Combinations of active ingredients for inhibiting or controlling nitrification

Abstract

This patent describes nitrification inhibitors characterized by the fact that they contain as their active ingredients 1-hydro-1,2,4-triazole, a substituted 1-hydro-1,2,4-triazole, or their salts or metallic complexes, plus at least one other chemical compound, such as a substituted pyrazole, or its salts or metallic complexes, dicyanodiamide, guanyl thiocarbamide, thiocarbamide, ammonium rhodanide, or ammonium thiosulfate, where said combinations exhibit readily recognizable synergetic effects compared to the case where said chemical compounds are employed alone, and thus provide benefits in terms of better efficacies, reduced dosages, and/or cost savings.

Description

BACKGROUND OF THE INVENTION

The present invention concerns combinations of two or more active ingredients for inhibiting or controlling nitrification of ammonia in arable topsoil and subsoil.

Reduced nitrogen, such as that contained in ammonia, ammonium compounds, or nitramide, present in arable soil is rapidly transformed into nitrates via intermediate nitrite stages by bacterial action. The rates at which nitrification proceeds are largely determined by the temperatures, moisture contents, pH, and bacterial activities of the soils involved. A counteracting effect here is that, unlike the nitrogen of ammonia or ammonium compounds, that of nitrates will not be sorbed by the sorbing agents present in arable soil, and will thus either precipitate out and be washed away by surface runoff, or will end up being deposited in deep-lying strata extending down to the water table and below levels accessible to plants. Under adverse weather or soil conditions, runoff losses may exceed 20% of total available reduced nitrogen. To be added to these losses are denitrification losses due to reduction of nitrates formed by nitrification processes to gaseous compounds under anaerobic conditions, losses that may reach comparable levels.

Employing suitable chemicals to inhibit or control nitrification can promote utilization of nitrogen fertilizers by plants. Moreover, this approach provides further benefits in that it reduces nitrate concentrations in ground water and surface runoff, and counteracts nitrate enrichment in cultivated plants, particularly forage crops.

In addition to substituted pyrazoles (U.S. Pat. No. 3,494,757, DD 133088), other known solutions to these problems involve employing dicyanodiamide (DCD) (DE 2702284, DE 2714601), guanyl thiocarbamide (JP 7301138), thiocarbamide (DE 2051935), 1,2,4-triazole, 4-amino-1,2,4-triazole (JP 7104135), or other triazole derivatives (U.S. Pat. No. 3,697,244, U.S. Pat. No 3,701,645).

Combinations of active ingredients supposedly superior to the above-mentioned compounds when employed alone have also been recommended. Among those combinations worth noting here are admixtures of pyrazoles and DCD (DD 222471) or guanyl thiocarbamide (DD 247894), admixtures of 4-amino-1,2,4-triazole (ATC) and DCD (SU 1137096), and amalgams of, e.g., ATC in carbamide/thiocarbamide or carbamide/DCD-mixtures (DD 227957). Employing admixtures of dicyanodiamide and ammonium thiosulfate has also been recommended (DE 3714729).

The disadvantages of these known nitrification inhibitors are their low efficacies, which implies that large dosages will be required, volatilities or instabilities that are too high to allow them to be of much benefit in practical applications, or decomposition rates that are too rapid for the types of applications involved. Moreover, although some of these inhibitors retard nitrification to acceptable degrees, their efficacies are severely reduced by "incompatibility reactions" with several types of fertilizers.

SUMMARY OF THE INVENTION

The object of the present invention is identifying combinations of active ingredients suitable for employment in mineral and organic nitrogen fertilizers that will have synergetic effects on inhibition of nitrification, and will thus be more beneficial than either employing the compounds involved alone, or employing any of those combinations mentioned above.

Surprisingly, it has been found that when employed for inhibiting or controlling nitrification in arable topsoil and subsoil, combinations of active ingredients containing 1-hydro-1,2,4-triazole, a substituted 1-hydro-1,2,4-triazole, or their salts or metallic complexes, plus at least one other chemical compound, such as a substituted pyrazole, or its salts or coordination compounds, dicyanodiamide, guanyl thiocarbamide, thiocarbamide, ammonium rhodanide, or ammonium thiosulfate, exhibit marked synergetic effects, and are thus are more effective than any of these compounds when employed alone.

The ingredients of the combinations of the present invention may be admixed in proportions ranging from 0.5: 99.5 to 99.5: 0.5. Where combinations contain more than two ingredients, mixing ratios may be arbitrarily adjusted for each ingredient involved.

The combinations of the present invention are beneficial in the sense that they provide enhanced long-term effects, i.e., nitrification is inhibited over extended periods, and they thus contribute to providing that nitrogen released by nitrogen fertilizers will be better utilized, and that these fertilizers will therefore be more effective, even where lower dosages are employed. A related effect of employing such combinations is that cultivated plants have been observed to yield more biomass.

