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 argricultural 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 isothiocyanate 
     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, Georgia 
     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-limonene 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. 
     
           Peanut (Arachis hypogaea `Florunner`) D. W. Dickson and T. E. Hewlett Root-knot nematode; Meloidogyne Dept. of Entomology &amp; Nematology arenaria University of Florida Ring nematode; Criconemella Gainesville, Florida 32611 curvatum EVALUATION OF NEMATICIDES FOR MANAGING THE PEANUT ROOT-KNOT NEMATODE ON PEANUT, 1984: No. nematodes/250 cm.sup.3 soil Treatment and overall Methods of application &amp; Meloidogyne arenaria Criconemella curvatum rate per acre (active).sup.X rate per 1001. ft. row Yield lb/acre % Damage % SMK.sup.Y Value/acre Aug 10 Oct 9 Aug 10 Oct 9   Telone II 15.0 gal 7 days preplant, 2-chisels, 3,365a.sup.Z 2 70 $971  4 b 191de 86bcdefg 328bcdef  10 inches apart; 65 ml Telone II 15.0 gal 14 days preplant, 2-chisels, 3,332ab 3 69 944 10ab 211de 76bcdefg 276cdef 10 inches apart; 65 ml Vorlex 12.0 gal 14 days preplant, 2-chisels, 8 3,174abc 3 69 917 5ab 793ab 15fg 138f  inches apart.sup.ZZ ; 52 ml Telone II 12.0 gal + 14 days preplant, 2-chisels, 2,973abcd 1 74 884 30ab 110e 103bcdef 454abc Temik 15G 6.0 lb 10 inches apart + at-peg,  14 inch band; 52 ml + 49 g Vorlex 12.0 gal + 14 days preplant, 2-chisels, 8 2,919abcd 2 74 863 2b 864a 5g 150ef Furadan 15G 6.0 lb inches apart.sup.Z Z + at-peg, 14  inch band; 52 ml + 49 g Telone II 6.0 gal 14 days preplant, 2-chisels, 2,842abcd 2 71 832 38ab 246cde 140abc 196def  10 inches apart; 26 ml Chloropicrin 6.0 gal 14 days preplant, 2-chisels, 2,842abcd 1 73 850 4b 486bcde 67bcdefg 453abc  10 inches apart; 26 ml Untreated Control 2-chisels, 8 inches apart 2,793abcd 1 61 829 15ab 620abc 78bcdefg 346abcde Untreated Control 2-chisels, 10 inches apart 2,766abcd 3 64 776 17ab 367cde 132abcd 531a Telone II 12.0 gal 14 days preplant, 2-chisels, 2,717abcd 3 69 784 19ab 307cde 70bcdefg 512ab  10 inches apart; 52 ml Telone II 12.0 gal + 14 days preplant, 2-chisels, 2,690abcde 3 69 768 15ab 229cde 112abcde 378abcd Furadan 15G 6.0 lb 10 inches apart + at-peg, 14  inch band; 52 ml + 49 g Chloropicrin 3.0 gal 14 days preplant, 2-chisels, 2,624abcde 1 72 755 9ab 352cde 59cdefg 263cdef  10 inches apart; 13 ml Chloropicrin 9.0 gal 14 days preplant, 2-chisels, 2,467bcde 5 55 682 43a 752ab 78bcdefg 254def  10 inches apart; 39 ml Telone II 9.0 gal 14 days preplant, 2-chisels, 2,467bcde 8 65 688 26ab 337cde 193a 458abc  10 inches apart; 39 ml Busan 1020 30.0 gal 14 days preplant, 2-chisels, 2,412cde 5 68 679 16ab 576abcd 40efg 193def  8 inches apart; 130 ml Busan 1020 36.0 gal 14 days preplant, 2-chisels, 2,292de 5 71 662 37ab 465bcde 47defg 207def  8 inches apart; 156 ml Soilex C-17 15.0 gal 14 days preplant, 2-chisels, 2,129de 6 52 578 10ab 422bcde 148ab 382abcd  10 inches apart; 65 ml Telone II 15.0 gal at-plant, 2-chisels, 10 inches 1,851e 3 64 503 6ab 152e 50defg 502ab  apart; 65 ml .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. 
    
