Compositions and methods of treating edible matter and substrates therefor

Abstract

There are provided methods of treating edible matter comprising applying a composition comprising performic acid to the edible matter or a substrate therefor. Other embodiments are also disclosed.

Claims

1. A method for reducing at least one of: a) edible matter decay, b) pathogen load on a substrate; the method comprising: providing an edible matter or a substrate; and contacting said edible matter or said substrate with a composition comprising an effective amount of a sanitizing agent, wherein said sanitizing agent consists of a) an oxidizing agent comprising hydrogen peroxide; and b) a plurality of carboxylic acids, a plurality of carboxylate salts thereof, or both; and wherein: said plurality of carboxylic acids comprises citric acid, propionic acid and lactic acid; a concentration of said plurality of carboxylic acids within said composition is from 10 ppm to 90%.

2. The method of claim 1, wherein said edible matter decay is selected from the group consisting of: loss from pathogen load, decomposing, sprouting, loss from a disease, rotting, dehydration, blackheart formation, loss from a higher organism or any combination thereof.

3. The method of claim 1, wherein said substrate is selected for the group consisting of: a growth medium, a propagation medium, a harvesting surface, a container, a storage surface, a transport surface, a packaging surface, a treatment surface, and a processing surface or any combination thereof.

4. The method of claim 1, wherein said contacting is selected from the group consisting of: spraying, submerging, fogging, dipping, and injecting or any combination thereof.

5. The method of claim 1, wherein said contacting is for a time sufficient for reducing at least one of: a) said edible matter decay, b) said pathogen load on the substrate.

6. The method of claim 1, wherein the method is applied to said edible matter at one more stages throughout the life-cycle of the edible matter, comprising: pre-seeding stage, growth, harvest, post-harvest, storage and transport.

7. The method of claim 1, wherein said method is for reducing of colony forming units (CFU) on said substrate or said edible matter by a factor of 10 to 100,000, as compared to non-treated substrate or edible matter.

8. The method of claim 1, wherein a concentration of said plurality of carboxylic acids within said composition is less than 3000 ppm.

9. A method for reducing at least one of: a) edible matter decay, b) pathogen load on a substrate; the method comprising: providing an edible matter or a substrate; and contacting said edible matter or said substrate with a composition comprising an effective amount of a sanitizing agent, wherein said sanitizing agent consists of a) an oxidizing agent comprising hydrogen peroxide; and b) a plurality of carboxylic acids, a plurality of carboxylate salts thereof, or any combination thereof; wherein: said plurality of carboxylic acids is selected from citric acid, propionic acid and lactic acid, and is at a concentration of less than 3000 ppm within said composition.

10. A method for reducing at least one of: a) edible matter decay, b) pathogen load on a substrate; the method comprising: providing an edible matter or a substrate; and contacting said edible matter or said substrate with a composition comprising an effective amount of a sanitizing agent, wherein said sanitizing agent consists of a) an oxidizing agent selected from the group consisting of: hydrogen peroxide, urea hydrogen peroxide, sodium peroxide, calcium peroxide, sodium percarbonate, ozone, sodium periodate, sodium persulfate, ammonium persulfate, sodium perborate, silver (II) oxide, chlorine dioxide, benzoyl peroxide, a ketone peroxide, a peroxydicarbonate, a peroxyester, a dialkyl peroxide, a hydroperoxide, a peroxyketal or any combination thereof; and b) phosphorous acid, a salt of phosphorous acid, or both.

11. The method of claim 1, wherein the w/w concentration of said oxidizing agent within said composition is from 8 to 30%.

12. The method of claim 1, wherein said composition further comprises a compound selected from the group consisting of: a surfactant, an additive, and a stabilizer or any combination thereof.

13. The method of claim 12, wherein said additive comprises: a base, a pH regulator, an organic additive or any combination thereof.

14. The method of claim 12, wherein said surfactant is selected from the group consisting of: a non-ionic surfactant, an anionic surfactant, a cationic surfactant and an amphoteric surfactant or any combination thereof.

15. The method of claim 12, wherein the w/w concentration of: a) said surfactant and b) said stabilizer within said composition is in a range from 0.1 to 10%.

16. The method of claim 1, wherein said composition is characterized by a pH in a range from 0.1 to 8.

Description

EXAMPLES

a. Preparation of Compositions

(1) Compositions described in the following Examples 1-2 were prepared in the following manner; where multiple ranges or multiple values are listed for a given component, corresponding component amounts were used or contemplated for use over the course of the trial. Oxidizing agents were mixed in a first composition with any stabilizers, metal ions, or chelators. Next, in a second composition, acids were mixed with deionized water, and the pH was elevated to the target level with one or more bases. Next, in separate compositions, any solid/powder ingredients were dissolved to liquid stages. Finally, all the above compositions were slowly mixed to create a mixture comprising all the ingredients except the performic acid source.

(2) The performic acid source was added to the mixture on-site, to generate the compositions comprising performic acid. The performic acid in the compositions was not stable, and the compositions were not active, for extended periods of time. That is, the performic acid concentration is not constant, as performic acid tends to decay to yield CO.sub.2. When prepared at ambient or warm temperatures (50-60° C.) the compositions comprising performic acid were applied to the edible matter within 1-2 hours after combining performic acid with the mixture; application of the compositions under these conditions was also done immediately after mixing. At lower temperatures (below 20° C.), the composition comprising performic acid was more stable, and was applied from 5 hours to up to two months after combining the performic acid source with the mixture.