PREFERRED EMBODIMENTS OF THE INVENTION

The combinations of active ingredients of the present invention may be employed admixed with liquid or solid mineral or organic fertilizers containing nitramide or ammonium compounds, in which case they should be applied in dosages ranging from 0.5 kg/ha to 20 kg/ha.

The following examples will serve to clarify the present invention, but shall not be construed as imposing any restrictions on same. Table 1 lists a selection of those triazoles and their salts and metallic complexes employed as basic ingredients of those combinations studied, while Table 2 lists several of the other ingredients that were admixed with said triazoles.

TABLE 1______________________________________Symbol Designation/Chemical Formula______________________________________Tr 1-hydro-1,2,4-triazoleTr .times. HCl 1-hydro-1,2,4-triazole .times. HClHMT 1-hydroxy-methyl-1,2,4-triazole .times. HClNa--Tr 1-sodium-1,2,4-triazolateFe--Tr �Fe(Tr).sub.6 !Cl.sub.3GTr 1-guanyl-1,2,4-triazole .times. HClCTS �Cu(Tr).sub.2 !SO.sub.4 .times. 2H.sub.2 OMT �Mn(Tr).sub.4 !Cl.sub.2______________________________________ TABLE 2______________________________________Symbol Designation/Chemical Formula______________________________________GTH guanyl thiocarbamideTH thiocarbamideAR ammonium rhodanideDCD dicyanodiamideATS ammonium thiosulfateMP 3-methylpyrazoleCMP 1-carbamyl-3-methylpyrazoleGMP 1-guanyl-3-methylpyrazole .times. HClMg--MP Mg-3-methylpyrazolateZn--MP �Zn(MP).sub.2 !SO.sub.4GZC (GMPH).sub.2 ZnCl.sub.4GM Mg(GMP).sub.2 Cl.sub.2 .times. H.sub.2 O______________________________________

The results of employing such combinations in the examples presented below were all obtained using the same methodology.

EXAMPLES

The combinations of the present invention, along with carbamide (urea), which served as a source of nitrogen, were admixed with a sandy loam similar to humus in the concentrations listed in the following tables (all concentrations stated in ppm are by weight, referred to the total weight of soil involved), brought up to 50% of their maximum moisture-retention capacities, and then vigorously mixed. The concentration of elemental nitrogen employed was 10 mg/100 g of soil. Soil samples prepared in this fashion were placed in plastic bottles, the bottles sealed, incubated at 20.degree. C., and the resultant rates of nitrate formation and declines in ammonia concentrations monitored.

Percentage nitrification inhibitions were computed from the relation ##EQU1## where

K is the nitrate concentration in soil samples that were admixed with nitrogen fertilizer, but had no active ingredients added,

A is the nitrate concentration in soil samples that were admixed with both nitrogen fertilizer and active ingredients, and

B is the nitrate concentration in soil samples that were admixed with neither nitrogen fertilizer nor active ingredients.

Values of t.sub.50, which are efficacy factors representing those time periods, expressed in days, that had elapsed until nitrification inhibitions had declined to 50% of their initial levels, were determined from nonlinear regressions applied to the temporal degradation data

Values of t.sub.50 obtained in this fashion were subjected to Logit-Probit transforms (which linearize effect-dosage curves) in order to assess the effects of the combinations involved based on the independence model of Groeger, et al, �Pharmazle 36 (1981), pp. 81-87!, which incorporates a generalization of the theories of Gowing �Weeds 8 (1960), pp. 379-391! and of Colby �Weeds 15 (1967), pp. 20-22!, according to which the effects of such combinations were regarded as synergetic if they were better than those of the ingredients involved when employed alone, or if the dosages required to yield given effect; were less than those predicted by the independence model.

Example 1

Combinations of 1-hydro-1,2,4-triazole (Tr) and dicyanodiamide (DCD)

Values of t.sub.50 were computed and compared for cases where Tr alone, DCD alone, and admixtures of the two were employed, following the methodology referred to above.

