METHOD AND COMPOSITION FOR CONTROL OF NITROGEN-FIXING ANIMALS

Abstract: Animal pests capable of nitrogen fixation are controlled by treatment with a metal compound of either molybdenum or tungsten. Such metal salts are uniquely toxic to termites and shipworms in low dosages, and may be inorporated into direct control agents, termite baits or soil inoculants, for example, or may be incorporated with other ingredients in a wood treating dip or pressure treating composition for wood preservation.

Description: METHOD AND COMPOSITION FOR CONTROL OF NITROGEN-FIXING ANIMALS The present invention is in the field of methods and compositions for the control of animals capable of nitrogen fixation in general, and particularly for the control of termites and shipworms. While the present invention is broadly directed toward animals capable of nitrogen fixation, it is particularly useful in the control of termites. The prior art is generally cognizant of a wide variety of compounds which are useful either for introduction into wood for preserving the wood fiber from termite infestation, or for directly controlling termites. Wood infestation and destruction by termites is a widely recognized-problem, particularly in tropical and sub-tropical areas of the world, and much research has been directed towards methods arid compositions for controlling termite activity. Generally, in the prior art, it has been the practice to use either general organic insecticides or toxic metallic compounds to control or to kill termites. These Cosapositiolls may be utilized directly to control termites by incorporation in a bait or attractant composition, but are typically utilized by injection or saturation in wood members so as to preserve wood which may come in contact with termite colonies. Exemplary of the prior art illustrating the use of general or garlic insecticides against termites is the disclosure of U.S. Patent No. 3,070,495, which describes tile use of a decayed wood extract as a termite attractant so that the termites can be controlled by a conventional general oryanic insecticide, such as DDT, dieldrin, chlordane, parathion, malathion or others. Other examples are known in the art of packaging techniques for including such organic pesticides in baits, traps, or other devices intended to attract termites. The use of several metallic compounds have been proposed or disclosed for termite control. U.S. Patent No. 2,784,139 discloses a composition for preserving wood including, as a mycocidal ad insecticidal ingredient, one of a variety of metal compounds including chromated zinc chloride, copper sulphate, arsenic compounds, and mercury colapounds. Similarly U.S. Patent No. 2,886,486 discloses a wood impregnating compound including therein chromated zinc sulphate. More recently, the disclosure of U.S. Patent No. 3,832,463 illustrates the use of hexavalent chromium in a wood treating composition intended to preserve wood from microbial aird insecticidal activity. It has also been proposed, in accordance with the disclosure of U.S. Patent No. 3,993,752, to utilize an alkali metal cyanide added to a liquid fungicide including organic or inorganic sales of mercury, lead, tin, copper, or zinc to provide a wood treating composition having fungicidal and bactericidal properties. Further, it has been disclosed, in U.S. Patent No. 4,132,780, that certain azide and metal salt formulations, including salts of iron, aluminum, nickel, maganese, colbalt, zinc, tin, or magnesium are capable of being used to control fungi aid other micro-organisms. It has been proposed, in one known teaching in the prior art, to utilize molybdenum iii a composition claimed to have biological activity. In the disclosure of U.S. Patent No. 2,025,405, a method for producing a water soluble colloidal molybdenum compound contains valuable "pharmaceutical ad bacteriological" properties. In addition, U.S. Patents Nos. 3,290,343 and 3,317,571 disclose certain compounds including molybdenum which are recited to be biologically active having use as pesticides. It has been known and understood for some time that a very small number of animals, including termites and shipworms, are capable of nitrogen fixation, in a fashion aiialogous to the nitrogen fixation of legumes. The animals themselves actually do not fix nitrogen. Instead, it has been discovered that among the microflora living in symbiotic relationship in the gut of termites are some capable of nitrogen fixation and they supply nitrogen in a fixed form to the host termite for protein synthesis. For example, Benemann in "Nitrogen Fixation in Termites, Scieiice, Volume 181, page 164, July 13, 1973, discusses the phenomenon of nitrogen fixation in termites and suyyests that title nitrogen-fixing agent is the intestinal bacterial flora of the termites. It is assumed that these symbiotic bacteria in the termite gut play an essential