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Transport of Agricultural Transport of Agricultural Chemicals: Atmosphere to Chemicals: Atmosphere to
Land SurfaceLand Surface
Michael S. MajewskiMichael S. MajewskiJason R. VogelJason R. VogelPaul D. CapelPaul D. Capel
National Water Quality Monitoring Conference, San Jose, California, 9 May, 2006
The Hydrologic CycleThe Hydrologic Cycle
ApplicationsApplicationsPost-ApplicationPost-ApplicationAtmospheric MovementAtmospheric MovementRemoval/DepositionRemoval/DepositionACT DataACT Data
How do Pesticides Become Airborne How do Pesticides Become Airborne and What Happens to Them Once and What Happens to Them Once
They are Up There?They are Up There?
Irrigation – Irrigation – Very little, if anyVery little, if anyGround Rig - Ground Rig - < 0.5 to 10%< 0.5 to 10%
Injected (Fumigation)Injected (Fumigation)SurfaceSurfaceSurface-Incorporated Surface-Incorporated
Aerial - Aerial - 10 to 30, > 50%10 to 30, > 50%
Orchard Mister/Blowers - Orchard Mister/Blowers - 2 to 3 times greater than aerial 2 to 3 times greater than aerial methodsmethods
Agricultural Application MethodsAgricultural Application Methods
Increasing Drift Increasing Drift PotentialPotential
Post-Application VolatilizationPost-Application VolatilizationAndAnd
Wind Erosion of SoilWind Erosion of Soil
PARTICLE SORPTION PARTICLE SORPTION
GAS GAS
DRY REMOVALDRY REMOVAL SCAVENGING SCAVENGING(Fallout) (Rain/Snow)(Fallout) (Rain/Snow) (Rain/Snow) (Gas Exchange)(Rain/Snow) (Gas Exchange)
SCAVENGING DRY REMOVALSCAVENGING DRY REMOVAL
Aerial Distribution and Removal of Trace Organic Aerial Distribution and Removal of Trace Organic ChemicalsChemicals
ACT StudyACT Study
Atmospheric Transport Atmospheric Transport and Deposition of Pesticidesand Deposition of Pesticides
ObjectivesObjectivesQuantify the concentration and load of Quantify the concentration and load of
pesticides in rain, and determine the pesticides in rain, and determine the contribution of pesticides from wet deposition contribution of pesticides from wet deposition to runoff. to runoff.
Determine the seasonal, and in-season Determine the seasonal, and in-season variation of pesticides in rain. variation of pesticides in rain.
Identify the important pesticide Identify the important pesticide transformation processes in air and determine transformation processes in air and determine if these differ from those in water.if these differ from those in water.
Map of USA showing each of the ACT study areas
Sampling MethodsSampling MethodsSingle location Single location (except California)(except California)Wet/Dry Autosampler (modified)Wet/Dry Autosampler (modified)
Weekly Integrated Samples Weekly Integrated Samples (except in California)(except in California)Fully instrumented meteorological station atFully instrumented meteorological station at
each siteeach siteAnalytical MethodsAnalytical Methods
21 Insecticides21 Insecticides 18 Herbicides18 Herbicides 3 Fungicides3 Fungicides 36 Transformation Products36 Transformation Products
Pesticide Use by ScalePesticide Use by Scale
Small watershedSmall watershed
Scale- Small Intermediate Large
Maryland 33 km² 724 km² 5280 km²
Indiana 7.2 km² 243 km² 29,400 km²
Nebraska 1.5 km² 955 km² 15,200 km²
California 17.5 km² 831 km² 9300 km²
Intermediate watershedIntermediate watershed
Pesticide Use by ScalePesticide Use by Scale
Use- Small(33 km²)
Intermediate(724 km²)
Large(5280 km²)
Maryland
Atrazine, Metolachlor,
Simazine, Dimethoate
Acetochlor, Alachlor,
Dimethenamid, Hexazinon, Metribuzin,
Pendimethalin, Carbaryl,
Chlorpyrifos, Diazinon,
Methyl Parathion, Permethrin
DCPA, Malathion,
Methidathion, Phosmet, Iprodione, Metalaxyl,
Myclobutanil
Total 4 4 + 11 4 + 11 + 7
Atrazine Use: Small- Intermediate- Large- kg/yr 244/NR 12,242 836,930
15
-Ap
r
22
-Ap
r
29
-Ap
r
06
-Ma
y
13
-Ma
y
20
-Ma
y
27
-Ma
y
03
-Ju
n
10
-Ju
n
17
-Ju
n
24
-Ju
n
01
-Ju
l
08
-Ju
l
15
-Ju
l
22
-Ju
l
29
-Ju
l
27
-Ap
r
04
-Ma
y
12
-Ma
y
18
-Ma
y
25
-Ma
y
01
-Ju
n
08
-Ju
n
15
-Ju
n
29
-Ju
n
06
-Ju
l
13
-Ju
l
20
-Ju
l
27
-Ju
l
03
-Au
g
10
-Au
g
17
-Au
g
24
-Au
g
2003 2004
0
50
100