TABLE 3a______________________________________Values of t.sub.50 for Tr alone, DCD alone, and admixtures of the two.1-Hydro-1,2,4-Triazole DicyanodiamideConcentration Concentration Tr:DCD t.sub.50�ppm! �ppm! Mixing Ratio �days!______________________________________0.096 5.50.227 14.00.545 30.00.909 41.51.25 46.02.0 50.03.0 52.35.0 57.0 1.25 10.0 2.0 14.3 3.0 17.6 3.846 19.7 5.0 22.0 5.882 23.6 8.333 27.3 9.091 28.4 10.0 29.65.0 5.0 50:50 73.83.0 3.0 58.22.0 2.0 57.11.25 1.25 52.51.667 8.333 17:83 106.61.0 5.0 71.50.667 3.333 53.70.417 2.083 37.10.909 9.091 9:91 111.80.545 5.445 69.40.364 3.636 45.50.227 2.273 28.70.25 3.75 6:94 37.30.156 2.344 23.90.19 3.81 5:95 32.10.119 2.38 22.20.385 9.615 4:96 73.50.231 5.769 41.50.154 3.846 29.60.096 2.404 21.30.196 9.804 2:98 48.10.118 5.882 31.2______________________________________ TABLE 3b______________________________________Percentage savings of active ingredients and incrementalimprovements in efficacies, relative to those predictedby the independence model (IM). Con-Tr:DCD centration Empirically Efficacy DosageMixing in Host Soil Determined Predicted by Efficacy SavingsRatio �ppm! Efficacy the IM Increment �%!______________________________________50:50 10 74 82 -8 -53 6 58 72 -14 -68 4 57 61 -4 -17 2.5 52 48 4 1417:83 10 100 64 36 -- 6 71 50 21 55 4 54 39 14 42 2.5 37 29 8 319:91 10 100 53 47 -- 6 69 40 29 69 4 45 31 14 47 2.5 29 23 6 296:94 4 47 37 10 36 2.5 30 28 2 125:95 4 40 34 6 25 2.5 28 26 2 114:96 10 92 52 40 -- 6 52 61 9 40 4 37 33 4 21 2.5 27 25 2 112:98 10 60 46 14 48 6 39 36 3 17______________________________________

Example 2

Combinations of 1-hydro-1,2,4-triazole (Tr) and guanyl thiocarbamide (GTH)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 4a______________________________________Values of t.sub.50 for Tr alone, GTH alone, and admixtures of the two.1-Hydro-1,2,4-Triazole Guanyl ThiocarbamideConcentration Concentration Tr:GTH t.sub.50�ppm! �ppm! Mixing Ratio �days!______________________________________0.096 5.50.227 14.00.545 30.00.909 41.51.25 46.02.0 50.03.0 52.35.0 57.0 2.0 1.0 4.0 9.3 6.0 18.4 8.0 28.0 10.0 37.4 12.0 47.25.0 5.0 50:50 63.42.5 2.5 53.81.25 1.25 40.30.909 9.091 9:91 81.80.545 5.445 70.30.227 2.273 19.20.385 9.615 4:96 60.50.231 5.769 35.40.154 3.846 25.10.196 9.804 2:98 49.40.118 5.882 28.9______________________________________ TABLE 4b______________________________________Percentage savings of active ingredients and incrementalimprovements in efficacies, relative to those predictedby the independence model (IM). Con-Tr:GTH centration Empirically Efficacy DosageMixing in Host Soil Determined Predicted by Efficacy SavingsRatio �ppm! Efficacy the IM Increment �%!______________________________________50:50 10 95 95 0 -4 5 81 86 -6 -29 2.5 68 68 0 19:91 10 100 74 26 89 6 100 53 47 93 2.5 29 21 8 234:96 10 91 59 32 62 6 54 38 16 32 4 38 24 14 342:98 10 74 51 23 44 6 43 32 11 27______________________________________

Example 3

Combinations of 1-hydro-1,2,4-triazole (Tr) and thiocarbamide (TH)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 5a______________________________________Values of t.sub.50 for Tr alone, TH alone, and admixtures of the two.1-Hydro-1,2,4-Triazole ThiocarbamideConcentration Concentration Tr:TH t.sub.50�ppm! �ppm! Mixing Ratio �days!______________________________________0.1 5.80.25 14.30.5 29.01.0 42.12.0 49.13.0 51.95.0 56.2 2.0 6.5 4.0 8.5 8.0 10.5 10.0 12.6 16.0 17.33.0 3.0 50:50 58.22.0 2.0 54.80.909 9.091 9:91 49.90.545 5.445 42.20.227 2.273 27.10.385 9.615 4:96 37.10.154 3.846 24.70.096 2.404 14.90.196 9.804 2:98 26.40.118 5.882 18.0______________________________________ TABLE 5b______________________________________Percentage savings of active ingredients and incrementalimprovements in efficacies, relative to those predictedby the independence model (IM). Con-Tr:TH centration Empirically Efficacy DosageMixing in Host Soil Determined Predicted by Efficacy SavingsRatio �ppm! Efficacy the IM Increment �%!______________________________________50:50 6 87 80 7 40 4 82 72 10 429:91 10 75 63 12 39 6 63 49 14 41 2.5 40 28 12 424:96 10 55 48 8 24 4 37 26 11 40 2.5 22 18 5 252:98 10 40 38 1 5 6 27 27 0 2______________________________________

