Abstract:
Improved fertilizer mineral compositions are provided by coating a mineral, such as gypsum, a member of the Kieserite Group, potassium magnesium sulfate, elemental sulfur, and mixtures thereof, with low pH maleic-itaconic copolymers. The preferred copolymers are aqueous dispersions of acid or partial salt maleic-itaconic copolymers, and are applied by spraying or other means onto the surface of the mineral and allowed to dry. The copolymer coatings increase the solubility of sulfate and calcium or magnesium ions from the fertilizer minerals, allowing accelerated plant availability and uptake of such nutrients.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention is broadly concerned with fertilizer compositions and methods wherein the compositions include agriculturally valuable minerals, such as gypsum, members of the Kieserite Group, potassium magnesium sulfate, and elemental sulfur, together with an amount of a copolymer adjuvant or additive serving to significantly increase the availability of sulfate and other ions in soil, particularly during the early stages after application of the fertilizer compositions. More particularly, the invention is concerned with such fertilizer compositions and methods wherein the dried residue of an aqueous, very low pH copolymer dispersion (e.g., either a true solution or a mixture) coats the minerals and wherein the copolymer includes respective quantities of maleic and itaconic moieties. 
     2. Description of the Prior Art 
     Gypsum is a soft mineral compound formed of calcium sulfate (CaSO4), usually found in nature in the dihydrate form (CaSO4.2H2O). It is colorless to white with a silky, pearly, or waxy luster, and commonly has various colored impurities. Gypsum occurs in nature as flattened and often twinned crystals and transparent cleavable masses called selenite. It may also be granular or quite compact. Gypsum has a number of commercial uses, and is well known as a fertilizer and soil conditioner. In the late 18th and early 19th centuries, Nova Scotia gypsum, often referred to as plaister, was a highly sought fertilizer for wheat fields. Gypsum is also used in ameliorating sodic soils. A significant advantage of gypsum is that it is relatively low in cost, while containing substantial quantities of nutrients; e.g., commercial gypsum grades normally contain about 22% Ca and 17% S. 
     When applied to soils, gypsum supplies crop-available forms of calcium and sulfate ions. However, owing to the very limited solubility of gypsum in water, positive fertilizing results or soil amendments may require a two or three year program of applications. Hence, although gypsum fertilizer use is well-recognized, the slow action of gypsum does not provide immediate help, either in the form of plant nutrition or soil remediation. 
     Kieserite is a form of magnesium sulfate (MgSO 4 .H 2 O) having a monoclinic crystalline system. There are a number of related minerals, known as the Kieserite Group, which includes other hydrated forms of magnesium sulfate, such as Epsomite (MgSO 4 .7H 2 O); the group also includes a relatively rare zinc-rich mineral Gunningite (Zn,Mn)(MgSO 4 .H 2 O). Comprehensive lists of Kieserite Group minerals may be found in Hammel (1939) Annales de Chimie, Paris: 11:247, and Palache, C., Berman, H., &amp; Frondel, C. (1951), The System of Mineralogy of James Dwight Dana and Edward Salisbury Dana, Yale University 1837-1892, Volume II. John Wylie and Sons, Inc. New York, 7 th  Edition, Revised and Enlarged, 1124 pp. 477, both of the foregoing being expressly incorporated in their entireties by reference herein. The Kieserite Group, because of the valuable plant nutrients therein, can be used as plant fertilizers. 
     Elemental sulfur is also commonly applied to soils in order to supply sulfate ion. However, elemental sulfur is converted to sulfate very slowly in normal soils, and thus the beneficial effects of sulfur applications may take several growing seasons to appear. 
     There is accordingly a need in the art for enhanced forms of fertilizer minerals which accelerate the availability of sulfate and other ions (e.g., Ca and Mg) in the soil. 
     SUMMARY OF THE INVENTION 
     The present invention overcomes the problems outlined above and provides improved mineral fertilizer compositions comprising respective quantities of a mineral together with a copolymer in contact with the mineral and containing individual quantities of maleic and itaconic moieties. The minerals used in the invention are generally selected from gypsum (either in the refined anhydrous or hydrated form), the Kieserite Group, potassium magnesium sulfate, elemental sulfur, and mixtures thereof. 
     When gypsum is employed, it may be of any commercial grade suitable for fertilizer use, and may be naturally occurring or synethized as a byproduct. Advantageously, the gypsum is in the form of granules or pellets having a maximum dimension of up to about one inch, and more preferably up to about one quarter inch. As used herein, “commercial grade agricultural gypsum” refers to a gypsum product containing at least about 80% by weight calcium sulfate (more preferably from about 84-97% by weight), from about 19-27% by weight elemental calcium equivalent (more preferably from about 21-25% by weight), and from about 15-23% by weight elemental sulfur equivalent (more preferably from about 16-21% by weight). Such gypsum would also include impurities such as calcium carbonate and other trace materials. 
