EMICUPE
Emission, Fate and Impact of
Currently Used Pesticides
FATE
Emissions
into air
IMPACTS
USE-EU
SPAIN
EMICUPE
TOTAL ESPAÑA: 31815 (14% EU-25)
EMICUPE
EMMISSION OF PESTICIDES INTO AIR
GAS/PARTICLE PARTITIONING OF CUP
ATMOSPHERIC TRANSPORT, TRANSFORMATION AND
DEPOSITION
CV’s agricultural area: 789.900 Ha
OCCURRENCE OF PESTICIDES IN AIR
Tons of active ingredients: 2.7
SAMPLING AND ANALYTICAL PROCEDURES
EMISSIONS INTO AIR
EMISSIONS DURING APPLICATION
Gas-Phase
Aerosols
Application Technique
20-50 %
of the dosage
Formulation
Wind speed
DRIFT
Environmental
T ºC)
conditions
Humidity
Atmospheric
stability
EMISSIONS INTO AIR
EMISSIONS FROM SOIL
Ph-Ch of Pesticide
Vp
Solubility
Adsorcion coefficient
Persistence in soil
Soil propertiees
SOIL
Organic matter content
pH,…
Wind speed
10-50 %
Environmental
conditions
WIND EROSIÓN
Public Health Laboratory of Valencia
Water content
Public Health Laboratory of Valencia
T ºC)
Humidity
Atmospheric
stability
Phisico-chemical properties
EMISSIONS FROM SOIL
Table 1 Physico-chemical properties and agricultural usage of pesticides1 studied
Way of application
Analyte
Type
Vapour pressure
(mPa)
Henry’s law
constant
(Pa m3 mol-1)
logP
Period of application
Carbendazim (CBZ)
fungicide
0.15
3.6 x 10-3
1.38
Spring-Autumn
Spraying
Imidacloprid (IMCP)
insecticide
9x 10-7
2 x 10-10
0.57
March-October
Spraying
Thiabendazole (TBZ)
fungicide
4.6x 10-4
2.7 x 10-8
2.39
all year
Indoor
Imazalil (IMZ)
fungicide
0.158
2.61 x 10-4
3.82
all year
Indoor
Methidathion (MTD)
insecticide
0.25
3.3 x 10-4
2.2
May-September
Spraying
Methiocarb ( MTC)
helicide
0.036
1.2 x 10-4
3.08
Spring
Granulate bait,
spraying
November-January;
March-May
Spraying
February-September
Spraying
Spring-Summer
Spraying
Bitertanol (BTN)
fungicide
2.2x 10-7
Pyriproxyfen ( PYPF)
insecticide
<0.013
Hexythiazox (HXTZ)
acaricide
0.0034
1
2 x 10-8
4.1
5.37
2.4 x 10-3
2.53
These pesticides are used in citric, grapes and other fruits treatments
Public Health Laboratory of Valencia
EMISSIONS FROM SOIL
EMISSIONS FROM CROPS
Ph-Ch of Pesticide
Vp
Solubility
Adsorcion coefficient
Persistence in plant
CROPS
Wind speed
25-50%
Environmental
conditions
Public Health Laboratory of Valencia
Public Health Laboratory of Valencia
T ºC)
Humidity
Atmospheric
stability
EMISSIONS FROM CROPS
GAS-PARTICLE PARTITIONING
Pesticides (SOC) ares simultaneously present in GAS
and PARTICULATE phase (G/P)
The distribution depends on:
* Ph-Ch properties : Vp, Water solubility
*Environmental conditions: Tº, Humidity, TSP, …
The environmental fate in the air depends on G/P (wet and dry
deposition, photochemical degradation, atmospheric transport,…)
Public Health Laboratory of Valencia
Public Health Laboratory of Valencia
Ilmo. Sr. D. Manuel Escolano Puig
GAS-PARTICLE PARTITIONING
Director General para la Salud Pública
OCCURRENCE
Vapor/Particle distribution
% in g a s p h a s e (2 8 8 K )
100
80
60
40
20
0
-8
-7
-6
-5
-4
-3
-2
-1
0
1
log vapor pressure (mP)
Public Health Laboratory of Valencia
Public Health Laboratory of Valencia
OCCURRENCE
Public Health Laboratory of Valencia
OCCURRENCE
Public Health Laboratory of Valencia
OCCURRENCE
SAMPLING
Sampling volume
SORBENT:
HVS:30 m3/h: 720-760 m3
XAD-2 (20 -40g)
HVS: 10-15 m3/h : 240-360
m3
PUF
LVS: 77L/min (24h): 110 m3
TENAX
HVS: 140-700m3
HVS: 10-15 m3/h
HVS: 500 m3
HVS: 34 m3/h (24h): 816 m3
Public Health Laboratory of Valencia
FILTERS:
HVS _EPA> 300 m3/24h
(210L/min)
Public Health Laboratory of Valencia
PUF/XAD-2/PUF
GFF; QFF
(2,54-33 cm)
TPM
PM10
Ilmo. Sr. D. Manuel Escolano Puig
ANALYTICAL METHODS
Director General para la Salud Pública
ANALYTICAL METHODS
EXTRACTION
CLEAN-UP
DETERMINATION
Shoxlet, 24 h, ether
Alumina
GC-MS-NCI
Shoxlet, 24h, ch-ac.
Silica gel
GC-ECD; GC-MS
Shoxlet, 16h, DCM
Florisil
GC-MS
MATERIALS AND METHODS
EXTRACTION
DETECTION
SAMPLE
Shoxlet, 12 h, Hx-DCM
HPLC-silica
GC-ECD; HPC-UV
Shoxlet, 18h, ether
Alumina
GC-MS
Shoxlet, 24 h, Hx-ac
Florisil
GC-MS
ASE, ethyl acetate (OP)
C18
LC-MS/MS
ASE, Hx-DCM/Ee (OC)
Silica
GC-MS
ASE, Ac,
-
LC-MS/MS
Public Health Laboratory of Valencia
ASE
HPLC-MS-MS
PM10
FILTER
MAE
Public Health Laboratory of Valencia
SAMPLING
Ilmo. Sr. D. Manuel Escolano Puig
Director General para la Salud Pública
MATERIALS AND METHODS
Monitoring pesticide residues in air samples (PM2.5) from
Valencia Region
32 STATIONS
PM10/PM2.5
FILTERS
Public Health Laboratory of Valencia