Example 4

Combinations of 1-hydro1,2,4-triazole (Tr) and ammonium rhodanide (AR)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 6a______________________________________Values of t.sub.50 for Tr alone, AR alone, and admixtures of the two.1-Hydro-1,2,4-Triazole Ammonium Rhodanide Tr:ARConcentration Concentration Mixing t.sub.50�ppm! �ppm! Ratio �days!______________________________________0.096 5.50.227 14.00.545 30.00.909 41.51.25 46.02.0 50.03.0 52.35.0 57.0 2.0 3.1 4.0 6.3 8.0 8.5 10.0 9.3 16.0 11.93.0 3.0 50:50 56.92.0 2.0 52.51.25 1.25 46.30.545 5.445 9:91 61.60.364 3.636 40.80.227 2.273 35.10.19 3.81 5:95 33.70.119 2.38 25.70.196 9.804 2:98 29.10.118 5.882 22.4______________________________________ TABLE 6b______________________________________Percentage savings of active ingredients and incrementalimprovements in efficacies, relative to those predictedby the independence model (IM). Con-Tr:AR centration Empirically Efficacy DosageMixing in Host Soil Determined Predicted by Efficacy SavingsRatio �ppm! Efficacy the IM Increment �%!______________________________________50:50 6 57 57 0 -2 4 52 49 3 15 2.5 46 39 7 299:91 6 62 30 32 79 4 41 24 17 62 2.5 35 17 18 685:95 4 34 18 16 66 2.5 26 12 14 662:98 10 29 22 7 36 6 22 16 6 41______________________________________

Example 5

Combinations of 1-hydroxy-methyl-1,2,4-triazole.times.HCl(HMT) and guanyl thiocarbamide (GTH)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 7a______________________________________Values of t.sub.50 for HMT alone, GTH alone, and admixtures of the two.1-Hydroxy-Methyl-1,2,4-Triazole .times. HCl Guanyl ThiocarbamideConcentration Concentration HMT:GTH t.sub.50�ppm! �ppm! Mixing Ratio �days!______________________________________0.25 14.80.5 22.90.75 29.71.0 37.42.0 44.15.0 50.07.5 57.1 1.0 1.1 2.0 3.4 4.0 10.2 8.0 29.1 10.0 38.25.0 1.0 83:17 53.12.5 0.5 44.21.25 0.25 38.73.0 3.0 50:50 52.11.5 1.5 43.11.0 5.0 17:83 56.90.5 2.5 29.10.545 5.445 9:91 64.90.273 2.727 28.30.286 5.714 5:95 61.70.143 2.857 23.90.118 5.882 2:98 39.4______________________________________ TABLE 7b______________________________________Percentage savings of active ingredients and incrementalimprovements in efficacies, relative to those predictedby the independence model (IM).HMT: Con-GTH centration Empirically Efficacy DosageMixing in Host Soil Determined Predicted by Efficacy SavingsRatio �ppm! Efficacy the IM Increment �%!______________________________________83:17 6 80 87 -7 -50 3 66 73 -7 -32 2.5 58 54 4 1150:50 6 78 80 -2 -10 3 65 62 3 817:83 6 85 59 26 59 3 44 36 8 219:91 6 97 47 50 88 3 42 26 16 425:95 6 92 38 56 85 3 36 20 16 472:98 6 59 31 28 59______________________________________

Example 6

Combinations of 1sodium-1,2,4-triazolate (Na-Tr) and dicyanodiamide (DCD)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 8a______________________________________Values of t.sub.50 for Na--Tr alone, DCD alone, and admixtures of thetwo.1-Sodium-1,2,4-Triazolate DicyanodiamideConcentration Concentration Na--Tr:DCD t.sub.50�ppm! �ppm! Mixing Ratio �days!______________________________________0.25 9.70.5 21.40.75 26.11.0 31.91.5 33.72.0 38.45.0 41.8 1.0 12.4 2.0 22.1 4.0 26.1 6.0 29.6 10.0 38.15.0 1.0 83:17 52.12.5 0.5 46.73.0 3.0 50:50 60.11.5 1.5 51.91.0 5.0 17:83 73.20.5 2.5 51.40.545 5.445 9:91 64.20.273 2.727 42.90.231 5.769 4:96 47.90.115 2.885 35.1______________________________________ TABLE 8b______________________________________Percentage savings of active ingredients and incrementalimprovements in efficacies, relative to those predictedby the independence model (IM).Na--Tr: Con-DCD centration Empirically Efficacy DosageMixing in Host Soil Determined Predicted by Efficacy SavingsRatio �ppm! Efficacy the IM Increment �%!______________________________________83:17 6 78 79 -1 -5 3 70 65 5 2050:50 6 90 77 13 55 3 78 61 17 5117:83 6 100 68 32 -- 3 77 50 27 669:91 6 96 63 33 -- 3 64 45 19 534:96 6 72 57 15 47 3 53 40 13 41______________________________________