role in the nutrition of these insects since the wood used as food for the termite is very low in nitrogen. Another pest species that lives in and feeds n wood is the shipworm, a mollusk that is responsible for. significant damage to wood in marine environments. The shipworm also supports large numbers of nitrogen fixing bacteria in its intestines, Carpenter et al., "Nitrogen Fixation in Shipworms", Science, Volume 187, pps. 551-552, 1975. It is known that alaollg the nitrogen-fixing bacteria symbiotic with legumes, the enzyme nitrogenase, which is the-exlzyme responsible for nitrogen fixation, requires several atoms of molybdenum to be effective. It has been disclosed iii literature that tungsten competes with molybdenum and may serve as an antagonist of molybdenum in the formation of this enzyme, Nagatani and Brill, "The Effect of Mo,- W, and V on the Synthesis of Nitrogenase Components in Azotobacter vinelandii", Bioch. et Biophys. Acta, 362, 160-166 (1974). Summary of the Invention The present invention is summarized in that a composition for control of nitrogen-fixing pests includes a pesticidal amouiit of an effectively soluable compound of a metal selected from the group consisting of molybdenum and tungsten. An object of the present invention is to also provide a method for the control of wood pests such as termites and shipworms aid for the preservation of wood in which wood is treated with a composition including a pesticidal amount of a metal compound wherein the metal is selected from a group consisting of molybdenum and tungsten. It is an object of the present invention to provide a highly effective composition for termite and shipworm control which is economical to utilize and effective in its application. It is also an object of the present invention to provide such a control composition for termites and shipworms to which the oryanisms have no avoidance mechanism such that they will not actively avoid treated material. Detailed Description of the Invention Broadly stated, the present inventon envisions a pest control agent for pests capable of nitrogeil fixation which may be administered directly to the pests, or which may be used to protect wood from termite or shipworm infestation, aNd which includes, as its active inyredient, a compound, preferably a salt, of either or both of molybdenum or tungsten. These metal salts of molybdenum and tungsten exhibit pesticidal activity in concentrations as low as 500 parts per million (ppm) of the metal ingredient. The concentrations of these metals may be reduced even lower if a more yradual rate of kill is acceptable and may, of course be increased to higher concentrations if it is economically feasible. The molybdeiium or tungsten compounds conveniently may be iiltroduced to the pests by treating the wood upon which pests would otherwise feed, or by inclusion into a pellet or other bait which is deposited in a location which the pests would frequent. It is envisioned, in particular, that salts of these metallic elements may be incorporated into wood treating dips or impregnating compounds which may be introduced under pressure iiito wood in a conventional treatment process to inhibit termite or shipworm feediny on that wood. The exact mechanism of molybdeiium and tungsten toxicity on these organisms is not presently completely understood. The toxicity of tungsten was investigated under the thesis that tungsten would be an antagonist for tile active metal cofactor of the enzyme nitrogenase, which is molybdenum. The enzyme nitrogenase is manufactured by the microflora in the gut of termites and shipworms. While the feeding of tungsten dosed cellulose to termites has proven toxic, it has been discovered unexpectedly in the course of the research on tungsten that small concentrations of molybdenum were equally, and, in some cases, even more toxic to termites than the dosages of tungsten. It is believed that either the termites, or more probably the microflora in their gut, include a biological "scavenging" mechanism specifically designed to isolate and absorb molybdenum from the environment This same mechanism should exist in shipworms which feed on a similar diet. Since molybdenum is normally a relatively rare element in the diet of wood-eating oryanisms, providing these organisms with an excess supply of dietary molybdenum appears to cause the scavenging mechanism to introduce such a quantity of molybdenum into the animal's yut that the organisms die of molybdenum toxicity. It is believed that the tungsten toxicity to termites may be due either to the antagonistic activity of tungsten on the nitrogenase enzyme or to the molybdenum scavenging mechanism which might also accumulate tungsten. It is known, for example, that in some nitrogen fixing bacteria the mechanisms for molybdenum uptake also accumulate tungsten, wMolybdenurl Accumulation and Storage in Klebiella