Example 1—Controlling Silver Scurf

(3) The effect of compositions comprising performic acid on spore production of the silver scurf causal agent, Helminthosporium solani, on infected potato tubers was investigated. Silver scurf is widely considered to be a major source of quality loss in the fresh potato market. The four treatments for the study were: 1) 30 tubers were hand sprayed once with a 19:1 solution of tap water:performic acid composition (H.sub.2O.sub.2 7 wt. %, 2 wt. % phosphonic acid, 1 wt. % phosphoric acid, HEDP (etidronic acid) 0.5 wt. %, glycerin 0.5 wt. %, silver 100 ppm, formic acid 3 wt. %, surfactant 0.1 wt. %, remainder distilled water, pH 2.8) (Table 2, treatment “A”); 2) 25 tubers were hand sprayed once with distilled water (Table 2, treatment “C”); 3) 25 tubers were hung in plastic mesh onion bags and fogged with the same formula of performic acid composition approximately once a month from December to March and twice a month from March to June (Table 2, treatment “B”); and 4) a fourth bag of tubers were kept in a separate cold storage room for the duration of the test (Table 2, treatment “D”). The performic acid composition in the fogging applications was as described below in Table 1.

(4) TABLE-US-00001 TABLE 1 Silver Scurf Treatment Formulations Fogging Formulation Hydrogen peroxide (HP)  5% to 10% Phosphonic acid 1% to 5% pH regulators (caustic to adjust pH to range 1 to 5 soda and/or ammonia Silver 0, 50, 100, 250 or 500 ppm Formic Acid 1% to 7% Alcohol 0.5% to 3%   Benzoic Acid 0.1% Glycerin 1% to 5% HEDP 0.5% to 2%  

(5) Fogs were generated using ultrasonic foggers (compressed air combined with liquid, or electric ultrasonic foggers). The fogs were applied to potatoes at ratios of 200 cc to 1,000 cc per ton of potatoes at a holding temperature of from 7 to 9° C. at time periods of once per month to once every two weeks. Sprays were applied to potatoes at a volume of from 2 to 10 L per ton of potatoes with from 0.1% to 2% surfactant.

(6) Hand sprayed tubers were laid out on a tarp in a single layer and the test solution or water was misted onto the tubers until glistening. The tubers were allowed to dry for 5 minutes, turned over, and the other half was sprayed until glistening. Tubers were allowed to dry for an additional 15 minutes and then placed into plastic mesh bags. Hand sprayed tubers were hung in a storage container and kept at 7.5° C. and 92% room humidity (RH). The fogged tubers were placed in the same container. During each fog treatment in the container, the hand sprayed tubers were removed and kept in the dark at room temperature. The hand sprayed tubers where then returned to the container after all the fog had been exhausted from the container. Tubers treated with the fog were treated approximately nine times. After the last fog treatment tubers were washed and placed in plastic potato bags with holes. These bags were placed in potato boxes and incubated at 20° C. at 95% room humidity for 3 weeks.

(7) This temperature and humidity treatment is used to induce conidia production in H. solani. After incubation, the area of the tubers surface covered with H. solani spores was estimated by inspecting the tubers with a dissecting microscope. The results are summarized in Table 2 below.

(8) TABLE-US-00002 TABLE 2 Number of Tubers with 0, 1, and 5% surface covered by Helminthosporium solani spores. Silver Scurf Coverage Treatment 0% 1% 5% A. Treated Hand Spray 25 0 0 B. Treated Fogged 25 0 0 C. Untreated Hand Spray 18 11 1 D. Untreated Controls 24 3 2

(9) As can be seen in Table 2, there were no H. solani spores observed on the surface of the 25 fogged or hand spray treated tubers. Of the 30 tubers hand sprayed with distilled water, eleven had 1% of their surface covered with spores, one had 5%, and 18 had no spores.

(10) Three of the untreated tubers kept in cold storage had 1% of their surface covered with spores, 2 had 5%, and 24 had no spores.

Example 2—Controlling Potato Sprouting

(11) For part of a sprouting trial, compositions not comprising performic acid were applied to tubers (composition A), with tubers stored in a separate storage locker serving as an additional control. After several months, compositions comprising performic acid (composition B) were applied to the potatoes. The applied compositions were as described in Table 3.

(12) TABLE-US-00003 TABLE 3 Sprouting Compositions Composition A Composition B Hydrogen peroxide 7%  5% to 10% Phosphonic acid 3% 1% to 5% HEDP (HP stabilizer) 1% 0.5% to 2%   Silver 50 ppm 0, 50, 100, 250 or 500 ppm Benzoic Acid 0 0.1% Surfactant 0 0% to 2% Sulfuric Acid 0.5% to 2%   Stabilizer (Solvay) about 1% Glycerin 0.5% to 5%   Pure Formic Acid 0 1% to 9% D.I. water qs. qs pH regulators (caustic sufficient to sufficient to raise pH soda and/or ammonia) raise pH pH 2.8 2.8

(13) A fog was applied at ratios of from 200 cc to 1,000 cc per ton of potatoes with an ultrasonic fogger (compressed air plus liquid) at a holding temperature of 3 to 4° C. at time intervals ranging from once a month up to every two weeks from 14 Feb. 2010 to May 2010.