     Any suitable Kieserite Group mineral can also be used, and especially Kieserite itself. The only real criteria are commercial availability and cost. The same sizes of granules or pellets described with reference to gypsum may also be used with the Kieserite Group minerals. In general, it is preferred that Kieserite be used having a minimum of about 14% by weight Mg and 20% by weight S therein. 
     Potassium magnesium sulfate, sometimes referred to as “KMag,” has the formula K2Mg(SO4)2 and analysis of 0-0-22. It contains about 22% K2O, 11% Mg, and about 22% S. It is available in anhydrous and hydrated form, the latter usually a hexahydrate. 
     Elemental sulfur in granular or other forms can also be used in the invention as a soil nutrient. 
     The preferred copolymer adjuvants of the invention are applied to or used with the mineral fertilizers as aqueous, low pH copolymers containing maleic and itaconic moieties, usually derived from the corresponding acids or anhydrides. While other monomers may form apart of the maleic-itaconic copolymers, the itaconic and maleic monomers should together form the preponderant fraction of the copolymers. Advantageously, other monomers should be present only in minor amounts of up to about 7% by weight, more preferably up to about 4% by weight, based upon the total weight of the copolymer taken as 100% by weight. Stated otherwise, the copolymers should comprise at least about 93% by weight, more preferably about 96% by weight, of a combination of itaconic and maleic monomers. Most preferably, the copolymer consists essentially of or is entirely made up of maleic and itaconic moieties. Ideally, the polymer fraction consists essentially of the itaconic/maleic copolymers, i.e., it is essentially free of other types of monomers. The copolymer is preferably an aqueous solution or dispersion and is highly acidic. The pH usually ranges from about 0.1-2.2, more preferably from about 0.1-2, and most preferably from about 0.2-0.8. Where partial salt forms of the copolymer are employed, the pH levels would be on the higher end of the foregoing ranges. A variety of salt-forming cations may be used, but sodium and potassium are preferred. 
     Generally, the fertilizer compositions include predominant amounts of mineral fertilizers of from about 95-99.95% by weight, more preferably from about 97-99.93% by weight, and most preferably from about 98-99.9% by weight, with the total weight of the composition taken as 100% by weight. Correspondingly, the copolymer fraction is the dried residue of the initially aqueous copolymers described above, and such residue should be present at a level such that the plant availability of calcium and/or sulfate ion (in the case of gypsum or elemental sulfur) or magnesium and/or sulfate ion (in the case of the Kieserite Group minerals) is greater than the corresponding plant availability of the untreated fertilizer minerals; more preferably, the plant availability of such ions in the case of the compositions of the invention is at least about 15%, and most preferably at least about 30%, greater than that of the respective uncoated fertilizer minerals. In terms of weight amounts, the dried residue of the copolymers is generally from about 0.05-5% by weight, more preferably from about 0.07-3% by weight, and most preferably from about 0.1-2% by weight, with the total weight of the composition taken as 100% by weight. 
     The compositions may be simply prepared by spraying or otherwise applying the low pH aqueous copolymer to the mineral fertilizers, followed by drying to yield the dried residue of the copolymer on the surfaces thereof. Such coated compositions are then used in the usual fashion by application to soils, with or without incorporation into the soil. Although less desirable, it would also be possible to initially apply fertilizer minerals followed by an application of copolymer as a field dressing. 
     A particular advantage of the fertilizer compositions of the invention is the enhanced availability of sulfate and other ions when applied to soil. Further, the fertilizer compositions generate continuing quantities of these nutrients. This results from the fact that the highly acidic copolymer reacts in the soil with calcium or magnesium sulfate to yield sulfuric acid plus a partial calcium or magnesium salt of the copolymer formed in situ. The so-formed partial copolymer salt then reacts in the soil to generate further quantities of the acid form of the copolymer and sulfates. Thus, a cyclic reaction is generated in the soil, which provides sustaining quantities of plant nutrients. Such a beneficial result arises from the use of the low pH copolymers, as compared with copolymers of higher pH. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Maleic-itaconic copolymers are described in U.S. Pat. Nos. 6,515,090 and 6,706,837, both fully and completely incorporated by reference herein, with special reference to the operative examples of the &#39;837 patent. In general, the copolymers should desirably contain from about 10-90% by weight maleic moieties (more preferably from about 25-75% by weight), and correspondingly from about 90-10% by weight itaconic moieties (more preferably from about 75-25% by weight). One particularly preferred copolymer of this class is a 40% by weight solids aqueous copolymer dispersion of substantially equimolar amounts of itaconic and maleic anhydride moieties and having a pH of about 0.5. 
     The most preferred polymers of the invention are reaction products of the following maleic acid and itaconic monomers: 
                                