pneunoniae and A. zobacter vinelandii, Pienkos and Brill, Jour. of Bact., 145: 2 pp. 743-751.It is to be understoou, however, that the hypothesis for the mechanism of toxicity of molybdenum and tunysten is unproven at this stable. It is also possible that other mechanism may be responsible for the molybdenum toxicity disclosed here. For instance, it is conceivable that the highly reducing characteristic of the microflora environment in the animal gut may cause metal salt precipitation in the gut which ay interfere with other metabolic processes. in order to give those skilled in the art a better understanding of this invention and appreciation of the advantages of the compounds formulated in accordance with the present invention, the following illustrative experimental examples are given: Example 1 The terinicidal toxicity of various molybdenum and tunysten compounds were compared against various controls by testiny of identical sets of 60 termite larvae which were isolated in separate vials. All of the termite larvae were of the species Reticulitermes flavipes and were gathered from the wild in and around the area of Ingham County, Michigan. Each of the groups of termites in the experiment were fed alpha-cellulose dosed with a solution containing the molybdenum, tungsten, or control salt dissolved in aqueous solution and formed into pellets. For low solubility compounds, a portion of the dosant was mixed as dry material in the pellets to complete the dosage amount. The pellets were, as indicated in the chart below, dosed with several test compounds. In each of the samples, the termites were observed over a period of thirty-two days or until the date at which 50% of the termites were killed due to chemical toxicity. Results of these experiments and observations are summarized in the following Table I: Table I Dosant to the Concentration Days to Published Alpha-Cellulose of Metal 50% Kill Solubility p.p.m. p.p.m. wt/wt) ¯¯¯¯¯¯¯¯ in grams/lOOcc 1120 (control) ?'32 CaSO4 (control) 3,000 (Ca) > 32 .209 at 30 0C no food (control) --- 22 - CaC12 (control) 2,600 (Ca) > 32 - MoO3 4,000 (Mo) 13 .049 at 28 C H2MoO4 5,000 (Mo) 13 .133 at 180C CaMoO4 3,000 (Mo) 22 .0050 at 250C Na2MoO4 5,000 (Mo) 13 39.38 at 28 0C Na2MoO4 500 (leo) 22 39.38 at 280C Na2MoO4 50 (Mo) > 32 39.38 at 280C FeMoO4 3,600 (Mo) 17 .0076 at 250C Na2W 4 9,000 (W) 16 57.5 at <RTI ID=7.11> OOC Na2W 4 90 (W) > 32 57.5 at 0 C Materials providing 50% mortality to the termites within the experimental period are considered to be active against termites. In the experimental samples in which a 50% kill was achieved during the 32 day span of the experiment, most of the remaining termites typically died shortly thereafter. Note that higher level of the toxic additives caused termite mortality well before the termites which were starved (no food control) died. The symptoms of the molybdenum toxicity to the termites included that the abdomens of the termites turned blue-grey after a relatively short period, i.e. three days, of feeding on the dosed cellulose samples. No such phenomenon was observed with control termites or termites feeding on tungsten dosed pellets. Also in the above experiment, in the sample of termites which were fed sodium molybdate at a concentration of 5000 p.p.m., the termites were also allowed access to pellets inoculated only with distilled water. The termites in this sample exhibited no avoidance of the molybdenum dosed pellets thus suggesting that termites would Iiot be capable of avoiding molybdenum treated wood or cellulosic baits containing molybdenum or tunysten in their environment. Example II To verify that the observed toxicity is attributable to molybdenum, and not simply to the presence of a metal salt, an additional test was run with a variety of metal salts. Two samples each of fifty individual Reticulitermes flavipes worker larvae were fed kraft paper pellets dosed with metal salts. The metal salt compounds were dosed onto the pellets by being dissolved in water and deposited on the paper. The temperature and environmental conditions were constant and the pellets were periodically moistened with water. Results of these tests for each of the following metal salts are summarized in Table II below: Table II Dosant Dosage (mg per Days to Percent 5 5 gram paper) 50% Kill Survival at 48 days NaNbO3 9.03 -- 95 NaBiO3 14.80 -- 88 None (Control) -- -- 91 NaVO3 6.50 -- 58 Na2B4O7 10H2O 19.80 8-10 0 CuCl2#2H2O 9.38 -- 81 Na2MoO4 #2H2O 12.5 24-28 1 Na2SnO3#3H2O 13.9 -- 89 CoCl2#6H2O 12.4 -- 83 Na2WO4#2H2O 17.30 37-49 19 NaCl 9.18 -- 91 Fe2(S04)3 3H2O 12.20 -- 93 SrCl2#6H2O 13.90 -- 88 FeCl3#6H2O 14.30 -- 90 MnCl2 4H20 10.30 -- 92 NiSO4#6H2O 13.30 -- 62 TiO4 4.37 -- 81 <RTI ID=9.13> NH4Al(S 4)2 12H2O 23.60 -- 92 MgSO4#7H2O 12.50 -- 90 BaCl2#2H2O 12.50 -- 87 Nal 7.83 17-24 18 Ce(S04)2 #4H2O 21.50 -- 92 NaTaO3 4.37 -- 88 LiCl 2.20 -- 86 ZnSO4 7H2O 