CA2182011C - Combination of active substances for inhibiting or regulating nitrification - Google Patents

Abstract

This patent describes nitrification inhibitors characterized by the fact tha t 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, dicyanodiamid e, 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 bene- fits in terms of better efficacies, reduced dosages, and/or cost savings.</S DOAB>

Description

1$2011 Combinations of active ingredients for inhibiting or controlling nitrification The present invemion 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 imermediate nitrite stages by bacterial action. The rates at which nitrification proceeds are largely determined by the tem-peratures, moisture contents, pH, and bacterial activities of the soils involved. A counteract-ing effect here is that, unlike the nitrogen of ammonia or ammonium compounds, that of nit-rates will not be sorbed by the sorbing agents present in arable soil, and will thus either pre-cipitate 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 nit-rogen 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 (US 3494757, 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 (US
3697244, US 3701645).
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 "incompat-ibility reactions" with several types of fertilizers.
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 com-pounds involved alone, or employing any of those combinations mentioned above.

221820 ~ 1 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-tri-azole, 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, guauyl 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.
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 com-pounds, 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-triazole Tr x HCl 1-hydro-1,2,4-triazole x HCl HIvIT 1-hydroxy-methyl-1,2,4-triazole x HCl Na-Tr 1-sodium-1,2,4-tri azolate Fe-Tr [Fe(Tr)6]Cl3 GTr 1-guanyl-1,2,4-triazole x HCl CTS [Cu(Tr~]SOQ x 2H20 M'I' fMn(Tr)4]Cla 2 l X3201 1 Table 2:
Symbol Desigoation/Chemical Formula GTH guanyl thiocarbamide TH thiocarbamide AR ammonium rhodanide DCD dicyaaodiamide ATS ammonium thiosulfate MP 3-methylpyrazole CMP 1-carbamyl-3-methylpyrazole GMP 1-guanyl-3-methylpyrazole x HCl Mg-MP Mg-3-methylpyrazolate Zn-MP [Zn(MP)2]S04 GZC (GMPH~ZnCl4 GM Mg(GMP~Cl2 x H20 The results of employing such combinations in the examples presented below were all obtained using the same methodology.
Eaamnles 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 cap-acities, and then vigorously mixed The concentration of elemental nitrogen employed was mg/100 g of soil. Soil samples prepared in this fashion were placed in plastic bottles, the bottles sealed, incubated at 20°C, and the resultant rates of nitrate formation and declines in ammonia concentrations monitored.
Percentage nitrification inhibitions were computed from the relation K-A
percentage nitrification inhibition = K - B x 100, 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 fer-tilizer nor active ingredients.

2?82Q11 Values of t~, which are e~cacy 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 demon data.
Values of t~ obtained in this fashion were subjected to Logit-Probit transforms (which lin-earize effect-dosage curves) in order to assess the effects of the combinations involved based on the independence model of Groeger, et al, [Plturn:azle 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 effects were less than those predio-ted by the independence model.

2182~~1 Eiample 1: Combinations of 1-hydro-1,2,4-triazole (Tr) and dicyanodiamide (DCD) Values of t~ were computed and compared for cases where Tr alone, DCD alone, and admix-tures of the two were employed, following the methodology referred to above.
Table 3a: Values of t~ for Tr alone, DCD alone, and admixtures of the two.
1-Hydro-1,2,4-TriazoleDicyanodiamide Tr : DCD t~

Concentration Concentration Mixing Ratio [days]

IPPmJ IPPmJ

0.096 5.5 0.227 14.0 0.545 30.0 0.909 41.5 1.25 46.0 2.0 50.0 3.0 52.3 5.0 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 5.0 5.0 50 : 50 73.8 3.0 3.0 58.2 2.0 2.0 57.1 1.25 1.25 52.5 1.667 8.333 17 : 83 106.6 1.0 5.0 71.5 0.667 3.333 53.7 0.417 2.083 37.1 0.909 9.091 9 : 91 111.8 0.545 5.445 69.4 0.364 3.636 45.5 0.227 2.273 28.7 0.25 3.75 6 : 94 37.3 0.156 2.344 23.9 0.19 3.81 5 : 95 32.1 0.119 2.38 22.2 0.385 9.615 4 : 96 73.5 0.231 5.769 41.5 0.154 3.846 29.6 0.096 2.404 21.3 0.196 9.804 2 : 98 48.1 0.118 5.882 31.2 2182;1 1 Table 3b: Percentage savings of active ingredients and incremental improvements in efficaciea, relative to those predicted by the independence model (I11~.
Tr : DCD ConcentrationEmpiricallyEfEcacy Efficacy Dosage ~