     
         __________________________________________________________________________SOIL FUMIGANTS COMPANY, INC.P. O. Box 7801 - Orlando, Florida 32854Tel. 305/293-8034BOCA WEST TEST PLOTSBELONOLAIMUS ONLYPRE-TEST, 11 DAYS, &amp; 34 DAYS AFTER INJECTION       SAMPLE NUMBER                                   #6             #2   #3         #5    C-17 +                                        #7           #10       #1    TEL- C-17 +                        #4   C-17 +                                   DIAZ-                                        TEL- #8  #9  TEL-NEMATODE    CHECK ONE  SAROLEX                        C-17 SAROLEX                                   INON ONE  C-50                                                 C-17                                                     ONE__________________________________________________________________________STING-BELONOLAIMUS PRETEST       32    32   24    12   48    52   68   24  60  7211 DAYS     24     4   20     8    8    12    4   12   4  1634 DAYS     52     8   24     8    4    24   28    8  36ROOT RESPONSE @       NONE  4 new                  NONE  15 new                             4 new ro                                   4 new                                        11 new                                             NONE                                                 4                                                     6 new11 DAYS           root 11/2 &#34;                        r 3&#34; 1&#34; long                                   4&#34; long                                        3&#34; long  1&#34; long                                                     11/2&#34; long             long       longVISUAL RE-  POOR  GOOD POOR  POOR POOR  GOOD GOOD POOR                                                 POOR                                                     GOODSPONSE @ 102 days 5&#39; of                 6&#39; of turf                                        8&#39; of turf   6&#39; of turf             turf__________________________________________________________________________     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% ↓__________________________________________________________________________              SAMPLE NUMBER              #11               #14            #17              C-17 + #12  #13   C-17 + #15 #16 C-17                                                     #18NEMATODE           DIAZINON                     CHECK                          C-50  DIAZINON                                       C-50                                           C-17                                               SAROLEX                                                     CHECK__________________________________________________________________________STING-BELONOLAIMUS PRETEST              32     36   36    36     12  16  80    4811 DAYS            0      48   12    8      16  16  56    2834 DAYS            16     4    12    0      0   8   44    84ROOT RESPONSE @ 11 DAYS              NONE   NONE NONE  NONE   6 new                                           5 new                                               NONE  NONE                                       3&#34; long                                           2&#34; longVISUAL RESPONSE @ 102 days              GOOD 8&#39;                     POOR GOOD 5&#39;                                GOOD 20&#39;                                       POOR                                           POOR                                               POOR  POOR__________________________________________________________________________ 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: Sept. 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     4857ab             80.0                 3.1a                     3.3a                         12.0a                             3.5b                                 2425a 530.0aSoilex 117.6   A     5162a             79.7                 3.9a                     3.3a                         12.0a                             4.3ab                                 1545a 422.5aControl       4552b             78.7                 5.9a                     4.8a                         13.3a                             4.5a                                 2052a 1475.0a__________________________________________________________________________ .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 chemicals applied. 
     Planting dates: May 10 
     Treatment dates: Fumigants, May 2; Nemacur, May 10 
     Harvest dates: Sept. 24 
     Weather conditions: Adequate rainfall for good yields 
     Unusual circumstances: 
     Progress: See Table P6-84. 
     
                                           TABLE P6A-84__________________________________________________________________________Effects of three fumigant nematicides applied with moldboard plow andsingle chisel 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 37.2    A     4640ab              76.7                  4.3bc                      3.0b                          12.4a                              2.5bc                                  3097a                                       932.5bVorlex 38.4    A     2975c              74.0                  9.5a                      18.0a                          13.3a                              2.3c                                  1652bc                                       2297.5aTelone II 37.2    B     4852ab              79.7                  2.9cd                      3.3b                          11.6a                              3.5a                                  2782ab                                       435.0bVorlex 38.4    B     4360b              76.0                  3.4cd                      3.8b                          11.9a                              3.0a-c                                  1702a-c                                       522.5bSoilex CP 39.2    B     4476b              78.3                  4.1bc                      3.0b                          11.3a                              3.0a-c                                  2597ab                                       700.0bNemacur 15G 2.5    C     5064a              78.7                  1.4d                      3.3b                          11.6a                              3.3ab                                  667c 470.0bControl        4325b              77.0                  6.2b                      3.5b                          12.9a                              3.3ab                                  1350bc                                       1135.0b__________________________________________________________________________ .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.