(14) The compositions were also applied to the potatoes by direct spray with the compositions described, with and without formic acid and with and without phosphoric acid. In spraying applications, the compositions were diluted at a ratio of 1:9 with tap water and applied at a volume of 2-10 liters per 1 ton of potatoes with or without 0.1%-2% surfactant on the cleaning, sorting and packing line. The results are summarized in the following 4 and 5.

(15) TABLE-US-00004 TABLE 4 Treated Potatoes at 38° F. MEAN TUBER RATING* POTATO Nov. Dec. Dec. Dec. Jan. Feb. Mar. VARIETY 12 1 15 29 12 23 23 W2310 0.9 0.9 1.5 1.8 2.1 2.2 2.1 Blazer 0.2 0.3 0.2 0.1 0.1 0.1 0.0 Canela 0.1 0.0 0.0 0.0 0.0 0.0 0.0 Goldrush 0.5 0.4 0.2 0.1 0.1 0.1 0.1 Norkotah 0.1 0.1 0.0 0.0 0.0 0.0 0.1 Silverton 1.1 1.1 1.0 1.0 0.7 0.5 0.2 *0 = no sprout; 1 = peeping to 1 mm; 2 = 1-5 mm; 3 = >5 mm

(16) TABLE-US-00005 TABLE 5 Untreated potatoes stored at 55° F. POTATO MEAN TUBER RATING* VARIETY Nov. 12 Dec. 1 Dec. 15 Dec. 29 Jan. 12 Jan. 26 Feb. 23 Mar. 23 W2310 0.5 0.7 0.8 1.4 2.5 2.9 3.0 Blazer 0.2 0.4 1.0 1.7 2.1 2.3 2.3 2.3 Canela 0.1 0.1 0.0 0.0 0.2 1.2 2.9 3.0 Goldrush 1.0 1.4 2.3 2.9 3.0 3.0 3.0 Norkotah 0.1 0.0 0.1 0.3 1.0 2.4 3.0 Silverton 1.8 2.0 2.3 2.8 2.9 2.9 3.0 *0 = no sprout; 1 = peeping to 1 mm; 2 = 1-5 mm; 3 = >5 mm

(17) As can be seen in above Table 5, all varieties of potatoes, other than Blazer, reached an unacceptable rating of 3 by February 23 without treatment. In contrast, the treated samples (Table 4) suppressed sprouts in all varieties with the addition of a peroxide treatment (composition A), and then kept the same or better score following subsequent treatments with the inventive composition (composition B). For example, the W2310 and Silverton varieties unexpectedly showed a lower score following the formic acid treatment, indicating a reduction in the sprouting of the tubers.

Example 3—Citrus Treatment

(18) The effect of performic acid compositions was studied on citrus fruit. To prevent decay in citrus during storage, generally, people have applied fungicides, such as Imazalil and thiabendazole, during packaging and waxing to treat the citrus fruit. However, as fungicides can be toxic, many countries have instituted limits on the levels of such agents in edible matter. For example, the U.S. limits the level of Imazalil to 10 ppm. There is a need for reducing the levels of potentially toxic substances in citrus and/or replacing such materials with environmentally friendly and safe products.

(19) Approximately 1000 mandarin oranges were treated shortly after harvest with compositions comprising performic acid, water, or an Imazalil composition, and then stored at 2° C. After 22 days, the number of rotten fruits, and the percent decay were assessed. A second trial was conducted with ten tons of mandarin oranges treated with a performic acid composition or Imazalil and stored and then stored at 2° C. The study was repeated with Red Grapefruit. The compositions comprising performic acid and the manner of applying the compositions varied throughout the course of the study within the parameters summarized in Table 6.

(20) TABLE-US-00006 TABLE 6 Performic Acid Composition Hydrogen peroxide 2% to 20%* Phosphonic acid 1% to 10%** pH regulators (caustic to raise pH to range of 1 to 5 soda and/or ammonia) Surfactant 1% to 2%*** formic acid 1% to 15%**** Silver 0 ppm, 50 ppm or 100 ppm *depending on state of contamination: 4% to 8% for low state of contamination **depending on state of contamination: 1% to 5% for low state of contamination ***depending on state of contamination: 0.1% to 1% for low state of contamination ***depending on state of contamination: 1% to 5% for low state of contamination

(21) The compositions were applied to the citrus at room temperature with a fine spray of the performic acid containing composition and then treated either a) with a drain wash of water (either cold or heated to 55° C.) with a 1:9 dilution in tap water of the composition without formic acid, or b) with a drain wash of water (either cold or heated to 55° C.), followed by a fine spray at room temperature with a formulation identical to the performic acid formulation but without formic acid. Thus, the methods of applying in this study were:

(22) a. Application of the performic acid containing composition at room temperature with fine spray, then treatment with a drain wash of cold water, and then a fine spray at room temperature with a formula without formic acid (i.e. without the performic acid source)

(23) b. Application of the performic acid containing composition at room temperature with fine spray, then treatment with a drain wash of heated water (to about 55° C.), and then a fine spray at room temperature with a formula without formic acid

(24) c. Application of the performic acid containing composition at room temperature with fine spray and then treatment with a drain wash of cold water that contained the formula at a diluted state at a ratio of 1:9 but without formic acid

(25) d. Application of the performic acid containing composition at room temperature with fine spray and then treatment with a drain wash of heated water (to about 55° C.) that contained the formula at a diluted state at a ratio of 1:9 but without formic acid

(26) All treatments were conducted at a total rate of 5-20 liter of formula per ton of different Citrus varieties. The results are summarized in Table 7, below.