15.00 -- 86 The amount of metal salt in each of the above samples was formulated to give an effective concentration of 1000 p.p.m. of metal in the termite food, with the exception of NaCl (dose tripled) and Fe2(S04)3 (dose cut by one-half). The kill rate of the boron compound was expected inasmuch as borate is a previously documented termiticidal (and yeneral insecticidal) agent. However, borate is very soluble and not amenable to easy methods for making insoluble, and thus its effectiveness in wood treatment is very limited. The use of molybdenum does-not suffer from such a limitation. Example III To verify that a wide variety of molybdenum compounds are effective, another test was run using a variety of molybdenum and one tungsten compounds. The method of dosing the compounds onto the termite feed, again kraft paper pellets, varied according to the solubility of the compound. The more soluable compounds were introduced entirely in aqueous solution, while for some of the less soluble compounds part of the dosage included dry material added to the pellets. The molybdenum disulfide, which is absolutely insoluable in water, and the molybdenum were ground and added to the pellets only in granular form. The amount of metal compound in the paper pellets was selected to give a concentration of 500 p.p.m. of metal in the sample, escept for the MoS2, which was at a dosage of 5000 p.p.m. A single sample of 60 termites was used for each sample, and the results are summarized in Table III below: Table III Dosant Number dead (of 60) Published at end of Four weeks Solubility in grams per 100cc H20 (control) 3 - Na2MoO4 20 39.38 (at 28 C) (NH4 )2Mo207 13 43 (at 25 C) H2MoO4 16 .133(at 180C) MoO3 11 .049(at 280C) Mo ore 18 - MoS2 0 0(effectively insoluble) NaWO4 26 57.5 (at OOC) FeSO4 0 - Na2Cr207 0 238 (at 0 0C) Again in this test the metal salts were dissolved in water <RTI ID=11.1> awld deposited on the paper in solution. The molybuelxunl ore, which was raw ore obtained from Climax Molybdenum Co., was unrefined ore from a sample designated 77-2A by Climax. The assay of the ore was represented to be .263% Mo and 2.158 FeS2. This test showed tat a variety of very soluble and marginally soluble molybdenum compounds, ad even the unrefined ore itself, are effective termicidal agents, while the virtually insoluble molybdenum disulfide apparently is not, at least under these conditions. Very few animals are capable of fixing any appreciable amounts of nitrogen gas from the atmosphere, other than termites aiid shipworms. To verify that this pesticidal effect related to nitrogen-fixation ability, samples of molybdenum and tungsten compounds were fed, in dosages lethal to termites, to other pests such a fire ants, cockroaches and bark beetles. These pest insects were not killed by these compounds thus demonstrating that they are not broadly toxic to insect species. It is also known that molybdenum and tungsten compounds are relatively non-toxic to plants and to other aiiimals, in contrast to many currently used termicidal agents which are broadly toxic to many organisms. Thus, it can be readily appreciated that metallic salts aiid other effectively soluble compounds of molybdenum and tungsten exhibit significant and unusual toxicity to termites through some mechanism related to the ability to fix nitrogen. While it is believed that the mechanism of this toxicity is related to the mechanism for molybdetium uptake to create nitroyellase enzyme for the fixation of nitrogen, as stated, it is also possible that the toxicity mechanism results because of the strong reducing activity of the microflora gut. It is to be understood, therefore, that the present invention is not limited to the mechanism for this toxicity which is discussed here, but is instead directed toward both a composition for the control of nitrogen fixing pests including molybdeiium or tungsten and a method for using these compositions to coiitrol pests regardless of the details of the mechanism by which they function. It is envisioned that this termite control composition can De utilized in any conventional wood treating composition already containing fungicidal or other preservative compounds. The inclusion of a small amount of a molybdenura or tungsten metallic salt or derivative would also ensure that the treated wood would be safe from termite and shipworm infestation. Alternatively, these metallic salts for pest control could be incorporated in cellulosic pellets or baits which could be placed in pre-selected locations adjacent to the wood likely to be visited by the pests. A quantity of cellulosic material, such as wood, paper, paperboard, paper or paperboard products, or cotton, needs merely to be inoculated with a dose of a molybdenum or tungsten compound, and left as a bait iii a location likely to be frequented by the pests. Alternatively, to protect wood structures