Mixing Ratioin Host Determined Predicted Increment Savings Soil by [ppm] Efficacy the INi [%]

50 : 50 10 74 82 - 8 - 53 2.5 52 48 4 14 17 : 83 10 100 64 36 -2.5 37 29 8 31 9 : 91 10 100 53 47 ---2.5 29 23 6 29 6 : 94 4 47 37 10 36 2.5 30 28 2 12 : 95 4 40 34 6 25 2.5 28 26 2 11 4 : 96 10 92 52 40 --2.5 27 25 2 11 2 : 98 10 60 46 14 48 6 . 39 36 3 17 Ezample 2: Combinations of 1-hydro-1,2,4-trix~ole (Tr) and gaanyl thiocarbamide (GT)~
The experimental met>~odology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.
Table 4a: Values of t~ for Tr alone, C1TH alone, and admixtures of the two.
1 Hydro-1,2,4-TriazoleGuanyl ThiocarbamideTr : GTH t~

Concentration Concentration Mixing Ratio [days]

[PPmI LPPm]

0.096 5.5 0.227 14.0 0.545 30.0 0.909 41.5 1.25 46.0 2.o so.o 3.0 52.3 5.0 57.0 2.0 l.0 4.0 9.3 6.0 18.4 8.0 28.0 10.0 37.4 12.0 47.2 5.0 5.0 50 : 50 63.4 2.5 2.5 53.8 1.25 1.25 40.3 0.909 9.091 9 : 91 81.8 0.545 5.445 70.3 0.227 2.273 19.2 0.385 9.615 4 : 96 60.5 0.231 5.769 35.4 0.154 3.846 25.1 0.196 9.804 2 : 98 49.4 0.118 5.882 28.9 Table 4b: Percentage savings of active ingredients and incremental improvements in effcacies, relative to those predicted by the independence model (I11~.
Tr : GTH ConcentrationEmpiricallyEfficacy Efficacy Dosage Mixing Ratioin Host Determined Predicted Increment Savings Soil by [ppm) Efficacy the IM [%~

50 : 50 10 95 95 0 - 4 2.5 68 68 0 1 9 : 91 10 100 74 26 89 2.5 29 21 8 23 4 : 96 10 91 59 32 62 2 : 98 10 74 51 23 44 ~1820~ 1 Ezample 3: Combinations of 1-hydro-1,2,4-triazole (Tr) and thioearbamide (T)~
The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.
Table Sa: Values of t~ for Tr alone, TH alone, and admixtures of the two.
1 Hydro-1,2,4-TriazoleThiocarbamide Tr : TH t~

Concentration Concentration Mixing Ratio [days]

t~~J [l~l 0.1 s.s 0.25 143 0.5 29.0 1.0 42.1 2.0 49.1 3.0 51.9 5.0 56.2 2.0 6.5 4.0 8.5 g.0 10.5 10.0 12.6 16.0 17.3 3.0 3.0 50 : 50 58.2 2.0 2.0 54.8 0.909 9.091 9 : 91 49.9 0.545 5.445 42.2 0.227 2.273 27.1 0.385 9.615 4 : 96 37.1 0.154 3.846 24.?

0.096 2.404 14.9 0.196 9.804 2 : 98 26.4 0. I 18 5.882 18.0 2i8201~
to Table 5b: Percentage savings of active ingredients and incremental improvements in efficaciea, relative to thane predicted by the independence malel (I~.
Tr : TH ConcentrationEmpiricallyEi~cacy Efficacy Dosage Mixing Ratioin Host Determined Predicted Increment Savings Soil by [ppmJ Efficacy the IM

50 : 50 6 87 80 7 40 9 : 91 10 75 63 12 39 2.5 40 28 12 42 4 : 96 10 55 48 8 24 2.5 22 18 5 25 2 : 98 10 40 38 1 5 Eiample 4: Combinations of 1-hydro-1,2,4-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~ for Tr alone, AR alone, and admixtures of the two.
1-Hydro-1,2,4-TriazoleAmmonium RhodanideTr : AR t~

Concentration Concentration Mixing Ratio [days]

