Abstract:
In the control of nematodes, use is made of a formulation using D-limonene as a solvent to carry an effective dosage of chloropicrin. The formulation can also include an amount of methyl isothiocyanate corresponding in volume approximately to the amount of chloropicrin. The combination of these two components is synergistic. With the further addition of diazinon, a double synergistic effect is obtained.

Description:
BACKGROUND OF THE INVENTION 
     The present invention is directed to the control of undesirable soil components, and more particularly to the control of nematodes, symphylans wireworms, soil borne diseases, and weed seeds in crop land and ornamental gardens as well as commercial turf. Also included in the undesirable components are mole crickets. 
     BRIEF REVIEW OF THE PRIOR ART 
     Nematodes are a good example of undesirable soil components. Nematodes are microscopic eel worms and come in many varities. The dog hookworm is a nematode, i.e., it forms part of the animal parasitic group. But, there are also those forming part of the plant parasitic group. These plant parasitic components feed on plant roots and poisons the plant. They also cause damage to the mammals, including humans who eat the plants. These undesirable soil components have been controled by the injection into the soil of various formulations, one component suggested has been chloropicrin, but this component is very expensive and has not proven too effective, when carried out in practice. The use of chloropicrin has been suggested by Kirk et al, &#34;Encyclopedia of Chemical Technology&#34; in its several editions in the article on Chloropicrin. Nevertheless, in practice, chloropicrin or Cl 3  CNO 2  is not now used in the various commercially avilable formulations except as a warning agent for other fumigants. 
     Further inhibiting the use of chloropicrin is the tendency of chloropicrin to contaminate such items as beer and soda cans as described in the case of BURKE PEST CONTROL, INC. v. JOSEPH SCHLITZ BREWING COMPANY, 438 So. 2d 95 (Fla. App. 2 Dist. 1983), wherein the brewing company discovered that after a fumigation treatment, from ten to sixty-six nanograms of chloropicrin remained on the can liners which contaminated the cans and made them useless. 
     Now it has been discovered that the undesirable effects of chloropicrin can be minimized and eliminated by using D-limonene (also called dl-limonene) as a solvent. D-limonene is a material of the terpene family. The terpene family has been most bountiful in providing the means to produce synthetic rubber and other valuable discoveries because of isoprene and the isoprene rule wherein carbon skeletons made of isoprene units are joined in a regular head-to-tail way, repeating the double bonds between molecules or other chemical particles. However, dl-limonene (the &#34;dl&#34; signifying dextro-levo) is a solvent and as such usually does not enhance chemical reaction. 
     The present invention contemplates the use of D-limonene as a synergistic solvent in connection with the use of agricultural chemicals. Thus, it has now been discovered that a formulation can be provided for the control of nematodes and similar undesirable soil components where the formulation makes use of D-limonene as a solvent for the chloropicrin. Additionally, methyl isothiocyanate can be included in the formulation. Effective amounts of diazinon, if also added will provide a double synergistic effect, the first synergistic effect being the combination of the chloropicrin and D-limonene and the second synergistic effect will be the addition of diazinon. 
     SUMMARY OF THE INVENTION 
     Generally speaking the present invention contemplates the following formulations, the amounts being of the order of the quantities shown in parts by weight: 
     
         __________________________________________________________________________Formulation I    Formulation II              Formulation III                        Formulation IV__________________________________________________________________________83% D-limonene    70% D-Limonene              73% D-limonene                        65% D-Limonene17% Chloropicrin    18% Chloropicrin              14.5% Chloropicrin                        13% Chloropicrin    14% Methyl              12.5% Diazinon                        10% Methyl Isothiocyanate    Isothiocyanate              12% Diazinon__________________________________________________________________________ 
    
     DETAILED DESCRIPTION 
     As used herein, the terms hereinafter listed have the meanings shown next to the particular term: 
     D-limonene is 4-isopropenyl-1-methyl-1-cyclohexene. The structural formula is: ##STR1## methyl isothiocyanate is CH 2  SCN, being a member of the isocyanate family having the formula R--SCN, where &#34;R&#34; is a hydrocarbon radical 
     Diazinon is the trade name for phosphorothioic acid. The structural formula is: ##STR2## chloropicrin has the formula Cl 3  CNO 2  and is otherwise known as trichloronitromethane 
     T is Telone, a Dow Chemical Co. product which is dichloropropene and has the formula: ##STR3## C-17 is also known as Soilex is 17% Chloropicrin, 83% D-limonene C-50 is 50 % chloropicrin, 50% D-limonene 
     Telone II is 92% dichloropropene 
     C-17-S is C-17 in a diazinon solution 
     Vorlex is Telone II plus 20% methyl isothiocyanate 
     In carrying the invention into practice, various formulations were prepared having about 5 parts by weight and about 80 parts by weight of D-limonene as a solvent into which was added between about 10 parts by weight and about 90 parts by weight chloropicrin, namely, Cl 3  CNO 2 , additionally, in some of the formulations there was added about 80 parts by weight to about 20 parts by weight of methyl isothiocyanate. As a further formulation, several batches were prepared containing only D-limonene and methyl isothiocyanate, namely 10 parts by weight to about 50 parts by weight of the methyl isothiocyanate to about 50 parts by weight to about 90 parts by weight of the D-limonene solvent. Also, in some batches diazinon was added in quantities of from zero to about 20 parts by weight. 
    