(27) TABLE-US-00007 TABLE 7 Treated Citrus Fruit Days after No. Treated No. Rotten % Fruit treatment Treatment Fruits Fruits Decay Mandarin 22 Water 1008 32 3.17 Orange Imazalil 864 59 6.8 Performic acid 1008 7 0.6 composition Mandarin 46 Imazalil 7140 125 1.75 Orange Performic acid 7140 109 1.51 composition Red 35 Water 3575 167 4.67 Grapefruit Performic acid 3575 41 1.14 composition

(28) As can be seen in the above Table 7, the inventive method resulted in a lower level of decay in both mandarin oranges and Red Grapefruit, with reduced levels of chemical residue, in comparison to the prior art fungicidal treatment or water treatment.

Example 4—Seed Treatment

(29) Several compositions were prepared, as described in Table 8 below (percentages are given in weight percent), and applied to seeds.

(30) TABLE-US-00008 TABLE 8 Seed Treatment Compositions Composition Ingredients Control 9 8 7 6 5 4 3 2 1 H.sub.2O.sub.2 (%) 10 10 10 10 5 10 10 10 10 10 H.sub.3PO.sub.3 (%) 3 1 1 3 1 1 1.5 1.5 2 3 (COOH).sub.2 (%) 1 1 1.5 HCOOH (%) 3 3 1 1 1.5 H.sub.3BO.sub.3 (%) 1 ZnSO.sub.4 (%) 0.01 CUSO.sub.4 (%) 0.01 Ag (ppm) 250 250 250 250 250 250 250 250 500 250 Benzoic Acid (%) 0.10 Sorbic Acid (%) 0.10 Glycerin (%) 2 2 2 2 HEDP (%) 0.5 0.5 0.5 1 1 1 1 1 0.5 Alcohol (%) 2 Surfactants 0.10 + +

Example 5—Testing Stability of Hydrogen Peroxide Solutions in Soil Treatment

(31) 100 g of Loess soil from a potato field in the Negev were mixed with 40 ml water, 10.7 g H.sub.2O.sub.2 and Bayhibit® AM (2-phosphonobutane-1,2,4-tricarboxylic acid, up to 0.5% of the final solution) from a European source. The solution was checked as-is and the H.sub.2O.sub.2 concentration in the solution (before mixing with the soil) was 7.1%. The theoretical concentration of hydrogen peroxide in the mixture with the soil was 0.5% H.sub.2O.sub.2. Another sample was taken after 60 seconds of mixing with the soil and the H.sub.2O.sub.2 concentration was 1.1%; apparently the solution was not homogeneous, as there was effervescence in the solution. After 15 minutes the H.sub.2O.sub.2 concentration in the mixture was 0.51%, after 30 minutes the H.sub.2O.sub.2 concentration was 0.4% and after 60 minutes the H.sub.2O.sub.2 concentration was 0.19%. This procedure was repeated and parallel titrations of the H.sub.2O.sub.2 concentration were conducted; identical results were obtained.

(32) The procedure was repeated again, again using 100 g Negev Loess soil, 40 ml water, 10.7 g H.sub.2O.sub.2 solution with HEDP (etidronic acid) from a Chinese supplier. The theoretical concentration of H.sub.2O.sub.2 in the new mixture was 0.5%. The specific weight of the mixture was about 1.2. After 60 seconds of stirring the concentration of hydrogen peroxide was 0.661% (apparently the solution is not homogenous), after 15 minutes the H.sub.2O.sub.2 concentration was 0.510%, after 30 minutes the H.sub.2O.sub.2 concentration was 0.357%, after 60 minutes the H.sub.2O.sub.2 concentration was 0.2%. The solution was then left overnight without stirring; the H.sub.2O.sub.2 concentration in the morning was 0.02%.

Example 6: Stability of Phosphonic Acid in Contact with Hydrogen Peroxide

(33) 250 ml solutions were prepared, each containing 10% H.sub.2O.sub.2 and 10% phosphonic acid; these were kept in an incubator at 55° C. and at room temperature

(34) TABLE-US-00009 H.sub.2O.sub.2 concentration, wt. % Time at room temperature at 55° C. 0 minutes 11.1% 11.1% 15 minutes 11.1% 10.9% 30 minutes 10.7% 60 minutes 11.0% 10.7% 120 minutes 11.0% 10.9% 240 minutes 10.6% 360 minutes 10.8% 10.7% 24 hours 10.8%  9.9% 48 hours 10.3%  9.9% 168 hours 10.3%  6.4%

Example 7—Stability

(35) A concentrated aqueous 20% H.sub.2O.sub.2 solution was prepared containing H.sub.2O.sub.2 20%, phosphonic acid 8.0%, phosphoric acid 2.0%, glycerin 6.0%, silver 300 ppm. The H.sub.2O.sub.2 concentration was checked: 20.1%. A portion of the solution was placed in an incubator at 55° C. and a portion was stored at room temperature. To 95.5 g of the solution at 55° C. were added 4.5 grams of HEDP from a European supplier. The solution was checked for the H.sub.2O.sub.2 concentration therein:

(36) TABLE-US-00010 Concentration Concentration Concentration Day of H.sub.2O.sub.2 of H.sub.2O.sub.2 of H.sub.2O.sub.2 % at of % at 55° C. % at 55° C. room temperature test without HEDP with HEDP without HEDP 1 20.1 16.8 21.0 2 17.9 15.0 20.9 7 4.0 6.5 19.2 8 3.4 5.1 18.2

Example 7—Citrus Treatment Compositions

(37) While mixing with a mixer were added, in order, 75 g phosphonic acid; 700 g distilled water; approximately 83.5 g 47% sodium hydroxide carefully and slowly while mixing until a pH of 2.7 was reached (this resulted in an exothermic reaction which heated the solution); 10 g active material (STEPFAC 8182, a phosphate ester of an alkyl polyethoxyethanol that acts as a wetting agent); the solution was allowed to cool almost to room temperature; to the cooled solution were added 100 g 50% hydrogen peroxide into which had been mixed 5.7 g of 100 ppm silver solution; distilled water (approximately 13 g) was added to top off the amount to 987 g.

(38) At this point 500 g of the solution were poured off to a bottle to be used in the “hot” solution. The night before the experiment, 12.5 g formic acid were added to the remaining 487 g of solution to obtain 500 g of mixture to be used to prepare a “cold” solution.

(39) To prepare the “cold” solution; 4.5 liters of tap water at room temperature were mixed with the 0.5 liter solution; to prepare the “hot” solution, 4.5 liters of water at 56° C. were mixed with the 0.5 liter solution.

Example 8—Treatment of Citrus

(40) Five liters for use in a cold liquid wash were prepared, containing 0.1% silver solution (equivalent to 100 ppm silver), 7.5 wt. % phosphonic acid, 5 wt. % hydrogen peroxide, 0.1 wt. % alkyl glycoside surfactant, 2.5 wt. % formic acid, and the remainder water; the solution was prepared by mixing the ingredients in the order listed.

(41) Similarly, 5 liters for use in a hot liquid were prepared, containing 0.1% silver solution (equivalent to 100 ppm silver), 7.5 wt. % phosphonic acid, 5.0 wt. % hydrogen peroxide, 0.1 wt. % alkyl glycoside surfactant, and the remainder water; the solution was prepared by mixing the ingredients in the order listed.

(42) Prior to use, each of the two 5 liter solutions was diluted in 20 liters of tap water; a white precipitate formed.

(43) The efficacy of the solution was tested as follows: 150 kg of mandarins were divided into mesh bags and then sequentially submerged and shaken in the cold liquid so that each bag had the same contact time with cold liquid (about 60-90 seconds from initial immersion until the bag reached the next station in the production line). Next, each bag was submerged for about 30 seconds at 50° C. in the hot solution. The bags with the mandarins were then placed in a large container, from which they were transferred to the production line. At the next station they were passed through a dehydration cell, in which they were blown with hot air, after which they were waxed, hand sorted and packed in 10 cartons of 16 kg each. They were then palleted with an untreated control group and placed in cold storage (about 4±2° C.) for 3 weeks. The results in terms of percentage of rotten fruits (17 fruits out of 60 boxes, each box containing about 120 fruits) was about the same (21 fruits out of 60 boxes) as the old commercial process already in use on that particular production line for limiting rotting.

Example 9

(44) The goal was to form 20 liters of concentrated solution with the addition of a surfactant and to compare the activity of this surfactant-containing material to the activity of material without a surfactant. To a 1% phosphonic acid solution was added silver to a concentration of 2 ppm. A solution of 50% NaOH was mixed in until the pH of the solution was 3.8. A portion of this was separated and to that portion was mixed in an alkyl glycoside surfactant to a concentration of 0.1%. To compare the effects of the two solutions, 3 sweet potatoes were sprayed 7 times at intervals of 15-20 minutes with the non-surfactant solution and 3 sweet potatoes were sprayed 7 times with surfactant-containing solution; the vegetables were sprayed until dripping, then allowed to dry before being sprayed again. The effect of spraying was checked afterward; the treatment significantly improved shelf life and appearance. It was noted that there was a problem with foaming in the nozzles of the sprayer.

Example 10

(45) The goal of this experiment was to prepare 1.5 liters of a solution containing 0.1% silver, 7.5% phosphonic acid and 5.0% hydrogen peroxide; the solution could then be 5-fold diluted prior to use. Into 1155 g of water were mixed 112.5 g phosphonic acid; the pH value of the solution at this stage was 1.2. The pH value was raised to 2.5 by addition of 50 ml of 50% sodium hydroxide solution with mixing. This was an exothermic process. Into the resulting hot solution was added 7.5 g surfactant (alkyl polyglycoside), mixed until fully dissolved. After allowing to cool, to the solution were added 150 g of 50% 1-1202 in which was dissolved 8.6 g stabilizer-containing silver solution. This yielded approximately 1500 ml of solution, which was divided into two bottles of 750 ml each. To one of the bottles were added 18.75 g of formic acid. The H.sub.2O.sub.2 concentration before addition of formic acid was 5.3%, and after addition of formic acid, after 24 hours at room temperature, the H.sub.2O.sub.2 concentration was 5.1% (theoretically 5.15% after addition of formic acid).