Example 7

Combinations of 1-hydro-1,2,4-triazole (Tr) and 3-methylpynizole (MP)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 9a______________________________________Values of t.sub.50 for Tr alone, MP alone, and admixtures of the two1-Hydro-1,2,4-Triazole 3-Methylpyrazole Tr:MP t.sub.50Concentration �ppm! Concentration �ppm! Mixing Ratio �days!______________________________________0.1 5.30.25 14.90.5 27.80.75 36.81.0 41.91.5 48.73.0 56.9 0.1 9.1 0.25 24.5 0.5 43.6 0.656 46.3 1.0 48.7 2.0 52.31.0 1.0 50:50 95.60.5 0.5 72.71.818 1.182 91:9 69.80.909 0.091 51.71.923 0.077 96:4 59.80.962 0.038 42.80.077 1.923 4:96 61.00.038 0.962 52.4______________________________________ TABLE 9b__________________________________________________________________________Percentage savings of active ingredients and incremental improvements inefficacies, relative to these predicted by the independence model (IM) Concentration Empirically Efficacy DosageTr:MP in Host Soil Determined Predicted by Efficacy SavingsMixing Ratio �ppm! Efficacy the IM Increment �%!__________________________________________________________________________50:50 2 100 90 10 86 1 100 74 26 9391:9 2 100 83 17 88 1 77 64 13 3696:4 2 90 81 9 40 1 64 63 1 5 4:96 2 91 88 3 27 1 79 74 5 18__________________________________________________________________________

Example 8

Combinations of �Cu(Tr).sub.2 !SO.sub.4 .times.2H.sub.2 O hydrated cuprotriazole-sulfate complex (CTS) and (GMPH).sub.2 ZnCl.sub.4 1-guanyl-3-methylpyrazoline-chlorozincate complex (GZC)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 10a______________________________________Values of t.sub.50 for CTS alone, GZC alone, and admixtures of the twoCTS-Concentration GZC-Concentration CTS:GZC t.sub.50�ppm! �ppm! Mixing Ratio �days!______________________________________0.1 1.90.25 4.90.5 11.61.2 27.01.8 36.12.5 43.1 0.25 9.5 0.5 19.1 0.75 26.8 1.5 43.3 3.0 59.11.0 1.0 50:50 77.20.5 0.5 53.60.25 0.25 21.91.818 0.182 91:9 45.90.909 0.091 27.80.182 1.818 9:91 53.60.091 0.909 30.0______________________________________ TABLE 10b__________________________________________________________________________Percentage savings of active ingredients and incremental improvements inefficacies, relative to those predicted by the independence model (IM) Concentration Empirically Efficacy DosageCTS:GZC in Host Soil Determined Predicted by Efficacy SavingsMixing Ratio �ppm! Efficacy the IM Increment �%!__________________________________________________________________________50:50 2 100 72 28 84 1 80 42 38 61 0.5 33 19 14 3791:9 2 69 64 5 14 1 42 36 6 13 9:91 2 80 74 5 16 1 45 51 -5 -15__________________________________________________________________________

Example 9

Combinations of 1-hydro-1,2,4-triazole (Tr), dicyanodiamide (DCD), and ammonium rhodanide (AR)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 11a__________________________________________________________________________Values of t.sub.50 for Tr alone, DCD alone, AR alone, and admixtures ofall threeTr-Concentration DCD-Concentration AR-Concentration Tr:DCD:AR t.sub.50�ppm! �ppm! �ppm! Mixing Ratio �days!__________________________________________________________________________0.096 5.50.227 13.80.545 30.20.909 41.51.25 46.02.0 50.13.0 52.35.0 57.0 1.25 10.1 2.0 14.3 3.0 17.6 3.846 19.7 5.0 22.1 5.882 23.6 8.333 27.4 10.0 29.6 2.0 2.8 4.0 6.3 8.0 8.5 10.0 9.3 16.0 11.90.833 4.167 0.833 14.3:71.4:14.3 67.10.5 2.5 0.5 52.40.385 3.846 0.769 7.7:76.9:15.4 58.90.231 2.308 0.462 37.70.192 3.846 0.962 3.8:77:19.2 45.70.115 2.308 0.575 34.7__________________________________________________________________________ TABLE 11b__________________________________________________________________________Percentage savings of active ingredients and incremental improvements inefficacies, relative to those predicted by the independence model (IM) Concentration Empirically Efficacy DosageTr:DCD:AR in Host Soil Determined Predicted by Efficacy SavingsMixing Ratio �ppm! Efficacy the IM Increment �%!__________________________________________________________________________14.3:71.4:14.3 5.83 100 67 33 -- 3.5 79 53 26 61 7.7:76.9:15.4 5.0 89 53 36 75 3.0 57 39 18 46 3.8:77:19.2 5.0 69 44 25 56 3.0 52 31 21 54__________________________________________________________________________

