U.S. Department of the lnterior U.S.

Geological Survey

Controlled-Release Fertilizers Using Zeolites

Introduction The ultimate fertilizer should be inexpensive and long lasting, should tend to increase soil fertility through repeated use, and should release nutrients to plants as they are needed, thereby eliminating pollution and inefficiencies. Whether or not such systems will be realized will depend on agricultural research into technologies that are fine-tuned to ecologically sustainable methods. U.S. Geological Survey (USGS) preliminary experiments indicate that the use of zeolites in agriculture is a promising avenue for such research. Background The use of soluble fertilizers can lead to water pollution and to wasted nutrients. Nitrogen, for example, can leach into ground and surface waters, especially in sandy soils, and phosphate may become fixed and unavailable to plants, especially in tropical soils. Zeolites, porous minerals with high cation-exchange capacity, can help control the release of plant nutrients in agricultural systems. Zeolites also can free soluble nutrients already in soil for use by plants, and may improve soil fertility and water retention. Because zeolites are common, they could be useful on a large scale in agriculture. USGS research uses zeolites in several ways to control the release of nutrients in soil. Controlled-release nitrogen fertilizer Urea is one of the most common nitrogen fertilizers. It is very soluble in water, and can be leached through the root zone. In addition, urea is converted into ammonium ions by an enzyme found in most soils. Soil bacteria then convert these ammonium ions into readily leachable nitrate ions. Using zeolitic rocks in fertilizer can help prevent these nutrient losses. A controlled-release nitrogen (N) fertilizer can be produced by heating 0 zeolite rock chips to about 400 C to drive out all zeolitic and pore water, which is replaced with molten urea. 0 The urea crystallizes at about 132 C. The rate of nitrogen release from the zeolitic rock is slowed in three ways: (1) by containing urea in the rock pores and zeolite crystals, thus preventing the leaching of urea from the root zone; (2) by slowing the conversion of urea by soil enzymes, thus delaying the formation of ammonium ions; and (3) by taking up ammonium ions onto exchange sites in the zeolite, thus protecting them from nitrifying bacteria. Potassiumsaturated zeolite prepared by the above method contained approximately 17 wt. percent elemental N. The rate of N release can be controlled by changing the size of the rock chips. The smaller the size the quicker the release. The relationship is shown by the following equation: wt. percent N = 20 + 40 (log mean particle size in mm). Controlled-release phosphorous fertilizers Phosphate (H2PO4-) can be released to plants from phosphate rock (P-rock) composed largely of the calcium phosphate mineral apatite by mixing the rock with zeolite having an exchange ion such as ammonium. The approximate reaction in soil solution is as follows: (P-rock) + (NH4-zeolite) = (Ca-zeolite) + (NH4+) +(H2PO4-). The zeolite takes up Ca + from the phosphate rock, thereby releasing both phosphate and ammonium ions. Unlike the leaching of very soluble phosphate fertilizers (for example, superphosphate), the controlledrelease phosphate is released as a result of a specific chemical reaction in the soil. As phosphate is taken up by plants or by soil fixation, the chemical reaction releases more phosphate and ammonium in the attempt to reestablish equilibrium. The rate of phosphate release is controlled by varying the ratio of P-rock to zeolite. Phosphorus is also released from the rock by the lowering of soil pH as ammonium ions are converted to nitrate.
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Controlled-release fertilizers were tested in greenhouse pot experiments with sorghum-sudangrass using NH4saturated zeolite (clinoptilolite) and Prock with a phosphate application rate of 340 mg P per kg soil, and zeolite/Prock ratios ranging from 0 to 6. Total phosphate uptake and phosphate concentration measured for the grass were related linearly to the zeolite/Prock ratio, and yields summed over four cuttings were as much as four times larger than control experiments. Release of trace nutrients Experiments indicate that zeolite in soil can aid in the release of some trace nutrients and in their uptake by plants. The release of phosphorus, potassium (K), manganese (Mn), zinc (Zn), iron (Fe), and copper (Cu) was enhanced by the presence of zeolite in a neutral soil. The concentration of Cu and Mn in sudangrass (in mg/kg) was significantly related to the zeolite/Prock (x) in experimental systems that used two different NH4 saturated clinoptilolites, two different soils, and two different forms of P-rock. For example, the relation for one system 2 2 was: Cu = 2.78 + 0.83x -0.06x (R = 0.94), and Mn = 40.03 + 18.49x + 2 2 0 . 76x (R = 0.99). The mechanism for this effect may be similar to that discussed above: sparingly soluble minerals are dissolved as an effect of preferential exchange on the zeolite. Trace nutrients on the zeolite exchange sites are then freed for uptake by plants. Potential harmful effects Zeolites can be harmful as well as helpful to plant growth. For example, zeolites with sodium as the chief exchange ion can be toxic to plants,

and K-, Ca-, and NH4-poor zeolites can scavenge these ions from soil solutions and thereby limit plant growth when used in soils that am deficient in these nutrients. These negative results emphasize the need to use appropriate zeolites during agricultural experimentation. Selected references Barbarick, K.A., Eberl, D.D., and Lai, T.M., 1988, Response of sorghumsudangrass in soils amended with phosphate rock and NH4exchanged zeolite (clinoptilolite): Technical Bulletin TB88-1, Department of Agronomy, Colorado State University, 62 p. -1991, Pine Ridge zeolite and Fort Hall mill shale P effects on sorghum-sudangrass: Technical Bulletin TB9l-2, Department of Agronomy, Colorado State University, 47 p. Barbarick, K.A., Lai,T.M., and Eberl, D.D., 1990, Exchange fertilizer (phosphate rock plus ammoniumzeolite) effects on sorghumsudangrass: Soil Science Society of America Journal, v. 54, p. 911-916. Lai, T.M. and Eberl, D.D., 1986, Controlled and renewable release of phosphorus in soils from mixtures of phosphate rock and NH4exchanged clinoptilolite: Zeolites, v. 6, p. 129132. Pond, W.G. and Murnpton, EA., eds. 1984, Zeo-Agriculture: Use of natural zeolites in Agriculture and Aquaculture: Westview Press, Boulder, Colorado, 296 p.

Information For further information, contact: Dennis D. Eberl U.S. Geological Survey 3215 Marine Street Boulder, Colorado 80303 303-54 l-3028; Fax 303-447-2505 E-mail: ddeberl@brrcrmail.cr.usgs.gov

November 1993