Sorption of a hydrophilic pesticide: Effects of soil water content and

matric potential

Tyson E. Ochsner*1, Brandon M. Stephens2, William C. Koskinen1, and Rai S. Kookana3

1 USDA-ARS, Soil and Water Management Research Unit, St. Paul, MN 55108 2 Dep. Soil, Water, and Climate, Univ. of Minnesota, St. Paul, MN 55108 3 CSIRO Land and Water, PM B2, Glen Osmond, SA 5064, Australia

Introduction

• The leaching risk of a pesticide in soil is characterized primarily by the sorption coefficient (Kd).

• Lower Kd values indicate greater potential for leaching.

• The effects of soil water content and matric potential on Kd are not well understood.

• This is a serious gap because pesticides are often applied on or near the soil surface where the water content varies dramatically.

Pesticide -- Dicamba

• Dicamba is a widely used broadleaf herbicide sold under the trade names Banvel and Clarity.

• During 2002, approximately 11% of US corn was treated with dicamba at a rate of 0.22 kg active ingredient ha-1 yielding a total of 512 Mg of active ingredient applied.

Fig. 1. Molecular structure of dicamba, a hydrophilic, weakly-sorbing herbicide with pKa of 1.9.

Soils

Table 1. Basic properties for the three soils on which Kd was measured. Soil Location Texture Organic C

content Clay Sand Specific

surface area pH

Tifton Waukegan Drummer

Tifton, GA Rosemount, MN Oxford, IN

LS SiL

SiCL

g kg-1 7.0 18.0 39.5

% 11 23 34

% 82 22 19

m2 g-1

16.9 78.0 136

5.9 5.8 5.3

Texture: Si silt, C clay, L loam, S sand

• Sorption of dicamba was measured in three soils (Table 1), each at two initial water contents.

• Soils were moistened to the desired initial water content using a solution containing 14C-labeled dicamba; the resulting dicamba concentration was ~1 g g-1.

Unsaturated transient flow experiments

• After equilibration, the soil was packed into a column with 20 sections (0.9 cm thick). The column was positioned horizontally and connected to a Mariotte bottle (Fig. 2).

• The bottle supplied 5 mM CaCl2 solution (without dicamba) to the column inlet at a constant pressure.

• Infiltration terminated when the wetting front reached ¾ of the way through the column.

Fig. 2. Soil column and Mariotte bottle set-up used for horizontal infiltration experiments.

Water and pesticide distributions

0 2 4 6 8 10 12 14 16 180

0.1

0.2

0.3

0.4

0.5

Wat

er c

onte

nt (

m 3

m-3

) Loamy sand

0 2 4 6 8 10 12 14 16 180

1

2

3

4

5

Dic

amba

con

c. (

g

g-1 s

oil)

Water

Dicamba

0 2 4 6 8 10 12 14 16 180

0.1

0.2

0.3

0.4

0.5

Wat

er c

onte

nt (

m 3

m-3

) Silt loam

0 2 4 6 8 10 12 14 16 180

1

2

3

4

5

Dic

amba

con

c. (

g

g-1 s

oil)

0 2 4 6 8 10 12 14 16 180

0.1

0.2

0.3

0.4

0.5

Wat

er c

onte

nt (

m 3

m-3

) Silty clay loam

Distance (cm)0 2 4 6 8 10 12 14 16 18

0

1

2

3

4

5

Dic

amba

con

c. (

g

g-1 s

oil)

• Infiltrating water displaced the antecedent solution, creating a plane of separation (vertical line, Fig. 3).

• For positions beyond this plane, the total pesticide content per unit mass of dry soil was regressed against the solution volume per unit mass of dry soil.

Fig. 3. Distributions of water and dicamba after horizontal infiltration.

0 0.1 0.2 0.3 0.40

1

2

3

4

Dic

amba

con

c. (

g

g-1 s

oil)

Loamy sand

Kd = 0.013

y = 16x + 0.2

r2= 0.97

0 0.1 0.2 0.3 0.40

1

2

3

4

Dic

amba

con

c. (

g

g-1 s

oil)

Silt loam

Kd = 0.079

y = 3.9x + 0.31

r2= 0.99

0 0.1 0.2 0.3 0.40

1

2

3

4

Dic

amba

con

c. (

g

g-1 s

oil)

Silty clay loam

Kd = 0.056

y = 10x + 0.56

r2= 0.96

Solution volume per unit mass dry soil (cm 3 g-1)

• For positions beyond this plane, the total pesticide content per unit mass of dry soil was regressed against the solution volume per unit mass of dry soil (Fig. 4).

• The intercept divided by the slope gave the Kd.

Fig. 4. Dicamba concentration versus solution volume.

Determination of Kd

Sorption coefficientsTable 2. Dicamba sorption coefficients (Kd) determined by the unsaturated transient flow method for three soils each at two different initial water contents and matric potentials. Shown are mean and (standard deviation) of three replicates.

Initial condition

Water content Matric potential Kd

kg kg-1 kPa L kg-1

Loamy sand 0.05 -88 0.01 (0.02)

0.24 -4.3 0.00 (0.00)

Silt loam 0.05 -9.5 x 105 0.04 (0.00)

0.19 -137 0.08 (0.00)†

Silty clay loam

0.06 -1.1 x 105 0.07 (0.04)

0.23 -122 0.40 (0.12) † Two replicates only.

Table 3. Parameter estimates, 95% confidence intervals, coefficient of determination (r2), and F statistic for the regression model. The independent variable is the cross-product of organic carbon content (OC, g kg-1) and initial water content (g, kg kg-1). The dependent variable is the dicamba sorption coefficient (L kg-1).

Parameter 95% Confidence intervals

estimate lower upper r2 F

Intercept -0.030 -0.072 0.012 0.863 94.2***

OC x g 0.045 0.035 0.055

***Significant at the 0.001 probability level

Regression analysis

• No significant relationship existed between Kd and matric potential.

• We found a strong linear relationship between Kd and the product of soil water content and organic C content (r2 = 0.86, Table 3).

Conclusions

• The number of dicamba sorption sites increases with soil organic C content, while the accessibility of these sites increases with soil water content.

• This may be caused by the decreasing hydrophobicity of soil organic matter with increasing water content.

• The effects of water content on pesticide sorption require further research and may ultimately have implications for the methods used to determine sorption and for managing pesticide application.

ochsner@umn.edu