DISPERSION OF KAOLINITE BY DISSOLVED ORGANIC FROM DOUGLAS-FIR ROOTS1 PHILIP B. DURGIN and JESSE G. CHANEY2 Pacific Southwest Forest Experiment Station, U.S. Department of Agriculture, For- est Service, Berkeley, California 94701. Received 30 June 1983, accepted 15 Apr. 1984. DURGIN, P. B. AND CHANEY, J. G. 1984. Dispersion of kaolinite by dissolved organic matter from Douglas-fir roots. Can. J. Soil Sci. 64: 445-455. The organic constituents of water extracts from Douglas-fir (Pseudotsuga menziesii [Mirb.] Franco var. menziesii) roots that cause kaolinite dispersion were investi- gated. The dissolved organic matter was fractionated according to molecular size and chemical characteristics into acids, neutrals, and bases of the hydrophilic and hydrophobic groups. The dominant fraction causing dispersion included the hydro- phobic acids and organics with molecular sizes greater than 104 nominal molecular weight. Partial oxidation of the dissolved organic matter increased its carboxylic acid content and dispersion potential. Organic acids promoting kaolinite dispersion included aliphatic and aromatic carboxylic acids. The dispersing ability of a car- boxylic acid was related to its charge and charge density. Kaolinite has a pH-de- pendent surface charge; specific adsorption of carboxyl groups makes the clay more negative and promotes dispersion. Polycarboxylic acids appear to play the major role in kaolinite dispersion by dissolved organic matter in forests. Key words: Fulvic acid, specific adsorption, carboxylic acid, fractionation [Dispersion de la kaolinite par la matiere organique dissoute des racines de sapin de Douglas.] Titre abrégé: Dispersion de la kaolinite par la matière organique. Les éléments organiques des extraits aqueux de racines de sapin de Douglas (Pseu- dotsuga menziesii [Mirb.] Franco var. menziesii) qui entraînent la dispersion de la kaolinite ont fait l'objet de recherches. La matière organique dissoute a été frac- tionnée d'après sa taille moléculaire et ses propriétés chimiques en acides, en corps neutres et en bases à groupements hydrophiles et hydrophobes. La fraction domi- nante qui entraîne la dispersion comprend les acides et la matière organique hydro- phobes dont les molécules dépassent le poids moléculaire nominal de 104. Une oxydation partielle de la matière organique dissoute augmente la concentration d'acide carboxylique et la capacité de dispersion. Les acides organiques qui favo- risent la dispersion de la kaolinite comprennent les acides carboxyliques aroma- tiques et aliphatiques. Le pouvoir dispersif des acides carboxyliques dépend de la charge et de la densité de charge de ces derniers. La charge superficielle de la kaolinite dépend du pH; l'adsorption spécifique des groupements carboxylis ren- dent l'argile plus négative ce qui en facilite la dispersion. Les acides polycarboxy- liques semblent jouer le rôle principal dans la dispersion de la matière organique dissoute dans le sol forestier. Mots clés: Acide fulvique, adsorption spécifique, acide carboxylique, fractionne- ment 1Trade names and commercial enterprises and prod- dorsement by the U.S. Department of Agriculture is ucts are mentioned solely for information. No en- implied. 2Present address (J.G.C.): North Coast Laboratories Ltd., Can. J. Soil Sci. 64: 445-455 (Aug. 1984) Arcata, California 95521. 445 446 CANADIAN JOURNAL OF SOIL SCIENCE Dissolved organic matter — a common constituents of Douglas-fir (Pseudotsuga constituent of natural water — is generated menziesii [Mirb.] Franco var. menziesii). as organic matter decomposes (Hu et al. Leachate of Douglas-fir root was fraction- 1972). Dissolved organics leached from the ated and tested for dispersion potential, and leaves of some trees can effectively defloc- the functional groups most responsible for culate kaolinite (Bloomfield 1954). Kaolin- kaolinite dispersion were identified. ite has a variable surface charge. It can ad- sorb anions (i.e. specific adsorption) that MATERIALS AND METHODS will change its charge (Hingston et al. 1967) Live Douglas-fir roots less than 10 mm in di- and thereby influence its flocculation-dis- ameter were collected at random from the Lower persion state. Trinity District of the Six Rivers National Forest Dispersion can regulate a soil's erodibil- of northwestern California. The roots were washed with water and ground in a laboratory ity and promote soil development. Dis- mill then sieved through a 355-µm soil sieve and persed kaolinite has been associated with combined into a composite sample. The com- turbid and extremely turbid streams from a posite sample can not show the variance occur- mountainous watershed in Oregon (Young- ring between different Douglas-firs. Therefore, berg et al. 1975). Dispersion or defloccu- the variance of the replicates are more a reflec- lation not only influences surface erosion, tion of different lab conditions than of different but is also associated with subsurface ero- field conditions. sion (soil piping or suffusion), which can The dissolved organic matter was prepared by be a precursor to landsliding on steep