kill or control harmful organisms such as pests. At the same
time, they can cause unwanted adverse effects on non-target organisms, human health
and the environment.
Pesticides such as herbicides, insecticides and fungicides, are the most widely used
chemical compounds. Despite the existing policies and legislation aimed at protecting
human health and the environment, actual consumption and use of pesticides as not
decreased between 1992 and 2003. In this last year near to 300.000 tones of active
substances were sold in EU-15 (Eurostat and European Crop Protection Association).
During application, up to 30-50% of the total dose never reaches the target area and can
be lost to the air. The percentage of this spray drift depends on factors such as the type
of formulation, spraying technology, physicochemical properties of compounds and
climatic conditions.
Post-application volatilization represents further significant pesticide input into the
troposphere for several days or weeks following pesticide application. The dominant
factors that affect volatilization from soil and crops are vapor pressure, Henry’s law
constant and water solubility of pesticides, as well as its persistence in the soil or plant
surface, and environmental conditions. Another emission pathway for pesticides into
atmosphere occurs due to wind erosion process (soil tillage operations) that can remove
soil particles and dust loaded with pesticides. As a result of these three processes
significant fractions of applied pesticides are transferred into the atmosphere.
Once in the air, these compounds can be redistributed, degraded, transported, and
returned to the earth’s surface via wet and dry deposition.
In addition, these compounds have adverse health effects. Therefore, the emission,
atmospheric persistence and impact of these compounds should be well understood in
order to better evaluate their environmental impacts.
Although there are a lot of activities about pesticides in soil and in water, there is only a
limited number of projects about the emissions and fate of pesticides in air, specifically
regarding to the compounds used nowadays in Europe.
To improve the pesticide strategy, better systems for the collection of information on
use of plant protection products will be necessary, as well as the determination of
pesticide concentration in environmental compartments.
The main activities of this activity are:
1. Innovative control of pesticides in air
A new methodology to monitor CUP in air developed in our laboratory, and at
present only used at a pilot scale, will be applied in a large scale monitoring
program for control of pesticides in air.
The new approach uses high volume samplers, and evaluates the occurrence of CUP
in air through the fine particulate matter (PM10/2.5) and the gas phase.
The extraction step consumes less time y less solvent than the conventional methods,
with higher throughput.
Also it uses high sensitive and confirmatory techniques for determination of the
compounds such as GC-MS and LC-MS/MS.
This new approach has not been applied before in any national monitoring program,
and offers a potential advantage compared with the currently used methods. We
will compare our results using this new methodology with the more commonly
methods used in the main countries in the world.
2. Analysis of CUP from gas and particulate samples collected in monitoring
activity (WP2.3)
Samples collected in WP2.3 will be analyzed in this action by GVA, CEAM and
Gdansk University of Technology.
The three laboratories will use different standard operating procedures (SPO) and
different apparatus to carry out the analysis, but similar quality control and quality
assurances (QA/QC) procedures will be established in each laboratory, mainly based in
those promoted by the EU for the analysis of pesticides (SANCO/2007/3131)
Likewise, the three laboratories will define the minimum performance characteristics of
the analytical methods (LOD, recoveries, precision, linearity,...) in order to guarantee
the quality of results.
If some good reference materials could be prepared, some proficiency testing would be
carried out. In any case, the laboratories will participate in international proficiency
testing promoted by recognised institutions in matrices similar to those of the project
3. Analysis of CUP from urine samples collected in human monitoring
activities (WP3)
GVA and CEAM will analyze samples collected in WP3 (urine samples)
Methods employed
The new methodology to monitor CUP will be applied in the air monitoring network of
the Regional Valencia Government (Generalitat Valenciana), consisting of 32 stations
located in urban and rural areas, for collect the samples of particulate phase
(PM10/PM2.5 filters), and gas phase (sandwiched PUF/XAD-2 cartridges).
The extraction and clean up step is carried out by pressurised fluid extraction (PFE) and
SPE respectively.