IPPm] [PPm~

0.096 5.5 0.227 14.0 0.545 30.0 O,gp9 41.5 1.25 46.0 2.0 50.0 3.0 52.3 5.0 57.0 2.0 3.1 4.0 6.3 8.0 8.5 10.0 9.3 16.0 11.9 3.0 3.0 50 : 50 56.9 2.0 2.0 52.5 1.25 1.25 46.3 0.545 5.445 9 : 91 61.6 0.364 3.636 40.8 0.227 2.273 35.1 0.19 3.81 5 : 95 33.7 0.119 2.38 25.7 0.196 9.804 2 : 98 29.1 0.118 5.882 22.4 218201?

Table 6b: Percentage savings of active ingredients and incremental improvements in e~cies, relative to those predicted by the independence model (llVI).
Tr : AR Conce~ationEmpiricallyEfficacy Efficacy Dosagc Mixing Ratioin Host Determined Predicted Increment Savings Soil by IPPm) Eff~y the IM (%) 50 : 50 6 57 57 0 - 2 2.5 46 39 7 29 9 : 91 6 62 30 32 79 2.5 35 17 18 68 : 95 4 34 18 16 66 2.5 26 12 14 66 2 : 98 10 29 22 7 36 6 22 16 b 41 E=ample 5: Combinations of 1-hydrozy-methyl-1,2,4-triazole a HCI (HM1') and gaanyl 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~ for HMT alone, GTH alone, and admixtures of the two.
1-Hydroxy-Methyl-1,2,4-TriazoleGuanyl ThiocarbamideHMT : GTH t~
x HCl Concentration Concentration Mixing Ratio[days]

[PPm) [Ppm) 0.25 14.8 0.5 22.9 0.75 29.7 1.0 37.4 2.0 44.1 5.0 50.0 7.5 57.1 1.0 1.1 2.0 3.4 4.0 10.2 8.0 29.1 10.0 38.2 5.0 1.0 83 : 17 53.1 2.5 0.5 44.2 1.25 0.25 38.7 3.0 3.0 50:50 52.1 1.5 1.5 43.1 1.0 5.0 17 : 83 56.9 0.5 2.5 29.1 0.545 5.445 9 : 91 64.9 0.273 2.727 28.3 0.286 5.714 5:95 61.7 0.143 2.857 23.9 0.118 5.882 2:98 39.4 ~~~2011 Table 7b: Per~ge aaving~t of active ingredients and incremental i~provementa in efficacies, rdat'rve to thore predicted by the independ~tce ~odel (IM).
HMT : G'TH Coon EmpiricallyEfficacy Efficacy Dosage Mixing Ratioin Host Determined Predicted Increment Savings Soil by [ppm] Efficacy the IM [%]

83 : 17 6 80 87 - 7 - 50 2.5 58 54 4 11 50 : 50 6 78 80 - 2 -10 17 : 83 6 85 59 26 59 9 : 91 6 97 47 50 88 : 95 6 92 38 56 85 2 : 98 6 59 31 28 59 2 ~ X20 ~ ~
Ezample 6: CombinatioHS of 1-eodiam-1,2,4-triazolate (Na-Tr) and dicyanodiamide The experimental methodology and computerized data analyses employed here were similar to those employed in tl~e case of Example 1, above.
Tablc 8a: Values of t~ for Na Tr alone, DCD alone, and admixtures of the two.
1-Sodium-1,2,4-TriazolateDicyanodiamide Na Tr : DCD t~

Concentration Concentration Mixing Ratio [days]

[PPm] [PPm]

0.25 9.7 0.5 21.4 0.75 26.1 1.0 31.9 1.5 33.7 2.0 38.4 5.0 41.8 1.0 12.4 2.0 22.1 4.0 26.1 6.0 29.6 10.0 38.1 5.0 1.0 83 : 17 52.1 2.5 0.5 46.7 3.0 3.0 50 : 50 60.1 1.5 1.5 51.9 1.0 5.0 17 : 83 73.2 0.5 2.5 51.4 0.545 5.445 9 : 91 64.2 0.273 2.727 42.9 0.231 5.769 4 : 96 47.9 0.115 2.885 35.1 218201 i Table 86: Percentage savings of active ingredients and incremental improvements in ef5c, relative to those predicted by the independence model (nl~.
Na-Tr : Concenh~ationEmpiricallyEfficacy E~cacy Dosage DCD