    
     For the purpose of giving those skilled in the art a better understanding of the invention, the following illustrative examples are given: 
     Formulations prepared by the applicant herein were tested against formulations of the prior art at several locations in connection with various crops as shown: 
     (I) Location: Gainesville, Fla., University of Florida Institute of Food and Agricultural Sciences. 
     Crop: Peanuts; Time August/October 1984 
     Formulations: 
     (1) C-17 (hereinbefore described) &#34;SOILEX&#34; 
     (2) Telone II 1-3-dichloropropane 
     (3) Vorlex, 1-3-dichloropropane+20% methyl isothiocyonate 
     The formulation used, namely 17% chloropicrin and 83% D-limonene had a specific gravity of 0.961 or approximately 8 Lbs. per gallon, a boiling point of 112° C., a freezing point of -81° C., a flash point greater than 130° F., vapor pressure at 20° C. of -17 mm Hg. It is almost insoluble in water, soluble in alcohol, petroleum solvents, chlorinated solvents and carbon disulfide. In the presence of water, it becomes corrosive to steel, aluminum, magnesium alloys and vinyl plastics. 
     (II) Location: Boca Raton, Fla., Boca West Golf Course. 
     Time: April, 1985 
     Formulations: 
     (1) T, Telone (hereinbefore described) 
     (2) C-17 (hereinbefore described) 
     (3) C-17-S (hereinbefore described) 
     (4) C-50 (hereinbefore described) 
     (5) C-17-D is C-17 as hereinbefore described plus technical DIAZINON (92%) 
     (III) Location: Tifton, Ga., Costal Plain Experiment Station, Donald Benson Farm, Tift County, Ga. 
     Crop: Peanuts; Time May/September 1984 
     Formulations: 
     (1) T, Telone II 
     (2) Vorlex 
     (3) C-17, Soilex 
     (4) Nemacur 
     Conclusion, in all the aforementioned tests the formulations described herein namely, D-limonene as a solvent with an effective amount of chloropicrin, and, also by adding an effective amount of methyl-isothiocyanate, and/or with an effective amount of phosphorothioc acid were superior and usually vastly superior to the other formulations shown of the prior art. In the formulations tested, the D-lomonene solvent consist of between about 5 to about 80 parts by weight and the chloropicrin may consist of between about 10 and about 90 parts by weight, the methyl-isothiocyanate component may be from about 20 to about 80 parts by weight, and may include between about zero to about 20 parts by weight of phosphorothioc acid. Another formulation which is effective consists of about 10 to about 50 parts by weight of methyl-isothiocyanate mixed into about 50 to about 90 parts by weight of D-limonene solvent. The combination of chloropicrin and methyl isothiocyanate is synergistic. With the further addition of diazinon, a double synergistic effect is obtained. 
     