For determination the method uses both LC-MS/MS and GC-MS/MS
Pesticides analysed by HPLC-MS/MS: and GC-MS/MS
PESTICIDES LC-MS/MS (ESI +)
Omethoate
Imidacloprid
Carbendazima
Acetamiprid
Dimethoate
Thiabendazole
Imazalil
Thiophanate methyl
Malathion
Flusilazole
Metalaxyl
Methidathion
Azoxystrobin
Methiocarb
Fenhexamid
Iprovalicarb
Bitertanol
Myclobutanil
Tebuconazole
Tebufenozide
Prochloraz
Chlorpyrifos methyl
Pirimiphos methyl
Triflumizole
Cyprodinil
Tebufenpyrad
Buprofezin
Pyriproxyfen
Hexythiazox
Chlorpyrifos
Flufenoxuron
Pyridaben
Fenazaquin
PESTICIDES GC-MS
Acephate
ACRINATHRIN I LQM
ACRINATHRIN II
ACRINATHRIN III LQM
ACRINATHRIN IV LQM
Acrinatrin
Alfa cipermetrin
Azoxystrobin
Benalaxyl
Benfuracarb
Bifenthrin
Bitertanol I
Bitertanol II
Bromopropilate
Bupirimate
Buprofezin
Captan
Carbaryl
Chlorothalonil
Chlorpyrifos
Clofentezin
Cyfluthrin I
Cyfluthrin II
Cyfluthrin III
Cyfluthrin IV
Cyhalofop butyl
Cypermethrin I
Cypermethrin II
Cypermethrin III
Cypermethrin IV
Cyproconazole
Cyprodinil
Deltamethrin
Diazinon
Dicofol
Dimethoate
Dimethomorph
Diniconazole
Dinobuton
Endosulfan (alpha isomer)
Endosulfan (beta isomer)
Endosulfan ether
Endosulfan lactone
Endosulfan sulfate
Etoxazol
Famoxadone
Fenarimol
Fenazaquin
Fenbuconazole
Fenitrothion
Fenoxycarb
Fenthion
Fludioxonil
Fluquinconazole
Flusilazole
Folpet
Hexaconazole
Imazalil
Iprodione
Iprovalicarb
Kresoxim methyl
Lambda cyhalothrin
Malathion
Mepanipyrim
Metalaxyl
Metalaxyl M
Methidathion
Methomyl
Methyl azinfos
Methyl chlorpyrifos
Methyl pirimiphos
Methyl tolclofos
Myclobutanil
Orthophenilphenol
Oxadiazon
Oxamyl
Penconazole
Phosalone
Phosmet
Pirimicarb
Procymidone
Propamocarb
Propargite
Pymetrozine
Pyraclostrobin
Pyridaben
Pyrimethanil
Pyriproxyfen
Quinoxyfen
Tebuconazole
Tebufenpirad
Tetraconazole
Tolyfluanid
Triadimenol
Trichlorfon
Trifloxystrobin
Triflumizole
Zeta cypermethrin
The laboratory woks under quality assurance and quality control procedures established
by ISO 17025.
Expected Results:
Standard analytical method for pesticides in air
Guide for air monitoring programs of CUP.
Guidelines of Good Practices that could help in the creation of Manuals of Good
Practices
Report and evaluation of the emissions of pesticides in different European countries
The information obtained from this project will be able to help to the development of
new directives about pesticides in Europe with the purpose of adopt supporting
strategies to reduce and control the emissions and pollution problems related with the
use of pesticides, adopt good agricultural practices, minimize health and environmental
effects associated with the use of these compounds and also will be able to help in the
choice of standard methods of collection and analysis of air samples.
A final report will be prepared that should provide information about the possibility of
implement a Pesticide Air Monitoring Network using this sampling and analytical
methodologies.
DELIVERABLE PRODUCTS OF THE ACTION
-
Report on the methodologies currently used for detection of pesticides in
atmosphere (deadline: 30 /04/ 2010)
Report on new methodology to monitor CUP in air (30/05/2010)
Layman’s report 2010 (30/12/2010)
First report of results of the innovative control of pesticides in air (15/12/2011)
Second report of results of the innovative control of pesticides in air (15/12/2012)
First Report of results of analysis on the monitoring activity in WP2.3
(15/12/2011)
Layman’s report 2011(30/12/2011)
Second Report of results on the monitoring activity in WP2.3 (15/12/2012)
Report of results of urine analysis in WP3 (15/12/2012)
Final Layman’s report of the activity (31/12/2012)
MILESTONES OF THE ACTION
-
Definition of the QC/QA procedures that will be applied in the laboratories
To reach a consensus on the minimum performance parameters of the analytical
methods
To define the better methodologies for analysis of pesticides in urine
To participate in proficiency testing
INDICATORS OF PROGESS
GVA-Health Department-LSPV
Brief description of the Associated Beneficiary’s activities and experience in the
area
GVA-Regional Ministry of Health includes different departments and services. One of
them is the Public Health Laboratory of Valencia (LSPV).
The mission of the LSPV is to provide a reliable analytical system in support to the
programmes of food safety and environmental control promoted by the Valencia
Regional Government (Generalitat Valenciana). The LSPV also carry on some research
activities focused on the development of analytical methods for determination of
residues and contaminants in food, water and air.