where X is individually and respectively taken from the group consisting of cations, preferably hydrogen, Na, K, and mixtures thereof, and the m:n ratio ranges from about 99:1 to about 1:99. In order to obtain the desirable low pH values for aqueous dispersions of the copolymer, the copolymer may be used in acid form (i.e., all or essentially all X moieties are H), or partial salts wherein the preponderant amount of X moieties are H and some of the X moieties are Na, K, or mixtures thereof.
 
     This reaction product of the above-described reactants has the general formula: 
                                
where X is as defined above and p from about 10 to 500.
 
     The following examples set forth preferred fertilizer compositions of the invention. It is to be understood, however, that these examples are provided by way of illustration and nothing therein should be taken as a limitation upon the overall scope of the invention. 
     EXAMPLE 1 
     In this example, the preferred copolymer of the invention was used to coat gypsum, and the resultant improved solubility of the coated gypsum was evaluated. The coating material was an acid form aqueous copolymer (pH 0.5) having approximately 40% by weight solids and made up of substantially equimolar amounts of maleic and itaconic moieties. The copolymer was applied at two levels, namely 1 gallon per ton of gypsum and 1½ gallons per ton of gypsum. 
     Commercial grade agricultural gypsum pellets or granules were coated with the aqueous copolymer dispersion using a standard rotating cement mixer. The gypsum was first placed within the mixer, and thereafter the copolymer was applied in sufficient quantities to substantially completely coat all of the gypsum pellets. The rotation of the mixer was continued until the pellets were dry to touch. The dried coated pellets included about 0.2% or 0.3% by weight dried copolymer residue thereon, based upon the total weight of the fertilizer compositions taken as 100% by weight. 
     Next, average weight of uniformly sized coated gypsum pellets was determined. Triplicate samples were then prepared, each sample containing ten of the weighed pellets for the control (no copolymer), and coated pellets (0.2 and 0.3% by weight dried copolymer residue). Each sample was placed in a flask containing 5 ml of deionized water, and the respective sample sets were shaken for periods of five, ten, and twenty minutes using a standard laboratory rotary shaker. Next, each shaken sample was filtered to remove the pellets, and the liquid filtrate sample was analyzed in a Varian ICP-MS (inductively coupled plasma-mass spectrometer) to determine the concentrations of sulfate sulfur and Ca therein. The pH of each liquid sample was also determined. 
     The following Table 1 sets forth the results of this study. 
     