Example 11—Solutions for Treatment of Sweet Potatoes

(46) An aqueous solution containing 1 wt. % phosphonic acid, 0.5 wt. % or 0.25 wt. % glycerin, and 0.5 wt. % formic acid was prepared and sprayed seven times on sweet potatoes. In comparison to untreated controls, the sweet potatoes obtained had a longer shelf life and an improved appearance.

Example 12—Solutions for Arresting Sprouting of Potatoes Post-Harvest

(47) The following table list amounts of ingredients to be mixed to prepare one liter of solution

(48) TABLE-US-00011 Sol’n 1 Sol’n 2 Sol’n 3 Sol’n 4 Sol’n 4A H.sub.2O.sub.2 50% 116 g 116 g 116 g 116 g 116 g solution H.sub.3PO.sub.3, 95% 30 g 30 g 30 g 30 g 30 g solution Silver Sol’n 0.57 g 0.57 g 0.57 g 0.57 g 0.57 g (Stabiliser), 100 ppm HEDP, 50% 8.3 g 8.3 g 8.3 g 8.3 g sol’n Benzoic Acid 1.2 g 1.2 g 1.2 g 1.2 g Surfactant, 1 g 1 g 1 g 100% sol’n H.sub.2SO.sub.4, 98% 10 g 10 g 10 g sol’n Glycerin 5 g 5 g 5 g 5 g 5 g 100% H.sub.2O 788.9 g 788 g 778 g 786.2 g 778 g Formic acid, 50 g 50 g 50 g 50 g 50 g 95% sol’n

(49) Solutions 1 and 3 were prepared. The solutions were prepared without raising the pH and without formic acid; before use it is necessary to add to each bottle 40 ml (50 g) of 95% formic acid.

(50) Solution 1: H.sub.2O.sub.2 concentration before addition of formic acid was 7.4%, pH was not raised. Solution 2: not prepared. Solution 3: H.sub.2O.sub.2 concentration before addition of formic acid was 7.3%, benzoic acid was not added (doesn't dissolve in the solution), surfactant (alkyl polyglycoside) was added, the pH was not raised.

(51) Solution 4: formic acid was added immediately during preparation, pH was not raised, surfactant was not added, H.sub.2O.sub.2 concentration immediately after addition of formic acid was 7.03%. The solution was transferred to a closed bottle and the rate of performic acid formation checked. After 90 minutes the solution in the bottle was checked, the bottle expanded slightly, and the H.sub.2O.sub.2 concentration was 6.6%, i.e. a 5.7% drop in concentration. H.sub.2O.sub.2 concentration was still 6.6% after four days.

(52) Solutions 1 and 4 were sprayed on young potatoes. Results versus control: with solution 1, potatoes gained a brown tint (it should be noted that solution 1 was sprayed as-is without dilution with formic acid, i.e. the H.sub.2O.sub.2 concentration was 7.4%). With solution 4, the tint of the potatoes was browner than the control but less brown than with solution 1 (note that the concentration of the H.sub.2O.sub.2 at the time of spraying was 6.6%).

(53) After 3 days on the potatoes that were sprayed with the aforementioned solutions there was observed a blackening of the sprouts, in parallel these potato skins appeared as if they had undergone glazing. Since the goal was to find a concentration that would cause the aforementioned blackening but not glaze the skin, to 200 g of solution 4 were added 1.5 g glycerin and 48.5 g water.

(54) Solution no. 5 was prepared containing 5.56% H.sub.2O.sub.2, 2.4% phosphoric acid, 100 ppm silver, 0.8% sulfuric acid, 4.0% formic acid, and water to complete to 100%. Phytotoxic injuries were observed on the potatoes that were sprayed with solution 5. Solution 5 was diluted two-fold to yield solution 5 A; solution 5 A was diluted two-fold to yield solution 5B. These solutions were sprayed on potatoes.

(55) Solution 6 was prepared; this is like solution 4 but the H.sub.2O.sub.2/formic acid ratio was 1:1 and not like solutions 4, 5 and their derivatives, in which the ratio was is 3:7. Solution 6:50 g 3.0% H.sub.2O.sub.2, 30 g 3.0% phosphoric acid, 0.57 g 100 ppm silver, 10 g 1.0% sulfuric acid, 30 g 3.0% formic acid, 880 g water to fill to 100%. The solution was left for 60 minutes after preparation and afterward sprayed on potatoes. Phytotoxic injuries were observed on potatoes, but these were attributed to the variety of potato used (Vivaldi) which is an incomplete skin variety in which skin injuries are known to occur. The experiment was discontinued.

Example 13—Preparation of Various Formulations

(56) In this example, the ingredients were mixed in the order recited; in cases in which hydroxide was added to an acidic mixture to raise the pH, this resulted in an exothermic reaction which raised the temperature of mixture.