Mixing Ratioin Host Determined Predicted Increment Savings Soil by [ppm] Efficacy the IM [r6]

83 : 17 6 78 79 -1 - 5 50 : 50 6 90 7? 13 55 17 : 83 6 100 68 32 -9 : 91 6 96 63 33 ---4 : 96 6 72 57 15 47 Example 7: Combinations of 1-hydro-1,2,4-triazole (Tr) and 3-methylpyrazole (MP) The experimental methodology and compute data analyses employed here were similar to those employed in the case of Example 1, above.
Table 9a: Values of t~ for Tr alone, MP alone, and admixtures of the two.
1-Hydro-l,2,4-Triazole3-Methylpyrazole Tr : MP t~

Concentration Concentration Mixing Ratio [days]

Lt~] fl~l 0.1 5.3 0.25 14.9 0.5 27.8 0.75 36.8 1.0 41.9 1.5 48.?

3.0 56.9 0.1 9.1 0.25 24.5 0.5 43.6 0.656 46.3 1.0 48.7 2.0 52.3 1.0 1.0 50 : 50 95.6 0.5 0.5 72.7 1.818 1.182 91 : 9 69.8 0.909 0.091 51.7 1.923 0.077 96 : 4 59.8 0.962 0.038 42.8 0.077 1.923 4 : 96 61.0 0.038 0.962 52.4 21 ~g201 1 is Table 96: Per~xntage savings of active ingredients and incremental improvements in et8cacies, relative to those predicted by the independence model (I~.
Tr : MP ConcentrationEmpiricallyEfficacy Ei~cacy Dosage Mixing Ratioin Host Determined Predicted Increment Savings Soil by .

[ppm) Efficacy the IM [%]

50 : 50 2 100 90 10 86 91 : 9 2 100 83 17 88 96 : 4 2 90 81 9 40 4 : 96 2 91 88 3 27 ?_ 182 1 1 Ezample 8: Combinations of [Cn(Tr}~504 z 2HI0 hydrated cnprotriazole-e~nlfate com-plez (C'I'A and (GMPH~ZnCl4 1-gnanyl-3-methylpyrazolin~chlorozinc-ate complez (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~ for CTS alone, GZC alone, and admixtures of the two.
CTS-Concentration GZC-Concentration CTS : GZC t~

[PPm] (ppm] Mixing Ratio[days]

0.1 1.9 0.25 4.9 0.5 11.6 1.2 27.0 1.8 36.1 2.5 43.1 0.25 9.5 0.5 19.1 0.75 26. 8 1.5 43.3 3.0 59.1 1.0 1.0 50 : 50 77.2 0.5 0.5 53.6 0.25 0.25 21.9 1.818 0.182 91 : 9 45.9 0.909 0.091 27.8 0.182 1.818 9 : 91 53.6 0.091 0.909 30.0 Table lOb: Percentage savings of active ingredients and incremental improvements in e~cacies, relative to those predicted by the independence model ()ZVI).
CTS : GZC ConcemrationEmpiricallyEfficacy Efficacy Dosage Mixing Ratioin Host DeterminedPredicted Increment Savings Soil by [PPm] Efficacy the IM [%]

50 : 50 2 100 72 28 84 0.5 33 19 14 37 91 : 9 2 69 64 5 14 9 : 91 2 80 74 5 16 Eiample 9: Combinations of 1-hydro-1,2,4-triazole (Try dicysnodinmide (DCD~
and ammonium rhodaaide (AR) The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.
Tablc 11 a: Values of t~ for Tr alone, DCD alone, AR alone, and admixtures of all three.
Tr-ConcentrationDCD-ConcentrationAR-ConcentrationTr : DCD : t~
AR

fpP'ml (ppm) LPPmI Mixing Ratio (days) 0.096 5.5 0.227 13.8 0.545 30.2 0.909 41.5 1.25 46.0 2.0 50.1 3.0 52.3 5.0 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 11.9 0.833 4.167 0.833 14.3:71.4:14.367.1 0.5 2.5 0.5 52.4 0.385 3.846 0.769 7.7:76.9:15.4 58.9 0.231 2.308 0.462 37.7 0.192 3.846 0.962 3.8:77:19.2 45.7 0.1 i5 2.308 0.575 34.7 ?1~2~~~