       
         
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Dried Polymer 
                 5 Minute Extraction (Avg.) 
                 10 Minute Extraction (Avg.) 
                 20 Minute Extraction (Avg.) 
               
             
          
           
               
                 Concentration 
                 % S 
                 % Ca 
                 pH 
                 % S 
                 % Ca 
                 pH 
                 % S 
                 % Ca 
                 pH 
               
               
                   
               
             
          
           
               
                 None 
                 2.15 
                 3.63 
                 6.4 
                 1.49 
                 2.33 
                 6.4 
                 2.01 
                 3.13 
                 6.3 
               
               
                 0.2% 
                 2.03 
                 3.14 
                 5.9 
                 1.89 
                 2.99 
                 6.0 
                 2.58 
                 3.99 
                 6.1 
               
               
                 0.3% 
                 1.78 
                 2.86 
                 5.7 
                 1.94 
                 2.91 
                 6.0 
                 2.18 
                 3.46 
                 6.0 
               
               
                 p &gt; f 
                 0.47 
                 0.28 
                 &lt;0.01 
                 0.19 
                 0.23 
                 0.08 
                 0.16 
                 0.34 
                 0.10 
               
               
                 LSD (0.10)   
                 NS 
                 NS 
                 0.2 
                 0.47 
                 NS 
                 0.3 
                 0.51 
                 NS 
                 0.2 
               
               
                   
               
             
          
         
       
     
     EXAMPLE 2 
     In this study, the same copolymer coated gypsum pellets described in Example 1 were used. However, in this example, three sets of quadruplicate samples of the 0.2% by weight and 0.3% by weight compositions, and three sets of quadruplicate uncoated control samples, were prepared. Each such sample contained approximately 1 gram of the coated or uncoated pellets. These samples were each placed within 10 ml of deionized water and shaken using the laboratory shaker for periods of 5, 10, and 20 minutes. Thereafter the samples were filtered and the concentrations of Ca and sulfate sulfur in the filtered liquid were determined using the ICP-MS. pH values were also determined. The following Table 2 sets forth the results of this study. 
                                         TABLE 2                           % by wt   % by wt               Sample/Shaker Time   Ca   Sulfate Sulfur   pH                           Control/5 minutes   0.96   0.82   6.46           Control/5 minutes   0.96   0.82   6.62           Control/5 minutes   0.8    0.70   6.74           Control/5 minutes   0.94   0.82   6.65           0.2%/5 minutes   1.04   0.90   5.83           0.2%/5 minutes   0.94   0.80   5.75           0.2%/5 minutes   0.85   0.73   6.10           0.2%/5 minutes   1.21   1.02   5.83           0.3%/5 minutes   0.98   0.84   5.79           0.3%/5 minutes   0.99   0.87   5.76           0.3%/5 minutes   1.06   0.92   5.67           0.3%/5 minutes   1.05   0.92   5.66           Control/10 minutes   0.90   0.81   6.65           Control/10 minutes   0.86   0.77   6.72           Control/10 minutes   0.85   0.77   6.77           Control/10 minutes   1.00   0.81   6.71           0.2%/10 minutes   1.17   1.01   6.03           0.2%/10 minutes   0.90   0.80   6.16           0.2%/10 minutes   1.14   1.01   5.94           0.2%/10 minutes   0.93   0.84   5.94           0.3%/10 minutes   1.01   0.88   5.93           0.3%/10 minutes   1.12   1.00   5.76           0.3%/10 minutes   1.28   1.12   5.65           0.3%/10 minutes   1.25   1.11   5.71           Control/20 minutes   0.93   0.86   6.75           Control/20 minutes   0.95   0.87   6.80           Control/20 minutes   0.83   0.79   6.85           Control/20 minutes   0.85   0.80   6.88           0.2%/20 minutes   0.95   0.89   6.34           0.2%/20 minutes   1.11   1.01   6.23           0.2%/20 minutes   1.17   1.05   6.11           0.2%/20 minutes   1.36   1.23   6.17           0.3%/20 minutes   0.92   0.85   6.03           0.3%/20 minutes   1.11   0.98   6.09           0.3%/20 minutes   1.05   0.95   6.15           0.3%/20 minutes   0.93   0.85   5.97                        
The average sulfate sulfur and Ca values and statistical analyses were:
 
