Agriculture, Ecosystems and Environment, 18 (1987) 231-241 Elsevier Science Publishers B.V.

, Amsterdam - Printed in The Netherlands

231

Factors Affecting the Adsorption of 2,4-D and Methyl Parathion in Soils and Sediments
KONDA S. REDDY and ROBERT P. GAMBRELL
Laboratory for Wetland Soils and Sediments, Center for Wetland Resources, Louisiana State University, Baton Rouge, LA 70803-7511 (U.S.A.)

(Accepted for publication 26 August 1986)

ABSTRACT Reddy, K.S. and Gambrell, R.P., 1987. Factors affecting the adsorption of 2,4-D and methyl parathion in soils and sediments. Agric. Ecosystems Environ., 18: 231-241. The adsorption of methyl parathion and 2,4-dichlorophenoxyacetic acid (2,4-D) by 19 soil and sediment materials differing widely in their physical and chemical properties was investigated using a batch equilibration technique. Organic matter was the most important single factor affecting adsorption of methyl parathion and 2,4-D. Soil pH and cation exchange capacity were also reasonably well associated with 2,4-D adsorption whereas cation exchange capacity contributed significantly for methyl parathion. Data are presented which indicate that in soil and sediment materials where the organic matter content in less than l%, oxalate extractable Mn and Ca were associated with the adsorption of these synthetic organics. Additional work should be done in low organic matter soil materials to better quantify the relationship between adsorption and soil geochemical properties.

INTRODUCTION

The partitioning of pesticides between dissolved and adsorbed phases during runoff events, and especially in sediment-water systems receiving runoff, is an important process regulating their transport and potential availability to nontarget organisms away from the point of application. Numerous studies and reviews during the past two decades have examined soil and sediment properties affecting the distribution of various synthetic and energy related organics between soluble and adsorbed forms (Karickhoff et al., 1979; Peck et al., 1980). It is well established that organic matter content is the major factor influencing the immobilization of synthetic organics (Chiou et al., 1979; Karickhoff et al., 1979; Peck et al., 1980; Wilson et al., 1981). In recent years, it has been demonstrated that expressing the distribution coefficients in terms of the soil
Present address: Texas Environmental Services, Nederland, TX.

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0 1987 Elsevier Science Publishers B.V.

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or sediment organic matter content substantially reduces the variability of measured distribution coefficients from different soils and sediments. This implies that the organic matter in different soils and sediments tends to be similar in its affinity for synthetic organics. Knowledge of soil or sediment organic matter content and octanol-water partitioning coefficients have been found to be valuable parameters in predicting the immobilization of pesticides by adsorption in soil and sediment-water systems (Karickhoff et al., 1979; Hassett et al., 1980; Brown and Flagg, 1981; Wilson et al., 1981). Other factors have also been shown to influence the adsorption of pesticides; the importance of parameters other than organic matter often depends on the chemical nature of the particular synthetic organic being considered. In particular, free iron oxides have been reported to affect pesticide adsorption (Pionke and Chesters, 1973). This component can be highly variable in different local soils and sediments, and particularly between soils of different regions. This could be important in soils with a low organic matter content, and especially in subsoils at waste disposal sites for pesticides and other synthetic organics. The objectives of this study were to determine the role of selected physical and chemical properties of soils and sediments on the distribution of methyl parathion and 2,4-D between dissolved and solid phases using a batch equilibrium adsorption procedure.
EXPERIMENTAL METHODS

Soil.9

To study the factors affecting pesticide adsorption, 19 soil and sediment materials were selected to include a broad range of physical and chemical properties. Samples were air-dried and ground to pass through a 2-mm sieve for characterization and adsorption studies. Soil samples were characterized for pH, cation exchange capacity, organic carbon, particle size distribution, free iron oxides, and Ca, Al and Mn extracted with the free iron oxides. Sample pH was determined on a 1:l soil-water suspension (Peech, 1965). Cation exchange capacity was determined by the ammonium acetate method (Chapman, 1965). Organic carbon was determined by the Walkley and Black method (Jackson, 1967)) and organic matter content was calculated by multiplying organic carbon by a factor of 1.724. The particle size distribution was determined by the hydrometer method (Day, 1965)) and free iron oxide was extracted by an ammonium oxalate extraction procedure ( McKeague and Day, 1966). Iron, Al, Ca and Mn were measured in the ammonium oxalate extract by an ICP emission spectrometer.
Pesticides