slopes placing 2 g of Douglas-fir root powder in a bottle with 100 mL of reagent grade water. The bottle (Durgin 1984). Dispersed kaolinite can be was shaken for 6 h at 180 rpm, and filtered carried by water moving through the soil. through a prefilter and a 0.45-µm membrane fil- Bloomfield (1954) used this process to help ter. The dissolved organic matter was stored at explain the formation of podzols with their 4°C and used as soon as possible after extrac- clay-leached "A" horizon. Jenny and tion. Smith (1935) explained claypan formation as a result of dispersed clay being floccu- Size Fractionation lated or being attracted to sesquioxides. Size fractionation was done by pressure filtering Claypans did not develop if humus leach- a 15-mL, aliquot of root leachate through Milli- ates were applied to the clay. Apparently pore ultrafilters of 103, 104, or 105 nominal mo- lecular weights (NMW). Aliquots were also fil- the fulvic acid attached to the clay, dis- 4 5 persed it, and kept it in suspension as the tered through Amicon 3 × 10 and 3 × 10 water moved through the soil. NMW ultrafilters. Nitrogen was used to provide pressure for the filter cells in order to minimize While it is well established that sodium sample oxidation. Each 15-ml, aliquot was di- promotes clay dispersion, it remains un- luted to 80 mL, reduced by filtration to about 15 clear which organic constituents have dis- mL, diluted again, and refiltered. This rinsing persion potential. Bloomfield (1954) con- procedure helped sieve most of the appropriate cluded that polyphenols were the major material through the filter. The diluted filtrate contributors to kaolinite deflocculation but was then reduced to its original volume by rotary recommended that his work be repeated evaporation. The final six size fractions were: 3 4 4 5 5 more rigorously. Since then, new organic <10 , <10 , <3 × 10 , <10 , <3 × 10 NMW fractionation techniques have been devel- and the unsieved leachate. Amounts of organic carbon in each size class were estimated with an oped. Leenheer and Huffman (1976) de- infrared carbon analyzer. veloped a procedure that emphasizes the Each size fraction was tested for its ability to hydrophilic-hydrophobic nature of organic disperse kaolinite. One-half milliliter of leach- molecules. ate was added to 49.5 mL of reagent grade water. This paper reports a study of a strong dis- This solution was then added to 1 g of ceramic perser of kaolinite: water-soluble organic grade Georgia kaolinite and shaken in a 25 × DURGIN AND CHANEY - DISPERSION OF KAOLINITE BY ORGANIC MATTER 447 200-mm test tube. The suspension settled for 2 duced during the neutralization process, from h before the top 20 mL were pipetted off. This interfering with the kaolinite dispersion tests. suspension was placed in a beaker, oven-dried, The fractions were reduced to the original 50- cooled, and weighed. Each sample and a water mL volumes by the 103 ultrafilter cell. blank were replicated four times. The hydrophobic and hydrophilic acids, neu- trals and bases, and a water blank were tested Chemical Fractionation for kaolinite dispersion activity and total organic We used a modification of the Leenheer and content. The dispersion test was similar to the Huffman (1976) fractionation procedure for one used for the size fractionation. water-soluble organic matter. Their basic ap- proach was to separate out various organic con- Carboxylic Acids stituents of natural waters on the basis of mo- The root leachate was oxidized by slowly bub- lecular polarity and charge. A macroreticular bling air through it for a week. The carboxylic resin was used to absorb nonpolar or slightly po- acid content was determined in the unoxidized lar compounds, namely the hydrophobic frac- and oxidized root leachate by the decarboxyla- tions. The hydrophilic compounds were ad- tion method of Schnitzer and Gupta (1965). Rate sorbed on either a cation or anion exchange of kaolinite dispersion was measured by mixing resin. By elution of the columns with appropri- 2 g of kaolinite in water with 2 mL of root leach- ate solvents, the organic matter was further sep- ate. This amount is equivalent to 2% of dry root arated into both hydrophobic and hydrophilic per unit weight of clay. A paired t-test with seven acid, neutral, and base fractions. replications was used to analyze the carboxyl The size fractionation showed that the less contents and the dispersion capacities of the root than 103 NMW fraction of root leachate did not leachates. effectively disperse kaolinite. Since salts and Potassium carboxylates were tested for their light organics in this fraction tended to load the kaolinite dispersion activity. The potassium resin columns, they were removed by ultrafil- concentration was held constant at 0.002 M and tration through a 103 membrane. The remaining the molarity of carboxylates varied from that ac- organic carbon concentration in the leachate (103 cording to its charge. These solutions were each NMW to 0.45 µm) was determined and referred mixed with 2 g of kaolinite and the dispersion to as the whole root leachate.