                                                 Control/5 minutes   0.79           0.2%/5 minutes   0.86           0.3%/5 minutes   0.89           % S p &gt; f   0.24           % S LSD (0.10)     0.10           % Ca p &gt; f   0.29           % Ca LSD (0.10)     0.13           Control/10 minutes   0.81           0.2%/10 minutes   0.92           0.3%/10 minutes   1.03           % S p &gt; f   0.07           % S LSD (0.10)     0.14           % Ca p &gt; f   0.06           % Ca LSD (0.10)     0.17           Control/20 minutes   0.83           0.2%/20 minutes   1.04           0.3%/20 minutes   0.91           % S p &gt; f   0.06           % S LSD (0.10)     0.14           % Ca p &gt; f   0.07           % Ca LSD (0.10)     0.17                        
These data are statistically significant, as noted above, and demonstrate that the solubility of commercial grade granular or pelleted gypsum is enhanced by the copolymers of the invention. As such, the compositions hereof provide better and accelerated plant availability of sulfate and calcium. The quick-acting gypsum fertilizer composition made through use of the copolymer coatings provides an attractive S fertilizer and a more available source of soluble Ca for soil amendment (e.g., in peanut production where supplemental Ca is sometimes important), or where high concentrations of Na producing undesirable soil physical conditions may be replaced by the soluble Ca provided with the present fertilizer composition.
 
     EXAMPLE 3 
     In this series of tests, the preferred polymer-coated gypsum fertilizer was Example 1 was tested with bermudagrass to ascertain improvements in yield and quality of product. 
     Materials and Methods 
     Four repetitions of five plots each measuring 5′×20′ were randomly assigned on an established Tifton 44 bermudagrass pasture in Lafayette County, Arkansas. The soil type, Severn silt loam, had a pH of 7.6. The plots were on a deep, well drained, gently undulating soil located on the flood plain along the Red River. Slopes were 0-3%. Soil tests were taken before treatments were applied. Phosphorus (P) and potassium (K) were adequate at 75.4 ppm and 146.8 ppm, respectively. 
     Initial plot treatments were (1) a negative control (NC), no sulfur added; (2) uncoated gypsum (CaSO 4 ) at a rate of 20 lbs S/acre; (3) 0.2% polymer coating on gypsum applied at a rate of 20 lbs S/acre; (4) 0.3% polymer coating on gypsum applied at a rate of 20 lbs S/acre and (5) ammonium sulfate ((NH 4 )2SO 4 ) applied at a rate of 87 lbs/acre (21 lbs S/A). Ammonium nitrate (NH 4 NO 3 ) was also applied to all plots, both initially and on each harvest date at a rate of 96 lbs/acre, except for the ammonium sulfate plots. In the latter, ammonium nitrate was applied at 50 lbs/acre due to the N contribution from the ammonium sulfate. 
     The plots were harvested at four week intervals using a Craftsman 6.75 horsepower push mower with clipping bag to collect grass samples. Harvest swaths were 3″×22″×20′. After samples were collected, total sample weights were recorded, a grab sample was taken and weighed for fresh weight and dry weight to determine dry matter content (DM) and to compute yield per acre. 
     The plot samples were analyzed for feed quality. Specifically, the samples were dried at 60° C. and ground with a Wiley Mill through a 2 mm stainless steel screen, then scanned using the FOSS NIR 5000 to determine quality of the bermudagrass. Statistical analysis was performed using a randomized complete block design in SAS (8). 
     A second set of dry ground samples was analyzed for complete inorganic content. Using the dry weight and nutrient concentrations, nutrient uptake per acre was computed. 
     Results and Discussion 
     These field studies indicate that polymer coating of gypsum was most effective in the first cutting following application. Polymer coatings of 0.2 and 0.3% in the first cutting increased yield by approximately 19.5% over the no-polymer gypsum when evaluated as a source of sulfur for hybrid bermudagrass. There was no advantage for the higher polymer concentration. 
     In the second cutting, the lower polymer coating did not increase bermudagrass yield over the uncoated control but the higher 0.3% coating did provide a 10% yield increase. 
     Understandably, the coated gypsum did not perform as well as ammonium sulfate as a S source in the first cutting. However, by the second cutting the polymer-coated gypsum was more effective than the highly soluble ammonium sulfate suggesting luxury consumption of S by the crop in the first cutting when ammonium sulfate was the S source. On the other hand, S availability was extended by the slower solubility of the polymer-coated gypsum. 
     These studies confirm that the polymer coating can and does enhance S availability from granular gypsum, thereby increasing plant yields under S deficient soil conditions. The following Table 3 shows the yield results of this series of tests. The bermudagrass samples were also assayed for sulfur uptake, as set forth in Table 4 below. 
     