(57) SpuDefender Classic (preparation of 2000 g): 60% hydrogen peroxide, 223 g (7% in the final preparation); 85% phosphoric acid, 82.3 g (3.5% in the final preparation); silver solution, 1.6 g (140 ppm silver in the final preparation); remainder distilled water (1683.1 g)

(58) Classic+F SpuDefender (preparation of 2000 g): 60% hydrogen peroxide, 223 g; 85% phosphoric acid, 82.3 g; silver solution, 1.6 g (140 ppm in the final preparation); 60 g formic acid (3.0% in the final preparation); remainder distilled water (1623.1 g).

(59) Classic+F/2 SpuDefender: after waiting 2 hours to allow formation of performic acid in the Classic+F SpuDefender solution, this solution was diluted to half strength by addition of an appropriate amount of water to yield the title solution.

(60) SpuDefender Natural (preparation of 2000 g): 60% hydrogen peroxide, 223 g; formic acid, 60 g (3.0% in the final solution); remainder distilled water (1705.4 g).

(61) SpuDefender Natural/2: after waiting 2 hours to allow formation of performic acid in the SpuDefender Natural solution, this solution was diluted to half strength by addition of an appropriate amount of water to yield the title solution.

(62) SpuDefender Joker: this was prepared like the Classic SpuDefender solution, except the concentration of phosphoric acid in the final preparation was 7.5%.

(63) SpuDefender Joker+F: this was like the Classic+F SpuDefender solution, except the concentration of phosphoric acid in the final preparation was 7.5%; it was prepared by mixing 45 g formic acid into 1455 g SpuDefender Joker.

Example 14—SeedGuard Solutions

Preparation of SOL1+ Solution

(64) TABLE-US-00012 SOL1+ SOL4 SOL3 SOL2 SOL1 % SOL5 % % % % Ingredients 7 This is a 7 7 7 7 H2O2 solution 3 H3PO3 5 which — 3 3 5 H3PO4 100 ppm was 100 ppm 100 ppm 100 ppm 100 ppm Ag None bought None None 1 None H2SO4 0.5 from 0.5 0.5 0.5 0.5 HEDP 0.1 Solvay 0.1 0.1 None None Surfactant 0.5 0.5 0.5 0.5 0.5 Glycerin None 3 3 3 None Formic acid pH 2.8 pH 2.8 pH 2.8

(65) Performic acid-containing solutions: A working solution of 3 liters at pH 2.8 having the following concentrations was prepared: 2% phosphonic acid, 2.0% BLS, 0.5% Glycerin, 0.1% alkyl polyglycoside.

(66) A concentrated solution of 1 liter was prepared containing 20% phosphonic acid; the solution should be diluted with 9 parts water to obtain a 2% phosphonic acid solution or with 19 parts water to obtain a 1% phosphonic acid solution. In addition to 20% phosphonic acid, the concentrated solution should contain 20% BLS, 2% H.sub.2O.sub.2, 5.0% glycerin, and 1.0% surfactant at pH 2.8.

Example 15— Solutions for Arresting Sprouting

(67) Volume of each solution was 500 ml. The following were prepared: (1) SpuDefender: 5% H.sub.3PO.sub.3; 5% H.sub.3PO.sub.4; 5% formic acid; 7% H.sub.2O.sub.2+5% formic acid; 4% H.sub.2O.sub.2+4% H.sub.3PO.sub.4; (2) ½N SpuDefender; 2.5% H.sub.3PO.sub.3; 2.5% H.sub.3PO.sub.4; 2.5% formic acid; 5% H.sub.2O.sub.2+3% formic acid; 3% H.sub.2O.sub.2+4% H.sub.3PO.sub.4; (3) ½N Solvay solution 4+ formic acid; (5) control with water; (6) control without water.

(68) An experiment was conducted using the following formulation: 7.0% hydrogen peroxide, 100 ppm of 17% silver solution, 1.0% sulfuric acid, 0.5% glycerin, 5.0% formic acid. The formulation was applied to table potatoes of different varieties: Lady Rosetta, Morris Pfeifer, Nicola.

Example 16—SeedGuard Solution

(69) TABLE-US-00013 SOL2+ % Ingredients 7 H2O2 H3PO3 H3PO4 100 ppm Ag 1 H2SO4 0.5 HEDP None Surfactant 0.5 Glycerin 5 Formic Acid

(70) In order to obtain a solution that would not be phytotoxic, this solution did not contain phosphonic or phosphoric acids, and the concentration of formic acid was increased from 3% to 5%. The formulation was applied by spraying (hand spray till dripping) to table potatoes of various varieties: Lady Rosetta, Morris Pfeifer, Nicola. Five days after application and storage at room temperature, the potatoes were checked. There was slight phytotoxicity in places on the potatoes where the applied formulation didn't dry (for example due to contact with other surfaces), but as desired there was blackening, shrinking and drying of the sprouts. In one of the potatoes of the Nicola variety new white pips were observed.