         __________________________________________________________________________EVALUATION OF NEMATICIDES FOR MANAGING THE PEANUT ROOT-KNOTNEMATODE ON PEANUT, 1984:                                       No. nematodes/250 cm.sup.3                                       soil         Methods of appli-             Meloidogyne                                                CriconemellaTreatment and overall         cation &amp; rate per                    Yield %    %   Value/                                       arenaria curvatumrate per acre (active).sup.X         100 l. ft. row                    lb/acre                          Damage                               SMK.sup.Y                                   acre                                       Aug 10                                           Oct 9                                                Aug                                                     Oct__________________________________________________________________________                                                     9Telone II 15.0 gal         7 days preplant,                    3,365a.sup.Z                          2    70  $971                                       4b  191de                                                86bcdefg                                                     328bcdef         2-chisels, 10 inches         apart; 65 mlTelone II 15.0 gal         14 days preplant,                    3,332ab                          3    69  944 10ab                                           211de                                                76bcdefg                                                     276cdef         2-chisels 10 inches         apart; 65 mlVorlex 12.0 gal         14 days preplant,                    3,174abc                          3    69  917 5ab 793ab                                                15fg 138f         2-chisels, 8 inches         apart.sup.ZZ ; 52 mlTelone II 12.0 gal +         14 days preplant,                    2,973abcd                          1    74  884 30ab                                           110e 103bcdef                                                     454abcTemik 15 G 6.0 lb         2-chisels, 10 inches         apart + at-peg, 14         inch band; 52         ml + 49 gVorlex 12.0 gal +         14 days preplant,                    2,919abcd                          2    74  863 2b  864a 5g   150efFuradan 15 G 6.0 lb         2-chisels, 8 inches         apart.sup.ZZ + at-peg 14         inch band; 52         ml + 49 gTelone II 6.0 gal         14 days preplant,                    2,842abcd                          2    71  832 38ab                                           246cde                                                140abc                                                     196def         2-chisels, 10 inches         apart; 26 mlChloropicrin 6.0 gal         14 days preplant,                    2,842abcd                          1    73  850 4b  486bcde                                                67bcdefg                                                     453abc         2-chisels, 10 inches         apart; 26 mlUntreated Control         2-chisels, 2,793abcd                          1    61  829 15ab                                           620abc                                                78bcdefg                                                     346abcde         8 inches apartUntreated Control         2-chisels, 2,766abcd                          3    64  776 17ab                                           367cde                                                132abcd                                                     531a         10 inches apartTelone II 12.0 gal         14 days preplant,                    2,717abcd                          3    69  784 19ab                                           307cde                                                70bcdefg                                                     512ab         2-chisels, 10 inches         apart; 52 mlTelone II 12.0 gal +         14 days preplant,                    2,690abcde                          3    69  768 15ab                                           229cde                                                112bcde                                                     378abcdFuradan 15 G 6.0 lb         2-chisels, 10 inches         apart + at-peg, 14         inch band; 52         ml + 49 gChloropicrin 3.0 gal         14 days preplant,                    2,624abcde                          1    72  755 9ab 352cde                                                59cdefg                                                     263cdef         2-chisels, 10 inches         apart; 13 mlChloropicrin 9.0 gal         14 days preplant,                    2,467bcde                          5    55  682 43a 752ab                                                78bcdefg                                                     254def         2-chisels, 10 inches         apart; 39 mlTelone II 9.0 gal         14 days preplant,                    2,467bcde                          8    65  688 26ab                                           337cde                                                193a 458abc         2-chisels, 10 inches         apart; 39 mlBusan 1020 30.0 gal         14 days preplant,                    2,412cde                          5    68  679 16ab                                           576abcd                                                40efg                                                     193def         2-chisels, 8 inches         apart; 130 mlBusan 1020 36.0 gal         14 days preplant,                    2,292de                          5    71  662 37ab                                           465bcde                                                47defg                                                     207def         2-chisels, 8 inches         apart; 156 mlSoilex C-17 15.0 gal         14 days preplant,                    2,129de                          6    52  578 10ab                                           422bcde                                                148ab                                                     382abcd         2-chisels, 10 inches         apart; 65 mlTelone II 15.0 gal         at-plant, 2-chisels, 10                    1,851e                          3    64  503 6ab 152e 50defg                                                     502ab         inches apart; 65 ml__________________________________________________________________________ Peanut (Arachis hypogaea `Florunner`) Rootknot nematode; Meloidogyne Ring nematode; Criconemella curvatum D. W. Dickson and T. E. Hewlett Dept. Of Entomology &amp; Nematology University of Florida Gainesville, Florida 32611 .sup.X Rates calculated for row treatments were reduced from the overall (broadcast) dosage in proportion to the actual area tested. All dosages were calculated based on a 36 inch row .sup.Y Sound mature kernels based on government grading system. .sup.Z Means with the same letter are not significantly different according to Duncan&#39;s new multiple range test (P = 0.05). .sup.ZZ Ridged with diskhillers. 
    