       
         
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 3 
               
             
             
               
                   
                   
               
               
                   
                 Cutting 1 
                 Cutting 2 
                 Total 
               
             
          
           
               
                 Treatment 
                 lb/A 
                 *% inc 
                 lb/A 
                 *% inc 
                 lb/A 
               
               
                   
               
               
                 No gypsum control 
                 2465 
                 — 
                 1960 
                 — 
                 4424 
               
               
                 Uncoated gypsum 
                 2583 
                 — 
                 2087 
                 — 
                 4671 
               
               
                 Gypsum + 0.2% polymer 
                 3089 
                 19.6 
                 2082 
                 −0.2 
                 5170 
               
               
                 Gypsum + 0.3% polymer 
                 3088 
                 19.5 
                 2193 
                 10.1 
                 5232 
               
               
                 Am. sulfate 
                 3222 
                 — 
                 2043 
                 — 
                 5340 
               
             
          
           
               
                 p &gt; f 
                 0.005 
                 0.90 
                 — 
               
               
                 LSD .10   
                 340 
                 NS 
                  580 
               
               
                   
               
               
                 *% increase over uncoated gypsum 
               
             
          
         
       
     
     
       
         
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
             
             
               
                   
                   
               
               
                   
                 Cutting 1 
                 Cutting 2 
                 Total 
               
             
          
           
               
                   
                   
                 S Uptake 
                   
                 S Uptake 
                 S Uptake 
               
               
                 Treatment 
                 % S 
                 (lb/A) 
                 % S 
                 (lb/A) 
                 (lb/A) 
               
               
                   
               
             
          
           
               
                 No gypsum 
                 0.13 
                 3.20 
                 0.18 
                 3.53 
                 6.73 
               
               
                 Uncoated gypsum 
                 0.15 
                 3.88 
                 0.21 
                 4.38 
                 8.26 
               
               
                 Gypsum + 0.2% 
                 0.12 
                 3.71 
                 0.19 
                 3.96 
                 7.67 
               
               
                 polymer 
               
               
                 Gypsum + 0.3% 
                 0.14 
                 4.29 
                 0.24 
                 5.20 
                 9.49 
               
               
                 polymer 
               
               
                 Am. sulfate 
                 0.25 
                 8.24 
                 0.25 
                 5.11 
                 13.35 
               
             
          
           
               
                 p &gt; f 
                 0.001 
                 0.005 
                 — 
               
               
                 LSD .10   
                 0.034 
                 0.030 
                 —