( 0-0-dimethyl-O-p-nitrophenyl

The pesticides selected for this study were the insectide methyl parathion phosphorothioate) and the herbicide, 2,4-D

233

(2,4dichlorophenoxyacetic acid). The partitioning of these pesticides between dissolved and adsorbed forms would be expected to be affected differently by changes in soil properties. The solubility of methyl parathion in water at 25 C is 50 mg 1-l (Wauchope, 1978)) and the solubility of 2,4-D in water is approximately 620 mg 1-l (Loos, 1969). Pesticide standard compounds from Chem-Service, Inc. were amended with 14C-labeled materials obtained from Pathfinder Laboratories, Inc. for this study. Stock solutions containing labeled methyl parathion and 2,4-D (specific activity 1 PCi ml- ) were prepared in acetone and stored in the refrigerator. The stock solutions were diluted with water such that on a soil solids basis, the amended levels of compound and label were 1 ,ug compound and 0.1 PCi specific activity per g soil, respectively. A batch equilibrium technique described below was used for this study (Leenheer and Ahlrichs, 1971). Twenty milliliters of a given pesticide solution were added to 2 g of air-dried soil in a 50-ml stainless steel centrifuge tube. The tubes were capped with teflonlined, stainless steel lids and equilibrated for 2 h on a mechanical box shaker. Each soil treatment combination was replicated three times. Following equilibration, the tubes were centrifuged for 15 min at 12000 rpm in a DuPont Sorvall SA-600 rotor. Aliquots of the clear supernatant solution (1 ml) were transferred to counting vials and 14C-labeled materials were measured on a Beckman Model LSlOOC liquid scintillation counter. To prepare a sample for counting, 1 ml of an aqueous sample was mixed with 15 ml of a commercial liquid scintillation counting reagent. Decreases in pesticide solution concentration were attributed to adsorption by the soil. After the l-ml sample aliquot was removed at 2 h, the caps were replaced on the centrifuge tubes and the equilibration continued for another 22 h, when another l-ml aliquot was sampled. Thus data were obtained for 2-h and 24-h equilibrations. Each sample was counted for 10 min. Standards and blanks were also counted and included in calculations to obtain adsorption coefficients. The amount of pesticides adsorbed on soils has been expressed as the soil-water distribution coefficient (K) calculated by the formula given below * (Wahid and Sethunathan, 1978; Luchini et al., 1981). K= pg adsorbed/g soil M dissolved/g solution

When the sorption of compounds is expressed as a function of the organic carbon content of a soil or sediment, a coefficient (K,,) is generated that is dependent upon the organic component (Hamaker and Thompson, 1972; Briggs, 1973; Karickhoff et al., 1979; Khan et al., 1979).

Km= % OC (decimal equivalent)

234

K,,, is equal to the distribution coefficient (K) divided by percent organic carbon (OC) in the respective soil or sediment, and is a measure of the partitioning of the compound between an aqueous solution and a stationary organic phase ( humus ) .
RESULTS

The physical and chemical properties of the soil and sediment materials studied are given in Table I. Adsorption/desorption coefficients for methyl parathion equilibrated with the 19 soils and sediments are given in Table II. Distribution coefficients were calculated for 2 h and 24 h adsorption. Soils 1, 3,4,7, 11,14 and 15 adsorbed methyl parathion relatively strongly after a 2-h equilibration and soils 2, 5,9,16, 18 and 19 did not strongly adsorb this compound. Soils that adsorbed relatively strongly were generally those with the highest organic matter content and those in the group that weakly adsorbed tended to have the lowest organic matter levels. The adsorption coefficients were generally about the same or slightly higher after 24 h equilibration as at 2-h equilibration, except for the muck which adsorbed substantially more at 24 h. Distribution coefficients of 2,4-D are presented in Table III. The values in the table show about the same inter-soil trend as methyl parathion, except that the coefficients were less, indicating that 2,4-D is less tightly bound than methyl parathion. The data show that with the exception of the Shubuta series, adsorption coefficients for 2,4-D were greater as the pH of the soil decreased. The very low CEC in the Shubuta material compared to the others may have been an interacting factor contributing to very low adsorption. The relationship between sorption and the soil organic carbon content can be expressed by dividing the individual distribution coefficients of the samples by their respective organic carbon contents to produce Kc, values (Hamaker and Thompson, 1972; Karickhoff et al., 1979). Calculation of K,, values has the effect of putting the sorption on a uniform organic carbon basis, assuming that all the organic carbon is equally effective (Lambert, 1968) in sorbing methyl parathion and 2,4-D. The methyl parathion K,,, values obtained for all samples investigated in this research ranged from 466 to 2815 and 554 to 2831 for 2 h and 24 h adsorption, respectively, with average values of 1374 and 1516, respectively ( Table IV ) . The K,, values for 2,4-D were also lower than for methyl parathion, ranging from 9 to 330 and 40 to 415 for 2 h and 24 h adsorption, respectively, with an average value of 93 and 160, respectively. The substantially decreased eoefficients of variation [ (S/f) x 1001 of K,,, values compared to coefficients of variation of adsorption coefficients for both compounds indicate the reduced variability between soils when adsorption is considered on an organic carbon basis (Table IV). This supports what others have reported in the literature.