150
De
po
sit
ion
Flu
x (
µg
/m²)
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
DE
A F
lux
(µ
g/m
²)
AtrazineDEA
0.0
0.5
1.0
1.5
2.0
2.5
3.0C
on
ce
ntr
ati
on
in R
ain
(µ
g/L
)
0
50
100
150
200
Ra
infa
ll A
mo
un
t (m
m)
AtrazineAcetochlorMetolachlorRainfall
IndianaUSEPA MCL = 3.0 µg/L6.58 µg/L
12
-Fe
b
12
-Ma
r
26
-Ap
r
29
-Ap
r
11-D
ec
16
-De
c
23
-De
c
26
-De
c
31
-De
c
29
-Ja
n
16
-Fe
b
17
-Fe
b
24
-Fe
b
25
-Ma
r
2003 2004
0.0
0.5
1.0
1.5
2.0
De
po
sit
ion
Flu
x (
µg
/m²) Upper
MiddleLower
0.0
0.1
0.2
0.3C
on
cen
trat
ion
in
Rai
n (
µg
/L)
UpperMiddleLower
California - Diazinon
15.6 µg/m² 3.85 µg/m²
1.20 µg/L
Diazinon Use: Small- Intermediate- Large- kg/yr NR/NR 6273 32,782
Detected PesticidesDetected Pesticides
a Martin, J.D., Crawford, C.G., Larson, S.J., 2003, Pesticides in Streams: Summary statistics, 1992-2001. http://ca.water.usgs.gov/pnsp/pestsw/Pest-SW_2001_Text.html
Detection in Rain
Ranking Pesticide
2003 Rain Samples
(% Detections)
2004 Rain Samples
(% Detections)
2003 & 2004 Rain Samples (% Detections)
Stream Detection
Frequencya (1991-2001)
Total Sample # 54 62 1161 Metolachlor 85% 71% 78% 83%2 Atrazine 64% 63% 64% 80%3 Dacthal 62% 62% 62% 11%4 Chlorpyrifos 58% 59% 58% 11%5 Simazine 58% 46% 52% 57%6 Acetochlor 49% 52% 51% 31%7 Pendimethalin 42% 48% 45% 7%8 Alachlor 38% 51% 45% 37%9 Carbaryl 35% 33% 34% 9%
10 Diazinon 42% 22% 31% 13%
Seasonal Pesticide LoadingSeasonal Pesticide Loading
1 µg/m² ~ 10-5 lb/ac
2003 2004 2003 2004 2003 2004 2003 2004
Maryland Indiana Nebraska California
0
100
200
300
400
500
600
700
Flu
x (
µg
/m²/
se
as
on
)
Fungicides
Insecticides
Herbicides
Organophosphorus Insecticides Organophosphorus Insecticides
Acetanilide HerbicidesAcetanilide Herbicides
Transformation ProductsTransformation Products
Oxygen Analog of: Maryland Indiana Nebraska CaliforniaChlorpyrifos 1, (0.006 µg/L) 2, (0.012 µg/L) 1, (0.009 µg/L) 16, (0.022 µg/L)
Diazinon 0 0 0 16, (0.023 µg/L)
Malathion 0 8, (0.071 µg/L) 3, (0.027 µg/L) 5, (0.027 µg/L)
Me-Parathion 0 0 2, (0.025 µg/L) 0
Acetochlor ESA, OXA, SAA Alachlor ESA, OXA, SAA Matolachlor ESA, OXA
[# detections, (mean concentration)][# detections, (mean concentration)]
SummarySummary
A wide variety of pesticides were detected in A wide variety of pesticides were detected in every rainfall sample collectedevery rainfall sample collected
Herbicides detected more frequently and at Herbicides detected more frequently and at higher concentrations than insecticideshigher concentrations than insecticides
Detection frequencies and concentrations were Detection frequencies and concentrations were closely related to their useclosely related to their use
Atrazine concentrations in rain exceeded EPA Atrazine concentrations in rain exceeded EPA MCL value for drinking water in IN & NEMCL value for drinking water in IN & NE
Transformation ProductsTransformation ProductsOxygen analogs of organophosphorus Oxygen analogs of organophosphorus insecticidesinsecticidesNo acetanilide herbicide metabolites detectedNo acetanilide herbicide metabolites detected
Summary, Summary, continuedcontinued
Depositional fluxes ranged from:Depositional fluxes ranged from:Herb.Herb. - 1.6 to 623 µg/m²- 1.6 to 623 µg/m²
Insect.Insect. - 2.2 to 48 µg/m²- 2.2 to 48 µg/m²Fung.Fung. - ND to 16 µg/m² - ND to 16 µg/m²
What is the significance of pesticides in What is the significance of pesticides in rainfall?rainfall?
Many of the same pesticides detected in rainfall Many of the same pesticides detected in rainfall are also detected in surface and groundwaterare also detected in surface and groundwater
A wide variety of pesticides are being A wide variety of pesticides are being transported and deposited into non-target areas transported and deposited into non-target areas where their use was not intendedwhere their use was not intended
Contact InformationContact InformationMichael Majewski, Research ChemistMichael Majewski, Research ChemistUS Geological SurveyUS Geological Survey
6000 J Street, Placer Hall6000 J Street, Placer HallSacramento, California 95819Sacramento, California 95819
[email protected]@usgs.gov