     
         __________________________________________________________________________BOCA WEST TEST PLOTSBELONOLAIMUS ONLYPRE-TEST, 11 DAYS, &amp; 34 DAYS AFTER INJECTION__________________________________________________________________________   SAMPLE NUMBER              #3         #5    #6   #1   #2    C-17 +                    #4   C-17 +                               C-17 + #7    #8  #9  #10NEMATODE   CHECK        TELONE              SAROLEX                    C-17 SAROLEX                               DIAZINON                                      TELONE                                            C-50                                                C-17                                                    TELONE__________________________________________________________________________STING-BELO-   32   32    24    12   48    52     68    24  60  72NOLAIMUSPRETEST11 DAYS 24   4     20    8    8     12     4     12  4   1634 DAYS 52   8     24    8    4     24     28    8   36ROOT    NONE 4 new root              NONE  15 new                         4 new root                               4 new  11 new                                            NONE                                                4 new                                                    6 newRESPONSE @   11/2&#34; long  root 1&#34; long                               4&#34; long                                      3&#34; long   1&#34; long                                                    11/2&#34; long11 DAYS                  3&#34; longVISUAL  POOR GOOD 5&#39;              POOR  POOR POOR  GOOD 6&#39;                                      GOOD 8&#39;                                            POOR                                                POOR                                                    GOOD 6&#39;RESPONSE @   of turf                of turf                                      of turf       of turf102 DAYS__________________________________________________________________________               SAMPLE NUMBER               #11              #14            #17               C-17 +                     #12  #13   C-17 + #15 #16 C-17                                                     #18       NEMATODE               DIAZINON                     CHECK                          C-50  DIAZINON                                       C-50                                           C-17                                               SAROLEX                                                     CHECK__________________________________________________________________________       STING-BELO-               32    36   36    36     12  16  80    48       NOLAIMUS       PRETEST       11 DAYS 0     48   12    8      16  16  56    28       34 DAYS 16    4    12    0      0   8   44    84       ROOT    NONE  NONE NONE  NONE   6 new                                           5 new                                               NONE  NONE       RESPONSE @                      3&#34; long                                           2&#34; long       11 days       VISUAL  GOOD 8&#39;                     POOR GOOD 5&#39;                                GOOD 20&#39;                                       POOR                                           POOR                                               POOR  POOR       RESPONSE @       102 days__________________________________________________________________________NEMATODE Three Plot Average Below            CHECK TELONE                        C-17 + S                              C-17  C-17 + D                                          C-50__________________________________________________________________________      PRETEST            39    57    51    29    40                                          24      11 DAYS            33              15%↓                   8                    86%↓                        28                          45%↓                               9                                69%↓                                     7                                      83%↓                                          13                                            46%↓      34 DAYS            47              21%↑                  25                    56%↓                        24                          53%↓                              17                                41%↓                                    13                                      68%↓                                          7 71%↓__________________________________________________________________________ When the number of nematodes are estimated the following symbols are used VL--very light infestation; L--light infestation; MM--moderate infestation; H--heavy infestation; VH--very heavy infestation. 
    
     Experiment No. and Title: P5-84. Comparison of Soilex and Telone II applied to peanut 8 days preplant. 
     Work Unit/Project No.: 7702-20270-001 
     Address: Coastal Plain Experiment Station, Tifton, GA 31793 
     Investigator(s): Norman A. Minton and A. S. Csinos 
     Experiment Location: Donald Benson Farm, Tift, County 
     Type Experiment: Field 
     Nematode species: Meloidogyne arenaria, Criconemella ornata 
     Other Organisms: 
     Plant species and varieties: Arachis hypogaea, Florunner 
     Experimental design: Strip 
     Plot size and No. reps.: 2 rows, 25 ft long, 4 replications. 
     Soil type: Ocilla loamy soil 
     Soil moisture: 10.7%, May 2 when chemicals applied 
     Soil temperature: Maximum, 84 F., minimum, 73 F. at 4&#34; depth when chemicals applied. 
     Planting dates: May 10 
     Treatment dates: May 2 
     Harvest dates: September 24 
     Weather conditions: Adequate rainfall for good yields 
     Unusual circumstances: 
     Progress: See Table P5A-84. 
     
                                           TABLE P5A-84__________________________________________________________________________Effects of soilex and Telone II applied with the moldboard plow on peanutproduction, 1984..sup.1                                 Number nematodes/                                 150 cm.sup.3 soil,                                 9/14/84                 Root-                     White   Vigor                                 Crico-                                      Meloido-Treatment and   Method of .sup.2         Yield             %   knot                     mold                         Stand                             rating                                  nemella                                      gynerate (lb ai/A)   application         (lb/A)             SMK.sup.3                 index.sup.4                     hits.sup.5                         (5/21).sup.6                             (6/22).sup.7                                  ornata                                      arenaria__________________________________________________________________________Telone II 55.8   A     4857 ab             80.0                 3.1 a                     3.3 a                         12.0 a                             3.5 b                                 2425 a                                      530.0 aSoilex 117.6   A     5162 a             79.7                 3.9 a                     3.3 a                         12.0 a                             4.3 ab                                 1545 a                                      422.5 aControl       4552 b             78.7                 5.9 a                     4.8 a                         13.3 a                             4.5 a                                 2052 a                                      1475.0 a__________________________________________________________________________ .sup.1 Data within same column followed by the same letter are not significantly different (P = 0.05) according to Duncan&#39;s multiplerange test. .sup.2 Applied in moldboard plow furrow 10&#34;  deep on 8&#34; centers 8 days before planting. .sup.3 % sound mature kernel (SMK) determined from composit sample from four replications. .sup.4 Rootknot index based on rating of 0-10: 0 = no galling, 10 = 100% of roots and pods galled. .sup.5 White mold hits = number of hits per 50 ft row. One or more plants infected per ft of row in one hit. .sup.6 Stand = number of plants emerged per m of row. .sup.7 Vigor rating based on scale of 1-5: 1 = poor growth, 5 = excellent growth. 
    