TABLE I

Selected properties of 19 different soil and sediment materials CEC (meq/lOO g soil) Sand (%o) 36.2 91.8 21.3 27.1 35.0 40.0 33.8 33.2 73.7 17.5 56.5 94.2 53.1 65.7 46.9 74.7 27.8 76.2 87.0
4090

No. Silt (%) 52.6 1.7 36.6 45.0 35.0 30.0 23.2 55.6 19.0 39.0 15.3 2.1 45.0 13.8 36.2 16.0 59.7 17.1 4.4 2565 8190 4720 8165 1980 14100 9100 1155 37750 10100 699 16550 2940 23800 1758 9140 355 298 11.2 6.5 42.1 27.9 30.0 30.0 43.0 11.2 7.3 43.5 28.2 3.7 1.9 20.5 16.9 9.3 12.5 6.7 8.6 2110 422 2032 1553 2560 1755 3380 2220 512 4965 3120 238 1725 1387 2800 589 2030 273 354 36 19 42 30 92 2 45 18 29 122 43 63 88 23 65 29 180 26 40 Clay (%I Fe (,4? g- 1 Al (/lg g- ) Ca (mg- )

Soil material

PH

Organic matter (%o) 6.53 0.42 5.92 3.95 0.74 2.88 5.14 3.71 0.87 3.29 26.58 0.94 2.63 3.47 9.92 0.93 1.99 0.97 0.75

Particle size distribution

Ammonium oxalate extractable Mn (,% g- ) 16 126 253 200 36 126 61 499 91 786 43 40 565 90 502 144 559 76 110

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Airplane Lake AtchafaIaya River Bayou Chevreuil CaIcasieu River Cecil subsoil Cecil topsoil Chastain Crowly GaIIion Hartwell Lake Lafitte muck Lake Pontchartrain Lake Providence Leeville Loring Mhoon Mississippi River Norwood Shubuta

6.8 7.6 5.4 7.0 5.6 5.1 3.4 6.4 6.8 5.3 4.0 3.4 7.4 7.1 4.3 7.0 6.8 7.8 3.9

23.50 1.00 41.00 20.50 9.00 5.50 39.00 8.88 4.00 13.50 57.00 2.00 21.00 11.50 32.00 6.00 16.00 4.50 1.50

Sediment.

236 TABLE II Distribution coefficients Soil material for methyl parathion equilibrated with 19 soil and sediment materials

No.

K*
2-h 24-h 64.21+ 0.5Sb 2.52 + 0.07 64.15 + 0.40 49.28+ 1.17 4.62 + 0.52 23.36 +0.65 48.94 rL_ 0.39 19.53 & 0.11 3.85 +0.13 20.32f0.11 251.41 It8.93 15.57t0.91 20.40 + 0.63 40.17 + 2.05 153.88 _+2.59 7.54kO.14 24.54 + 0.45 3.10f0.09 3.13 rto.19

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19

Airplane Lake Atchafaiaya Bayou Chevreuil CaIcasieu River Cecil subsoil Cecil topsoil Chastain Crowley Gallion Hartwell Lake Lafitte muck Lake Pontchartrain Lake Providence Leeville Loring Mhoon Mississippi River Norwood Shubuta

70.63 rf:0.30b 2.03 + 0.08 60.85 + 0.56 56.35 Y? 1.40 2.58 rt 0.12 16.17 + 0.09 39.58 f 0.98 21.78 f0.26 3.46kO.14 18.16f0.10 79.93 + 3.69 14.08 + 0.59 18.77 + 0.93 50.48 + 3.92 162.45 t 3.25 5.80 rt 0.23 23.32 f 0.54 2.69kO.12 2.05rto.12

*Adsorption coefficient. Sediment. bMean of triplicate samples and standard

deviation.

