Instructor: Allan Felsot

afelsot@tricity.wsu.edu Proportional Disappearance of Pesticides

from Soil by Different Pathways
Fall 2005

volatilization
ES/RP 531 (up to ~75%)
uptake
Fundamentals of Environmental Toxicology (<5%)

Lecture 21
runoff leaching
Mass Transfer (Transport) degradation (<~10%)
transformation (<1%)
(up to ~90%)
Can We Generalize to Other
Contaminants????

Transport Processes
Tendency of molecules to be carried by a Transport Phenomena
medium (phase) from one place to another
Leaching Diffusion
Runoff
Volatilization xx x x
x
Volatilization
x
x Runoff & Erosion
x x
x x
x x x x x x Leaching
x xx x
xx x x
x x
xx x
x x x x
(Mass Transfer)

Diffusion Turbulent Diffusion

Molecular scale process
Movement of molecules within a medium Macroscopic level diffusion
Movement from higher concentrations to lower Movement of medium itself redistributes
concentrations the contaminant
Loss of spatial uneveness in the distribution of
mass (concentration, or heat) manifested because
Eddy diffusion
of the second law of thermodynamics
Entropy increases until equilibrium is reached
System at lowest energy state at equilibrium

Diffusion occurs quickly over short distances

(100 m) but very slowly over long
Diffusivity is related to molecular size of the
contaminant and viscosity of the medium distances.

1
 Volatilization Volatilization is influenced by temperature
60

35 35
50 20
% volatilization
40
20
30 5
35
20 5 20

10 5

0
trifluralin dieldrin atrazine

Pesticide

Volatilization is influenced by soil moisture and Effect of Sediment Perturbations on Volatilization of PCBs
organic carbon System Sediment 0- Water Surface Jetdrop
5 mm depth (ng/L) microlayer impactor
1000 (ng/g) (ng/cm2) (ng/cm2)
Midges 123 0 92 16
E Worm & Midges 37 6 76 8
Dieldrin
100 moist soil
E
vapor density E E Sterile 56 0 0 0
g/L 10 No animals 145 0 0 0

S collector
1
S dry soil
S S
S
0.1
0 5 10 15 20 25 bubbler
organic matter (g/kg)
Sodergren & Larsson 1982 Sediment + PCBs

Volatilization Pesticide Drift:

A Direct Route to the Atmosphere
% Volatilized Crop
Pesticide in 24 hours Movement of spray droplets during
alachlor (Lasso) 1.1 fallow application of pesticides
atrazine (Aatrex) 0.1 fallow Phenomenon can be applied to any application
simazine (Princep) 0.05 fallow of any chemical in which a liquid is sheared
EPTC (Eradicane) 33.6 alfalfa under pressure and released into the
2,4-D 4.2 wheat
environment
trifluralin (Treflan) 41.4 fallow (moist)
trifluralin (Treflan) 11.9 fallow (dry)

Spencer 1990

2
 Effect of Spray Particle Sizes on Downwind Drift Deposition
Effect of Droplet Size on Drift Distance
2
1000 Bode & Butler 81 1 Fine Spray (VMD=175 m)
Fraction of
500 Medium/Coarse Spray (VMD=341 m)
Application Rate
200 0.1 VMD = Volume Median Diameter
Droplet 50th percentile distribution of spray
150
Diameter particles
(microns) 100 0.01
50
20 0.001
Ground Sprayer, 45 ft swath
10 Low Boom Position (~2 ft off ground)
5 0.0001
0 50 100 150 200 250 300
1 10 100 1000 10000 100000
Distance (ft.) in 10 ft. fall with 3 mph wind Downwind Distance (feet)
AgDRIFT Modeling

Effect of Wind Speed on Downwind Drift Deposition Inversions (distinct layers of air at differential temperatures)
inhibit dispersion of particles and can cause movement of
highly concentrated particles over long distances
0.004
Wind Speed
5 mph
0.003 10 mph
Fraction of
Application Rate
Helicopter (Bell)
0.002 0.075 lb AI/acre
VMD ~340 m
5 ft boom ht
0.001

0
0 50 100 150 200 250 300
Downwind Distance (feet)
AgDRIFT Modeling

Runoff & Erosion

3-10 mm

URL: scarab.msu.montana.edu/extension/ MT_PAT/Pesticidesenvironment.ppt

3
 Only Pesticide in Top Centimeter Is Susceptible To Runoff
But Amount Moving Is Concentration Dependent
Effect of Rills On Pesticide Runoff
Herbicide in Runoff (water + sediment), mg/L