     Experiment No. and Title: P6-84. Fumigant nematicides: Methods of application to peanut 8 days preplant. 
     Work Unit/Project No.: 7702-20270-001 
     Address: Coastal Plain Experiment Station, Tifton, GA 31793 
     Investigator(s): Norman A. Minton and A. S. Csinos 
     Experiment Location: Donald Benson Farm, Tift County 
     Type Experiment: Field 
     Nematode species: Meloidogyne arenaria, Criconemella ornata 
     Other Organisms: 
     Plant species and varieties: Arachis hypogaea, Florunner 
     Experimental design: Strip 
     Plot size and No. reps.: 2 rows, 25 ft long, 4 replications 
     Soil type: Ocilla loamy soil 
     Soil moisture: 10.7% May 2 when fumigant nematicides applied. 
     Soil temperature: Maximum, 84 F.; minimum, 73 F. at 4&#34; depth when the chemicals applied. 
     Planting dates: May 10 
     Treatment dates: Fumigants, May 2; Nemacur, May 10 
     Harvest dates: September 24 
     Weather conditions: Adequate rainfall for good yields 
     Unusual circumstances: 
     Progress: See Table P6-84. 
     
                                           TABLE P6A-84__________________________________________________________________________ Effects of three fumigant nematicides applied withmoldboard plow and single chisel on peanut production, 1984..sup.1                                  Number nematodes/                                  150 cm.sup.3 soil,                                  9/14/84                  Root-                      White   Vigor                                  Crico-                                       Meloido-Treatment and    Method of.sup. 2          Yield              %   knot                      mold                          Stand                              rating                                   nemella                                       gynerate (lb ai/A)    application          (lb/A)              SMK.sup.3                  index.sup.4                      hits.sup.5                          (5/21).sup.6                              (6/22).sup.7                                   ornata                                       arenaria__________________________________________________________________________Telone II 37.2    A     4640 ab              76.7                  4.3 bc                      3.0 b                          12.4 a                              2.5 bc                                  3097 a                                       932.5 bVorlex 38.4    A     2975 c              74.0                  9.5 a                      18.0 a                          13.3 a                              2.3 c                                  1652 bc                                       2297.5 aTelone II 37.2    B     4852 ab              79.7                  2.9 cd                      3.3 b                          11.6 a                              3.5 a                                  2782 ab                                       435.0 bVorlex 38.4    B     4360 b              76.0                  3.4 cd                      3.8 b                          11.9 a                              3.0 a-c                                  1702 a-c                                       522.5 bSoilex CP 39.2    B     4476 b              78.3                  4.1 bc                      3.0 b                          11.3 a                              3.0 a-c                                  2597 ab                                       700.0 bNemacur 15 G 2.5    C     5064 a              78.7                  1.4 d                      3.3 b                          11.6 a                              3.3 ab                                  667 c                                       470.0 bControl        4325 b              77.0                  6.2 b                      3.5 b                          12.9 a                              3.3 ab                                  1350 bc                                       1135.0 b__________________________________________________________________________ .sup.1 Data within same column followed by the same letter are not significantly different (P = 0.05) according to Duncan&#39;s multiplerange test. .sup.2 Method of application: A = applied in moldboard plow furrow 10&#34; deep spaced 8&#34; apart 8 days before planting, B = injected 10&#34; deep in row with single chisel 8 days before planting, C = applied in 12&#34; band over row, rototilled 2&#34; deep at plant. .sup.3 % sound mature kernel (SMK) determined from composit sample from four replications. .sup.4 Rootknot index based on rating of 0-10: 0 = no galling, 10 = 100% of roots and pods galled. .sup.5 White mold hits = number of hits per 50 ft row. One or more plants infected per ft of row is one hit. .sup.6 Stand = number of plants emerged per m of row. .sup.7 Vigor rating based on scale of 1-5: 1 = poor growth, 5 = excellent growth.