Table V presents results of a statistical analysis examining the relationship between a number of soil properties and the adsorption coefficients of 24-D and methyl parathion after 2-h and 24-h equilibrations. The SAS RSQUARE procedure used employs linear regression to identify subsets of multiple independent variables, measured soil properties in this case, that best predict a dependent variable, or adsorption coefficients for this work ( SAS, 1985). Thus an R2 value was calculated for each adsorption coefficient for soil properties considered individually, and for every combination of pairs of soil properties. In a regression analysis, R2 represents the proportion of the total sum of squares of the dependent variable that is attributable to the independent varable ( s) (Steel and Torrie, 1960). Where all 19 soil and sediment materials were included, organic matter content gave the highest R2 values (except for methyl parathion with a 2-h adsorption). Cation exchange capacity was also reasonably well associated with 2,4-D adsorption where all 19 soils were included, and soil pH contributed significantly, though not with high R2 values. CEC contributed significantly for methyl parathion. The soil property most often cor-

237 TABLE III Distribution No. coefficients Soil material for 2,4-D equilibrated K* 2-h 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 Airplane Lake Atchafalaya River Bayou Chevreuil CaIcasieu Rivei Cecil subsoil Cecil topsoil Chastain Crowley GaIlion Hartwell Lake Lafitte muck Lake Pontchartrain Lake Providence Leeville Loring Mhoon Mississippi River Norwood Shubuta 0.85 f 0.05b 0.16f0.07 0.69 f 0.07 1.42f0.11 0.69 f 0.04 0.83 f 0.04 8.45f0.13 0.50 f 0.07 0.33 + 0.07 3.7550.10 20.16 f 0.24 1.82f0.08 0.19 f 0.09 1.29f0.02 8.96f0.31 0.05 f 0.08 0.51+ 0.03 0.31+ 0.07 0.09 f 0.02 24-h 1.52 f 0.06b 0.67 + 0.05 1.37+0.01 1.89?0.07 1.31+0.08 1.67kO.12 10.85 f 0.09 0.93 ? 0.06 0.87? 0.08 4.46 f 0.07 39.09 + 0.67 2.28 + 0.07 0.85 & 0.05 1.93 + 0.09 9.99zbo.11 0.38 f 0.05 1.17+0.08 0.70 f 0.04 0.44 f 0.03 with 19 soil and sediment materials

*Adsorption coefficient. Sediment. bMean of triplicate subsamples

and standard

deviation.

TABLE IV Means, standard deviations and coefficients of variation and 2,4-D adsorption in 19 soil and sediment materials Compound Equilibration time (h) 2 2 24 24 2 2 24 24 Parameter for K and K, values of methyl parathion

cv

Methyl Methyl Methyl Methyl 2,4-D 2,4-D 2,4-D 2,4-D

parathion parathion parathion parathion

34.3 1374 43.2 1516 2.7 93 4.3 160

39.9

782 61.8 642 5.0 93 8.9 115

114 57 143 42 185 100 206 72

TABLE V

R* w&es for 2-h and 24-h adsorption coefficients (K) for 2,4-D and methyl parathion vs. selected independent variables Single independent variables Best pair, RZ CEC Al Fe Mn Ca Organic matter o.a4** 0.15
0.00

Compound Clay Sand pH

Dependent parameter

No. of soils

2nd best pair, RZ

3rd best pair, R2

2,4-D 0.13 0.00 0.00 0.32 0.40 0.00 0.00 0.06 0.02 0.02 0.15 0.17 0.00 0.08 0.14 0.07 0.01 0.00 0.02 0.16 0.18 0.07 0.07 0.14 0.02 0.66 0.26* 0.15 0.16 0.32 0.36 0.01 0.12 0.03 0.17 0.7011 0.08 0.46** 0.34 0.00 0.03 0.31 0.00 0.00 0.00 0.62 0.22 0.02 0.56** 0.18 0.05 0.30* 0.60; 0.26* 0.12 0.90** 0.10 0.01 0.04 0.17 0.14 0.07 0.03 0.03 0.02 0.341 0.93** 0.10 0.11

K,

2h

19(all)

2.4-D

K, 24 h

19fall)

2,4-D

K,

2h

(low OM)

2,4-D

K,24h

K,

2h

(low OM) 19

K, 24 h

19

K,

2h

(low OM)