such as housing, etc., molybdellum or tungsten compounds could be directly inoculated in the soil surrounding the structures. By use of such a bait, termites could be controlled in a structure regardless of whether or not the remaininy wood ill a structure to be protected was susceptible to treatment. It is to be understood that a preferred method for using the compositions of the present invention is to impregnate the compositions directly into the wood to be protected. Such impregnated wood would be resistant to both termite aiid shipworm infestation. To be effective as a wood impregnant, the molybdenum compound must be in a form that prevents it from being immediately solubilized when the wood is exposed to water. One method would be soak the wood in a highly soluble molybdenum (i.e. molybdate) solution under heat or pressure to introduce the compoulid into the wood. The the molybdenum would be rendered more soluble, as for example by reaction with sodium sulfide or other reducing agent. Wood with insoluble molybdenum impregnated therein would be particularly useful in iariiie applications where shipworms are a problem. An alternative approach to introduce an relatively insoluble molybdenum compound into wood is to use a suspension of an insoluble compound as very fine particles which can be forced into wood pores under pressure. Another approach would be to use an organic solvent to dissolve a relatively water insoluble molybdenum compound to carry the compound into the wood. It should be appreciated that a wide variety of concentrations of many molybdenum or tunysten compounds is possible within te spirit of the present invention as long as verifiable toxicity to termites and shipworms can be achieved. It is believed that the reasonable interpretation of the test data presented here is that any molybdenum or tungsten compound which is either effectively soluble in water or which otherwise makes its metal constituent biologically available to a pest when digested will be effective. By effectively soluble as used herein it is intended to mean compounds having some measurable solubility. By bioloyically available it is intended to mean compounds wherein the molybdenum or tungsten molecules are available for uptake by the host animals. From these parameters, it should be clear that a wide variety of salts and other compounds of each of these metals can be efficacious. It is also envisioned that such coii0position5 in accordance with the present invention could be effectively used as soil inoculants in or around structures to be protected to prevent termite encroachment upon the structures throuyh subterranean tunnelling. It is understood that the present invention is not limited to the particular embodiments disclosed and illustrated herein, but embraces all such modified forms thereof as come within the scope of the following claims.

Claims: CLAIMS: 1. A method of controlling animal pests capable of nitrogen fixation, which comprises using a pesticidal amount of at least one effectively soluble compound of molybdenum or tungsten. 2. A composition for use in the control of animal pests capable of nitrogen fixation, which includes a pesticidal amount of at least one effectively soluble compound, preferably a salt, of molybdenum or tungsten. 3. A composition as claimed in claim 2, which comprises a molybdenum salt present in the composition at a metal concentration of greater than 50 parts per million, and/or tungsten present in the composition at a metal concentration of greater than 90 parts per million. 4. A composition as claimed in claim 2 or 3, which comprises one or more of sodium molybdate (Na2MoO4), molybdic anhydride (MoO3), molybdic acid (H2Mo04), ferrous molybdate (FeMoO4), sodium tungstate (Na2WO4), di-ammonium molybdate (NH4)2Mo207, or unrefined molybdenum ore. 5. A cellulosic material such as wood, paper, paperboard, paper or paperboard products, or cotton, which has been impregnated with a composition as claimed in claim 2,3, or 4. 6. A method of controlling animal pests capable of fixing nitrogen, which comprises treating cellulosic material with a pesticidal concentration of molybdenum or tungsten or salts thereof. 7. A method according to claim 6, wherein the cellulosic material is treated with a composition as claimed in claim 2,3, or 4. 8. A method as claimed in claim 6 or 7, wherein the pests to be controlled are termites or shipworms. 9. A method for safeguarding a wood structure from animal pests capable of nitrogen fixation, which comprises treating the soil around the structure with a pesticidal concentration of molybdenum or tungsten or salts thereof. 10. The use of molybdenum or tungsten in the control of termites capable of nitrogen fixation.

Inventors: BRILL, WINSTON J., VON MEYER, WILLIAM C.
Applicants: AGRACETUS
Application year: 1983
Main classification: A01N59
IPC codes: A01N59, B27K3