Table llb: Percentage aaving~ of active ingredients and incremental improvements in et~caciea, r~ative to those predicted by the independence model (IM).
Tr : DCD : ConcentrationEmpiricallyEfficacy Efficacy Dosage AR

Mixing Ratio in Host DeterminedPredicted Increment Savings Soil by [pp~] Ef~ca~y tl~ nH [/~]

14.3:71.4:14.35.83 100 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 ?_ ~ a201 ~

Ezample 10: Combinations of 1-bydro-1,2,4-triazole hydrochloride (Tr z HCI), guanyl t6iocsrbamide (G1'H~ and thiocarbamide (1'H) 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~ for Tr x HCl alone, GTH alone, TH alone, and adnnixtures of all three.
Tr x HCl- GTH-ConcentrationTH-ConcentrationTr x HCl : GTH t~
: TH

Concentration[ppm] [ppmj Mixing Ratio [days]

[PPm]

0.15 5.0 0.3 11.5 0.75 28.4 1.5 41.3 3.0 48.9 4.5 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 18.1 0.115 2.308 0.577 3.8:77:19.2 17.9 0.231 4.615 1.155 44.8 0.115 1.422 1.422 3.8:48.1:48.1 11.9 0.231 2.885 2.885 37.9 0.231 1.155 4.615 3.8:19.2:77 27.8 0.5 2.0 0.5 17 : 66 : 17 53.1 0.5 1.25 1.25 16.6 : 41.7 : 39.9 41.7 0.188 1.875 0.937 6.3:62.5:31.2 21.3 0.375 3.75 1.875 47.1 ?_ 18201 1 Table 12b: Penxntage aavin~ of active Ingredi~ts and incremental improvements in effiCacies, relsvtive to those predicted by the independence model (I~.
Tr x HCl : GTH ConcentrationEmpiricallyEfficacy Efficacy Dosage : TH

Mixing Ratio in Host Determined Predicted Increment Savings Soil by (ppm~ Efficacy the 1M I~l 3.8 : 77 : 19.23.0 27 16 11 36 6.0 67 35 32 57 3.8 : 48.1 : 3.0 19 12 7 28 48.1 6.0 57 30 27 51 3.8:19.2:77 6.0 42 25 1? 40 17:66:17 3.0 81 33 48 74 16.6:41.7:41.7 3.0 60 30 30 55 6.3:62.5:31.2 3.0 33 17 16 43 6.0 71 38 33 56 21 °2~1 1 Ezample 11: Combinations of 1-gannyl-1,2,4-trinzole hydrochloride (GTr~
dicyano-diamide (DCD), and thiocarbs~mide (T~
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~ for GTr alone, DCD alone, TH alone, and admixtures of all three.
GTr-ConcentrationDCD-ConcentrationTH-ConcentrationGTr : DCD t~
: TH

[PPm] [PPmI [pPm] ~8 Ratio [days]

1.4 27.5 2.14 37.5 4.3 47.3 8.5 49.2 10.0 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 18.1 0.192 3.840 0.968 3.8:76.8:19.443.8 0.308 6.160 1.54 61.7 0.192 2.404 2.404 3.8:48.1:48.137.4 0.308 3.846 3.846 57.8 0.192 0.968 3.840 3.8:19.4:76.827.9 0.308 1.540 6.160 32.7 2 ~ 82Q 1 1 Table 13b: Perc~tage aaving~ of active ingredients and incremental improvements in efficacies, relative to those predicted by the independence model (nVn.
GTr : DCD : TH ConcentrationEmpiricallyEfficacy Effcacy Dosage Mixing Ratio in Host Determined Predicted Increment Savings Soil by [ppm] Efficacy the IM ~%]

3.8:76.8:19.4 5.0 66 48 18 60 8.0 93 32 61 98 3.8:48.1:48.1 5.0 56 46 10 40 8.0 87 55 31 84 3.8 : 19.4 : 5.0 42 42 0 - 1 76.8 8.0 49 51 - 2 - 10 Ezample lZ: Combinations of 1-hydra-1,2,4-trinzole (Try dicyanodiamide (DCD), and ammoginm thiosalfate (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~ for Tr alone, DCD alone, ATS alone, and admixtures of all three.
Tr-Conce~rationIxD-ConcentrationATS-ConcentrationTr : DCD : t~
ATS