1.0

0.1

0.01

y = 0.05x 1.2
0.001 R = 0.93

0.01 0.1 1.0 10 100

(Leonard 1990) Herbicide in soil, 0 - 1 cm, mg/kg

Combination of Pesticide Degradation & Aging

Reduces Surface Runoff Over Time Factors Affecting Surface
Pesticide in Runoff (g/L, ppb)
1000 Transport
Atrazine
Rainfall timing & intensity
100
Location of contaminant
glyphosate
10 Contaminant properties
Topography
2,4-D
1

0.1
20 40 60 80
(Leonard 1990) Days After Application

Relationship Between Phase Transfer Properties and Appropriate

Best Management Practices to Allay Pesticide Mass Transfer
% of Pesticide Lost
Contaminant Properties
Affecting Leaching
Water solubility
surface runoff Sorption potential
subsurface flow Volatilization potential
Reactivity
1000 100 10 1 0.1

Appropriate BMP Kd
erosion & runoff timing, rate
sediment control & formulation
control chemical
additives
incorporation

4
 Field Factors Affecting Reality is Irregular
Leaching
Precipitation & Irrigation
Volume
Intensity Water
Table
Soil Properties & Structure
Organic matter content
Clay content
pH Soil particles are Old root channels or
Macropores irregular, creating small earthworm burrows
and large pores. create macropores.

Macropores
Macropores Pores formed by soil
Large continuous openings in field soils fauna
May be continuous for distances of ~1 mm - >50 mm
several meters in both vertical and lateral Pores formed by plant
directions roots
< 1 mm
Characteristic of structured soils
Pores formed by
Cause preferential flow cracks & fissures
aka macropore flow variable sizes
flow velocities ~0.3 mm/sec -- 20 mm/sec

Breakthrough Curves (BTC)

Preferential Flow IDEAL BTC

Rapid movement of water along

[C]
facilitated pathways resulting in water
movement through only a fraction of the Field BTC
available pore space
macropores
heterogeneous pore sizes
Volume of Water Leached
Note early elution of chemical C under field conditions
owing to preferential flow

5
 Importance of Preciptiation Rate &
Infiltration Rate
When precipitation rate is slow relative to
infiltration rate, flow occurs through
micropores
When precipitation rate is close to 1.0
infiltration rate, macropore flow occurs
Fraction
When precipitation rate exceeds of Chemical Piston-type Flow
0.5
infiltration rate, surface runoff occurs Eluted

0
0 1.0 2.0
Pore Volumes

1.0
Piston Flow 1.0

Fraction Fraction Flow Through

of Chemical 0.5 of Chemical 0.5 Heterogeneous Pores
Eluted Macropore Flow Eluted

0 0
0 1.0 2.0 0 1.0 2.0
Pore Volumes Pore Volumes

Uniform Pores
Piston Flow
Aging of Residues Slows Leaching
Velocity 1 Mixing > Convection 1.0 Fraction
Eluted
0.8
Heterogeneous Pores Atrazine, freshly injected
Convection > Mixing 0.6
Velocity 1
0.4

Macropore Flow Atrazine, aged residues

0.2
(Preferential Flow)
Mixing > Convection
Convection > Mixing 5 10 15 20 30 40 50 60
Velocity 2 Velocity 1 Pore Volumes
Pignatello et al. 1993

6
 Deeper Wells--Less Detections
Operational Factors Affecting Leaching USGS Analysis of Public Water Supply Wells
(Central Columbia Plateau -- 1994)
80
Depth of Well 70
Well Maintenance %
60
Detections
Timing of Application 50

Waste Disposal Practices 40

30
Irrigation System
20
10
0
<125 125 - 350 350 -1320
Well Depth (feet)

Velocity of Leaching Is Affected

Waste Disposal & GW by Concentration of Chemical
Fraction
Contamination Eluted tritiated water
1.0
Many agrichemical facilities with 5000 ppm
contaminated soil & wells 0.8

Historical dumping prior to Congressional 0.6 50 ppm

mandated waste regulations
RCRA; CERCLA 0.4
High concentrations favor
0.2
persistence 2,4-D amine Leaching
leaching
0.0
0 2 4 6 8 10 12 14
Pore Volumes Rao & Davidson 1979

Irrigation Style Affects Leaching

Recharge
Overhead
Irrigation in the Columbia Basin has Sprinkler
raised the water table and the yearly
recharge rate
Whitman Co.
Furrow
2 - 5 inches per yr
Franklin Co.
>10 inches per yr Microirrigation
(Surface or Subsurface)

7
 Leaching
volatilization
Volatilization Runoff
photodegradation

Sorption
penetration
Bioavailability Biodegradation
washoff Chemical &
Photodegradation