Methyl parathion Methyl parathion Methyl parathion Methyl parathion

K, 24 h

(low OM)

pH-OM, 0.90 pH-OM, 0.92** Mn-sand, o.r32** Mn-sand, o.s4** Iron-CEC, 0.47** CEC-OM, 0.93** Ca-clay, 0.74** Ca-clay, 0.74;

Iron-OM, 0.87** OM-sand, 0.91** Mn-clay, 0.78 Mn-clay, 0.77** Mn-CEC, 0.47** OM-clay, 0.93 ; Ca-Al, 0.68 Ca-Al, 0.66*

AI-OM, 0.85** Ca-OM, 0.91** Mn-AI, 0.73* Mn-CEC, 0.748 CEC-sand, 0.47** Iron-OM, 0.93** Mn-sand, 0.53 Iron-Ca, 0.50

**, R2 significant at the 1% level. *, R2 significant at the 5% level.

239

related with 2,4-D adsorption is organic matter (Bailey and White, 1964). Our data on 19 soil and sediment materials indicate that low pH also promotes 2,4D adsorption (Kuo, 1973).
DISCUSSION

In soil and sediment materials where the organic matter content is very low, such as typical subsurface soil horizons, other soil properties may then become substantially more important in regulating the mobility of synthetic organics. One object of this work was to examine the importance of properties other than organic matter content in adsorbing these pesticides in soil materials with low organic matter content. In particular, we were interested in examining the role of reducible iron levels as well as the Al extracted by an ammonium oxalate extractant. Therefore, R2 values describing the relationship between adsorption and soil properties were also determined on those soil and sediment materials with less than 1% organic carbon, an arbitrary cutoff on our part. In these low organic matter materials, pH gave low R2 values of 0.31-0.36 for both 2- and 24-h adsorption coefficients for both compounds, and all of the other properties we originally planned to examine gave much lower values. Oxalate extractable Fe and Al levels gave especially low R2 values. In these low organic matter materials, however, we observed that the relationship between adsorption and oxalate extractable Mn and Ca increased, especially for 2,4-D. Table V presents R2 values where the regression includes two independent variables. For each combination of compound, adsorption equilibration time, and level of soil organic matter, the pair of soil parameters giving the first, second, and third highest R2 values are presented. In the low organic matter soil and sediment materials, the R 2 values were greatly improved by including pairs of soil properties in the regression analyses. Oxalate extractable Mn or Ca appeared in all of the independent variable pairs giving the highest three R2 values. The reason for the frequent inclusion of oxalate extractable Ca and Mn as an independent variable contributing to some of the higher R2 values was not investigated further. However, a previous study has shown different saturating cations have an effect on the adsorption of Dasanit, another organosphate insecticide, (O,O-diethyl O-[p- (methyl sulfinyl) phenyl] phosphorothioate) in montmorillonite suspensions (Bowman, 1973). This effect was attributed to the nature of the cation-pesticide interaction, the limited water solubility of the compound, and the effect of the saturating cation on the aggregation of the clay in the suspension used. Thus in soil and sediment materials with low organic matter content, Ca and Mn, or factors associated with weak chelate extractable levels of these elements, may be important for regulating the mobility of these synthetic organics.

240 CONCLUSIONS

Organic matter content of the soil materials was generally indicated to be the most important property affecting adsorption. As expected, 2,4-D was less strongly associated with the solid phase than methyl parathion, and pH was more closely associated with the adsorption of 2,4-D than with methyl parathion. Data were presented indicating that in low organic matter content soils (1% organic matter was arbitrarily selected as the cutoff), the association between adsorption and oxalate extractable Mn and Ca may be an important relationship. Additional work should be done in low organic matter soil material to better quantify the relationship between adsorption and soil geochemical properties. As our work has demonstrated, those properties closely associated with the adsorption of some synthetic organics in typical surface soils may not be useful in predicting the immobilization of synthetic organics in subsoils Understanding the relationship between geochemical properties and the mobility of synthetic organics is especially important in typical, low-organic matter subsoil materials that have been contaminated with hazardous organics such as has occurred at many hazardous waste disposal sites.
ACKNOWLEDGEMENTS

This research was supported by the Environmental Research Laboratory, U.S. Environmental Protection Agency, Athens, GA. This support does not signify that the contents necessarily reflect the views and policy of the Agency; nor does mention of trade names of commercial products constitute endorsement or recommendation for use.

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