fpPml IPPmI fppml ~g ~tio ~daysJ

0.096 5.5 0.227 14.0 0.545 30.0 0.909 41.5 1.25 46.0 2.0 50.0 3.0 52.3 5.0 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 0 0.115 2.308 0.577 4:77:19 35.7 0.115 1.422 1.422 4:48:48 27.8 0.115 0.577 2.308 4 : 19 : 77 14.1 2 ~ ~'2~' i Table 14b: Percentage savinga of active ingredients and incremental improvements in ~caciea, relative to there predicted by the independence ~odel (llVn.
Tr : DCD : ATS ConcentrationEmpiricallyEfficacy Efficacy Dosage Mixing Ratio in Host DeterminedPredicted Increment Savings Soil Efficacy by [%]
[ppm] the IM

4:77:19 3.0 53 35 18 SS

4:48:48 3.0 42 30 12 42 4 : 19 : 77 3.0 21 24 - 3 - 20 Ezample 13: Combinations of [Fe(Tr~)Cl3 ferroc6lorotriazole complez (Fe'Tr~
dicyan-odiamide {DCD~ and am~oninm t6iosalfate (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~ for Fo-Tr alone, DCD alone, ATS alone, and admixtures of all three.
Fe-Tr-ConcentrationDCD-ConcentrationATS-ConcentrationFe-Tr.DCD:ATSt~

[PPm] [PPm] [PPm] axing Ratio [days]

0.072 3.9 0.163 10.3 0.39 21.2 0.65 29.4 0.9 33.3 1.44 35.7 2.15 39.4 4.0 42.9 6.0 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 0.1 2.0 2.0 2.0 33.3:33.3:33.354.6 1.0 1.0 1.0 45.8 0.231 4.615 1.154 3.8 : 77 : 51.2 19.2 0.115 2.308 0.577 35.8 0.231 2.885 2.885 3.8:48.1:48.144.9 0.115 1.422 1.422 28.8 0.231 1.154 4.615 3.8:19.2:77 29.5 0.115 0.577 2.308 16.7 0.545 4.364 1.091 9.1:72.7:18.257.9 0.273 2.182 0.545 39.7 Table 15b: Percentage savings of ac~ve ingredients and incremental improvements in eflicacies, relative to those predicted by the independence model (IM).
Fe-Tr : DCD : ConcentrationEmpiricallyEfficacy Efficacy Dosage ATS

Mixing Ratio in Host DeterrminedPredicted Increment Savings Soil by [ppm) Efficacy the IM [%]

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 ?' 82~~ ~ 1 Ezample 14: Combinations of (Mn(Tr)4]Cl= manganochlorotriazole complez (M'T), M~GMP~CI= z Hz0 hydrated 1-gaanyl-3~methyl pyrazole magneainm-chloride eomplea (GMT 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~ for MT alone, GM alone, DCD alone, and admixh~res of all three.
MT-ConcentrationGM-ConcentrationDCI7-ConcentrationMT : GM : t~
DCD

IPPm) LPPm~ IPPmI M~8 ~ L~Ys) 0.2 5.6 0.5 15.5 1.0 28.4 1.5 35.4 2.0 42.1 3.0 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 52.5 1.667 1.667 1.667 33.3:33.3:33.3106.9 1.0 1.0 1.0 85.7 0.667 0.667 0.667 61.8 0.417 0.417 4.166 8.3:8.3:83.4 64.1 0.25 0.25 2.5 44.8 0.167 0.167 1.666 34.1 0.185 0.185 4.630 3.7:3.7:92.6 60.7 0.111 0.111 2.778 40.1 0.543 0.109 4.348 10.9:2.1:87 54.6 0.109 0.543 4.348 2.1:10.9:87 61.4 31 2 ~ X201 I
Table 16b: Percentage savings of active ing~redient~ and incremental improvements in dies, retative to those predicted by the independence model (1~.
MT : GM : DCD ConcentrationEmpiricallyEfficacy EfEcacy Dosage Mixing Ratio in Host Determined Predicted Increment Savings Soil by [ppm] Efficacy the IM [%]

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 50 10.9:2.1:87 5.0 82 59 23 52 2.1:10.9:87 5.0 92 63 29 67 Ezample 15: Combin~ttiona of 1-hydro-1,2,4-trinzole (Try 3-methylpyrstzole (MP), and guanyl thiocarbamide (G'I~
The experimental methodology and computerized data analyses employed here were similar to those employed in the case of Example 1, above.
Table 17a: Valucs of t~ for Tr alone, MP alone, GTH alone, and admixtures of all three.
Tr-ConcentrationMP-ConcenhationGTH-Conce~ation Tr : MP : GTH t~