Example 10

Combinations of 1-hydro-1,2,4-triazole hydrochloride (Tr.times.HCl), guanyl thiocarbamide (GTH), and thiocarbamide (TH)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 12a__________________________________________________________________________Values of t.sub.50 for Tr .times. HCl alone, GTH alone, TH alone, andadmixtures of all threeTr .times. HCl- GTH-Concentration TH-Concentration Tr .times. HCl:GTH:TH t.sub.50Concentration �ppm! �ppm! �ppm! Mixing Ratio �days!__________________________________________________________________________0.15 5.00.3 11.50.75 28.41.5 41.33.0 48.94.5 52.1 2.0 1.9 4.0 9.5 8.0 28.1 10.0 37.0 16.0 60.1 2.0 6.3 4.0 8.7 8.0 10.9 10.0 13.0 16.0 18.10.115 2.308 0.577 3.8:77:19.2 17.90.231 4.615 1.155 44.80.115 1.422 1.422 3.8:48.1:48.1 11.90.231 2.885 2.885 37.90.231 1.155 4.615 3.8:19.2:77 27.80.5 2.0 0.5 17:66:17 53.10.5 1.25 1.25 16.6:41.7:41.7 39.90.188 1.875 0.937 6.3:62.5:31.2 21.30.375 3.75 1.875 47.1__________________________________________________________________________ TABLE 12b__________________________________________________________________________Percentage savings of active ingredients and incremental improvements inefficacies, relative to those predicted by the independence model (IM) Concentration Empirically Efficacy DosageTr .times. HCl:GTH:TH in Host Soil Determined Predicted by Efficacy SavingsMixing Ratio �ppm! Efficacy the IM Increment �%!__________________________________________________________________________ 3.8:77:19.2 3.0 27 16 11 36 6.0 67 35 32 57 3.8:48.1:48.1 3.0 19 12 7 28 6.0 57 30 27 51 3.8:19.2:77 6.0 42 25 17 40 17:66:17 3.0 81 33 48 7416.6:41.7:41.7 3.0 60 30 30 55 6.3:62.5:31.2 3.0 33 17 16 43 6.0 71 38 33 56__________________________________________________________________________

Example 11

Combinations of 1-guanyl-1,2,4triazole hydrochloride (GTr), dicyanodiamide (DCD), and thiocarbamide (TH)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 13a__________________________________________________________________________Values of t.sub.50 for GTr alone, DCD alone, TH alone, and admixtures ofall threeGTr-Concentration DCD-Concentration TH-Concentration GTr:DCD:TH t.sub.50�ppm! �ppm! �ppm! Mixing Ratio �days!__________________________________________________________________________1.4 27.52.14 37.54.3 47.38.5 49.210.0 55.2 1.0 8.9 2.0 14.2 3.0 17.1 5.0 22.3 8.0 26.8 10.0 30.1 2.0 6.3 4.0 8.7 8.0 10.9 10.0 13.0 16.0 18.10.192 3.840 0.968 3.8:76.8:19.4 43.80.308 6.160 1.54 61.70.192 2.404 2.404 3.8:48.1:48.1 37.40.308 3.846 3.846 57.80.192 0.968 3.840 3.8:19.4:76.8 27.90.308 1.540 6.160 32.7__________________________________________________________________________ TABLE 13b__________________________________________________________________________Percentage savings of active ingredients and incremental improvements inefficacies, relative to those predicted by the independence model (IM) Concentration Empirically Efficacy DosageGTr:DCD:TH in Host Soil Determined Predicted by Efficacy SavingsMixing Ratio �ppm! Efficacy the IM Increment �%!__________________________________________________________________________3.8:76.8:19.4 5.0 66 48 18 60 8.0 93 32 61 983.8:48.1:48.1 5.0 56 46 10 40 8.0 87 55 31 843.8:19.4:76.8 5.0 42 42 0 -1 8.0 49 51 -2 -10__________________________________________________________________________

Example 12

Combinations of 1-hydro-1,2,4-triazole (Tr), dicyanodiamide (DCD), and ammonium thiosulfate (ATS)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 14a__________________________________________________________________________Values of t.sub.50 for Tr alone, DCD alone, ATS alone, and admixtures ofall threeTr-Concentration DCD-Concentration ATS-Concentration Tr:DCD:ATS t.sub.50�ppm! �ppm! �ppm! Mixing Ratio �days!__________________________________________________________________________0.096 5.50.227 14.00.545 30.00.909 41.51.25 46.02.0 50.03.0 52.35.0 57.0 1.25 10.0 2.0 14.3 3.0 17.6 3.846 19.7 5.0 22.0 5.882 23.6 8.333 27.3 9.091 28.4 10.0 29.6 2.0 0 4.0 0 8.0 0 10.0 0 16.0 00.115 2.308 0.577 4:77:19 35.70.115 1.422 1.422 4:48:48 27.80.115 0.577 2.308 4:19:77 14.1__________________________________________________________________________ TABLE 14b__________________________________________________________________________Percentage savings of active ingredients and incremental improvements inefficacies, relative to those predicted by the independence model (IM) Concentration Empirically Efficacy DosageTr:DCD:ATS in Host Soil Determined Predicted by Efficacy SavingsMixing Ratio �ppm! Efficacy the IM Increment �%!__________________________________________________________________________4:77:19 3.0 53 35 18 554:48:48 3.0 42 30 12 424:19:77 3.0 21 24 -3 -20__________________________________________________________________________

Example 13

Combinations of �Fe(Tr).sub.6 !Cl.sub.3 ferrochlorotriazole complex (Fe--Tr), dicyanodiamide (DCD), and ammonium thiosulfate (ATS)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 15a__________________________________________________________________________Values of t.sub.50 for Fe-Tr alone, DCD alone, ATS alone, and admixturesof all threeFe-Tr-Concentration DCD-Concentration ATS-Concentration Fe-Tr:DCD:ATS t.sub.50�ppm! �ppm! �ppm! Mixing Ratio �days!__________________________________________________________________________0.072 3.90.163 10.30.39 21.20.65 29.40.9 33.31.44 35.72.15 39.44.0 42.96.0 49.9 0.5 4.8 1.0 9.3 2.5 15.4 5.0 22.6 7.5 27.3 10.0 32.8 2.0 0.09 4.0 0.09 6.0 0.1 8.0 0.1 10.0 0.12.0 2.0 2.0 33.3:33.3:33.3 54.61.0 1.0 1.0 45.80.231 4.615 1.154 3.8:77:19.2 51.20.115 2.308 0.577 35.80.231 2.885 2.885 3.8:48.1:48.1 44.90.115 1.422 1.422 28.80.231 1.154 4.615 3.8:19.2:77 29.50.115 0.577 2.308 16.70.545 4.364 1.091 9.1:72.7:18.2 57.90.273 2.182 0.545 39.7__________________________________________________________________________ TABLE 15b__________________________________________________________________________Percentage savings of active ingredients and incremental improvements inefficacies, relative to those predicted by the independence model (IM) Concentration Empirically Efficacy DosageFe-Tr:DCD:ATS in Host Soil Determined Predicted by Efficacy SavingsMixing Ratio �ppm! Efficacy the IM Increment �%!__________________________________________________________________________33.3:33.3:33.3 6.0 82 66 16 58 3.0 68 52 16 55 3.8:77:19.2 6.0 77 46 29 76 3.0 53 32 21 63 3.8:48.1:48.1 6.0 67 40 27 69 3.0 43 27 16 56 3.8:19.2:77 6.0 44 32 12 44 3.0 25 21 4 26 9.1:72.7:18.2 6.0 87 55 32 81 3.0 60 39 21 60__________________________________________________________________________

Example 14

Combinations of �Mn(Tr).sub.4 !Cl.sub.2 manganochlorotriazole complex (MT), Mg(GMP).sub.2 Cl.sub.2 .times.H.sub.2 O hydrated 1-guanyl-3-methyl pyrazole magnesium-chloride complex (GM), and dicyanodiamide (DCD)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 16a__________________________________________________________________________Values of t.sub.50 for MT alone, GM alone, DCD alone, and admixtures ofall threeMT-Concentration GM-Concentration DCD-Concentration MT:GM:DCD t.sub.50�ppm! �ppm! �ppm! Mixing Ratio �days!__________________________________________________________________________0.2 5.60.5 15.51.0 28.41.5 35.42.0 42.13.0 49.7 0.2 8.5 0.6 25.6 1.0 42.9 1.5 46.8 2.0 48.4 2.0 20.7 4.0 25.9 8.0 31.5 10.0 35.4 16.0 52.51.667 1.667 1.667 33.3:33.3:33.3 106.91.0 1.0 1.0 85.70.667 0.667 0.667 61.80.417 0.417 4.166 8.3:8.3:83.4 64.10.25 0.25 2.5 44.80.167 0.167 1.666 34.10.185 0.185 4.630 3.7:3.7:92.6 60.70.111 0.111 2.778 40.10.543 0.109 4.348 10.9:2.1:87 54.60.109 0.543 4.348 2.1:10.9:87 61.4__________________________________________________________________________ TABLE 16b__________________________________________________________________________Percentage savings of active ingredients and incremental improvements inefficacies, relative to those predicted by the independence model (IM) Concentration Empirically Efficacy DosageMT:GM:DCD in Host Soil Determined Predicted by Efficacy SavingsMixing Ratio �ppm! Efficacy the IM Increment �%!__________________________________________________________________________33.3:33.3:33.3 5.0 100 89 11 84 3.0 100 76 24 91 2.0 93 62 31 68 8.3:8.3:83.4 5.0 96 64 32 73 3.0 67 45 22 44 2.0 51 31 20 44 3.7:3.7:92.6 5.0 91 54 37 73 3.0 60 37 23 5010.9:2.1:87 5.0 82 59 23 52 2.1:10.9:87 5.0 92 63 29 67__________________________________________________________________________