[PPm] [PPm] [PPm] Mixing Ratio [days]

0.1 5.8 0.25 14.3 0.5 29.0 0.75 42.1 1.0 49.1 1.5 51.9 3.0 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 47.2 1.667 1.667 1.667 33.3:33.3:33.3112.1 1.0 1.0 1.0 105.7 0.227 0.227 4.546 4.5 : 4.5 : 73.4 0.136 0.136 2.727 47.8 0.119 0.119 4.762 2.4:2.4:95.2 44.9 0.071 0.071 2.857 29.3 Table 17b: Percentage savings of active ingredients and incremental improvements in effcacies, relative to those predicted by the independence model (I1H).
Tr : MP : GTH ConcentrationEmpiricallyEfficacy Efficacy Dosage Mixing Ratio in Host Determined Predicted Increment Savings Soil by [ppm) E~cacy the IM [%) 33.3:33.3:33.3 5.0 100 98 2 65 3.0 1~ 92 8 69 4.5:4.5:91 5.0 100 56 44 91 3.0 72 35 37 59 2.4:2.4:95.2 5.0 67 40 27 48 3.0 44 23 21 46 ?_ i ~2~ 1 1 Ezample 16: Combination9 of 1-hydro-1,2,4-triazole (Try 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~ for Tr alone, MP alone, DCD alone, and admixtures of all three.
Tr-ConcentrationMP-ConcentrationDCD-ConcentrationTr : MP : DCD t~

[ppm] (ppm] [ppm] Mixing Ratio [days]

0.1 5.2 0.25 13.4 0.5 28.1 0.75 40.7 1.0 46.9 1.5 49.8 3.0 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 41.8 1.667 1.667 1.667 33.3:33.3:33.3112.9 1.0 1.0 1.0 102.3 0.227 0.227 4.546 4.5 : 4.5 : 79.4 0.136 0.136 2.727 52.9 0.119 0.119 4.762 2.4:2.4:95.2 57.1 0.071 0.071 2.857 41.8 21~2~;I
Table 18b: percentage savings of active ingredients and incremental improvements in effcacies, relative to those predicted by the independence model (~.
Tr : MP : DCD ConcentrationEmpiricallyE~cacy Efficacy Dosage Mixing Ratio in Host Determined Predicted Increment Savings Soil by [ppm] Efl"'tcacy the IM [%]

33.3:33.3:33.3 5.0 100 95 5 82 3.0 100 88 12 89 4.5:4.5:91 5.0 100 64 36 94 3.0 79 47 32 63 2.4:2.4:95.2 5.0 86 54 32 66 3.0 63 38 25 54

Claims (3)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A method for inhibiting and controlling the nitrification of ammonium in arable soil and substrates comprising the step of applying to the soil as active ingredients a combination of two or more nitrification inhibitors in the form of 1H-1,2,4-triazole or a substituted 1H-1,2,4-triazole or a salt or metallic complex thereof, plus at least one other chemical compound selected from the group consisting of a substituted pyrazole, a salt or metallic complex thereof, dicyanodiamide, guanyl thiocarbamide, thiocarbamide, ammonium rhodanide and ammonium thiosulfate, said active ingredients being present in proportions by weight ranging from 0.5:99.5 to 99.5:0.5 in a case where two active ingredients are involved, or in any proportions in a case where more than two active ingredients are involved.

2. A method as claimed in claim 1, wherein the active ingredients are used in the form of a solution, suspension, sprayable powder, or emulsion concentrate, alone or in combination with a solid or liquid amide or mineral or organic ammonium fertilizer, where said composition is applied prior to, along with, or subsequent to, said fertilizer, or applied independently of said fertilizer in combination with other agrochemicals, or is applied in conjunction with an agricultural procedure, said composition being applied in a dosage of at least 0.5 kg active substance per hectare, or contains at least 0.2% by weight of active substances, based on their reduced-nitrogen contents, in cases where the composition is applied along with a mineral fertilizer.

3. A method as claimed in claim 2, wherein said agrochemicals are herbicides, pesticides, growth regulators, or soil-enrichment agents.