Example 15

Combinations of 1-hydro-1,2,4-triazole (Tr) 3-methylpyrazole (MP), and guanyl thiocarbamide (GTH)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 17a__________________________________________________________________________Values of t.sub.50 for Tr alone, MP alone, GTH alone, and admixtures ofall threeTr-Concentration MP-Concentration GTH-Concentration Tr:MP:GTH t.sub.50�ppm! �ppm! �ppm! Mixing Ratio �days!__________________________________________________________________________0.1 5.80.25 14.30.5 29.00.75 42.11.0 49.11.5 51.93.0 56.2 0.1 9.1 0.25 24.5 0.5 43.6 0.656 46.3 1.0 48.7 2.0 52.3 2.0 1.0 4.0 9.3 6.0 18.4 8.0 28.0 10.0 37.4 12.0 47.21.667 1.667 1.667 33.3:33.3:33.3 112.11.0 1.0 1.0 105.70.227 0.227 4.546 4.5:4.5:91 73.40.136 0.136 2.727 47.80.119 0.119 4.762 2.4:2.4:95.2 44.90.071 0.071 2.857 29.3__________________________________________________________________________ TABLE 17b______________________________________Percentage savings of active ingredients and incrementalimprovements in efficacies, relative to those predictedby the independence model (IM).Tr:MP: Con-GTH centration Empirically Efficacy DosageMixing in Host Soil Determined Predicted by Efficacy SavingsRatio �ppm! Efficacy the IM Increment �%!______________________________________33.3: 5.0 100 98 2 6533.3: 3.0 100 92 8 6933.34.5:4.5: 5.0 100 56 44 9191 3.0 72 35 37 592.4:2.4: 5.0 67 40 27 4895.2 3.0 44 23 21 46______________________________________

Example 16

Combinations of 1-hydro-1,2,4-triazole (Tr), 3-methylpyrazole (MP), and dicyanodiamide (DCD)

The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.

TABLE 18a______________________________________Values of t.sub.50 for Tr alone, MP alone, DCD alone,and admixtures of all three.Tr- MP- DCD-Concentration Concentration Concentration Tr:MP:DCD t.sub.50�ppm! �ppm! �ppm! Mixing Ratio �days!______________________________________0.1 5.20.25 13.40.5 28.10.75 40.71.0 46.91.5 49.83.0 52.1 0.1 7.6 0.25 19.4 0.5 35.7 0.656 40.1 1.0 46.1 2.0 49.7 0.5 4.1 1.0 9.1 2.5 14.2 5.0 22.3 10.0 30.7 13.0 41.81.667 1.667 1.667 33.3:33.3: 112.91.0 1.0 1.0 33.3 102.30.227 0.227 4.546 4.5:4.5:91 79.40.136 0.136 2.727 52.90.119 0.119 4.762 2.4:2.4:95.2 57.10.071 0.071 2.857 41.8______________________________________ TABLE 18b______________________________________Percentage savings of active ingredients and incrementalimprovements in efficacies, relative to those predictedby the independence model (IM).Tr:MP: Con-DCD centration Empirically Efficacy DosageMixing in Host Soil Determined Predicted by Efficacy SavingsRatio �ppm! Efficacy the IM Increment �%!______________________________________33.3: 5.0 100 95 5 8233.3: 3.0 100 88 12 8933.34.5:4.5: 5.0 100 64 36 9491 3.0 79 47 32 632.4:2.4: 5.0 86 54 32 6695.2 3.0 63 38 25 54______________________________________

Claims

1. A method for inhibiting and controlling the nitrification of ammonium nitrogen in arable soils and substrates, comprising the step of applying to the soil an amount effective therefor of a composition comprising:

1 to 35% by weight of a first compound selected from the group consisting of 1H-1,2,4-triazole, substituted 1H-1,2,4-triazole and their salts, and metallic complexes thereof;

1 to 80% by weight of dicyanodiamide,

10 to 98% by weight of a third compound selected from the group consisting of guanyl thiocarbamide, thiocarbamide, ammonium rhodanide and ammonium thiosulfate,

applied in an amount from 0.2 to 4 percent by weight with respect to a nitrogen content of a fertilizer containing at least one component selected from the group consisting of ammonium and amide.

2. The method of claim 1 wherein the composition is administered at a dosage of at least 0.5 kg per hectare.

3. In combination,

1 to 35% by weight of a first compound selected from the group consisting of 1H-1,2,4-triazole, substituted 1H-1,2,4-triazole and their salts, and metallic complexes thereof;

1 to 80% by weight of dicyanodiamide, and

10 to 98% by weight of a third compound which is selected from the group consisting of guanyl thiocarbamide, thiocarbamide, ammonium rhodanide and ammonium thiosulfate, applied in an amount from 0.2 to 4 percent by weight with respect to a nitrogen content of a fertilizer containing at least one component selected from the group consisting of ammonium and amide, for use in inhibiting and controlling the nitrification of ammonium nitrogen in arable soils and substrates.