Example 17

(71) The following solutions, which according to results obtained were most effective, were prepared again:

(72) TABLE-US-00014 SOL5 SOL2/2 SOL4 Solvay % SOL2/2B % Ingredients 7 7 5 5 H.sub.2O.sub.2 3 3 H.sub.3PO.sub.3 — H.sub.3PO.sub.4 100 ppm 100 ppm 100 ppm 100 ppm Ag 1 None 0.5 0.5 H.sub.2SO.sub.4 Solvay's 0.5 0.5 0.5 HEDP Solvay's 0.1 None None Surfactant 0.5 0.5 None 0.5 Glycerin 3 3 3 3 Formic Acid pH 2.8 pH 2.8 0.10 Benzoic acid

(73) Sol2/2 Solution: contains formic acid, dilutions were made on-site shortly before use. SOL2B/2B solution contains formic acid but not glycerin, dilutions were made on-site shortly before use. SOL5 solution contains formic acid, dilutions were made on-site shortly before use. SOL4 solution: contains formic acid, dilutions were made on-site shortly before use; there were only 270 grams of solution.

Example 18—Solutions for Disinfecting Potatoes Before Placing them in Storage Rooms

(74) A solution containing (after dilution) phosphonic acid 0.8%, H.sub.2O.sub.2 1%, silver 15 ppm, formic acid 0.5% was prepared. In order to prepare the solution before dilution, to 4.8 liters of concentrated solution were added 0.2 liters of formic acid. Formulation for concentrated solution: phosphonic acid 8%, NaOH 100% (solid): approximately 4%; 50% H.sub.2O.sub.2, 20%; silver 150 ppm; formic acid: 5%; alkyl polyglycoside 0.2%, remainder distilled water to 100%

(75) Solution 1: 25 kg were prepared as follows: phosphonic acid, 2.68 kg of 70% solution; NaOH 47%, 2.0 kg; H.sub.2O.sub.2 50%, 2.5 kg; 17% silver solution 0.015 kg; 85% formic acid, 0.625 kg; alkyl polyglycoside 0.04 kg; distilled water 17.175 kg. Following this, 1.5 parts solution were diluted with 8.5 parts water. Concentration of materials after dilution: phosphonic acid: 1.12%, H.sub.2O.sub.2 0.75%, silver 16 ppm, formic acid 0.375%. In order to prepare the solution before dilution, to 3.0 kg of concentrated solution were added 75 g of formic acid.

(76) Solution 2: 25 kg were prepared as follows: phosphonic acid, 2.15 kg of 70% solution; NaOH 47%, 1.5 kg; H.sub.2O.sub.2 50%, 7.5 kg; 17% silver solution, 0.02 kg; 85% formic acid, 1.65 kg; distilled water 11.64 kg. Following this, 1 part solution was diluted with 9 parts water. Concentration of materials after dilution: phosphonic acid, 0.602%; H.sub.2O.sub.2, 1.5%; silver, 14 ppm; formic acid: 0.66%. In order to prepare the solution before dilution, to 2 kg of concentrated solution 141.3 g of formic acid were added.

Example 19—SeedGuard Solution for Treatment at Azata

(77) For preparing 25 kg of solution 1:

(78) TABLE-US-00015 Amount for 25 kg SOL5 kg (%) Ingredient 3.5 (50% solution) 7 H2O2 1.071 (70% solution) 3 H3PO3 0.0143 100 ppm Ag 0.208 (60% solution) 0.5 HEDP 0.02 0.08 Surfactant 0.125 0.5 Glycerin 0.250 H2SO4 0.400 (100% analytical solution) 1.6 NaOH 0.750 (85% solution) 3 Formic Acid 18.48 To 100 Aqua Dis pH 2.8
Stable Performic Acid Formulations

(79) Also provided in accordance with embodiments of the invention are stable formulations of performic acid. While such formulations, like the performic acid-containing formulations described in the examples above, may be formulated on-site just prior to use, for example by adding one of the reactive ingredients (e.g. H.sub.2O.sub.2, ozone, or formic acid) shortly before use, in some embodiments of the present invention the formulations may be formulated off-site and stored, without significant loss of performic acid during storage. Such stable formulations may be made in concentrated form, so that an end user may dilute the formulation with tap water, for example in ratio of concentrated formulation:water of 1:1, 1:2, 1:5, 1:10, 1:20, 1:30, 1:50, 1:70, 1:100, 1:120, 1:150, 1:200, 1:250, 1:300, 1:350, 1:400, 1:450, or 1:500, to obtain a working solution on-site. In addition, there are provided in accordance with embodiments of the invention pre-mixes to which one of the reactive ingredients may be added on-site to make the performic acid just prior to use. The following examples illustrate some such stable performic acid-containing compositions.

Example 20

(80) A composition was prepared containing H.sub.2O.sub.2, phosphonic acid which had been partly neutralized with KOH, formic acid, citric acid, and one or more alkyl polyglycoside surfactants; as will be appreciated by persons skilled in the art, performic acid is formed in situ. It was found that stable, concentrated solutions, which may later be diluted on-site just prior to use, may be formed when the concentration of H.sub.2O.sub.2 (or other oxidizer, e.g. ozone) in the mixture is approximately 15 wt. %, and the concentration of formic acid is approximately 10-12 wt. %; these figures reflect the weight percentages upon completion of the mixture, before performic acid formation has proceeded appreciably, as the percentages of both H.sub.2O.sub.2 (or other oxidizer) and formic acid in the mixture drop from their initial values as performic acid formation proceeds. Of course, if it is desired to make a less concentrated solution, e.g. by forming the performic acid on-site using already diluted ingredients, the weight percentages of the ingredients may be significantly lower. Also, while herein formic acid has been used as the performic acid source, it will be appreciated that other compounds or mixtures of other compounds may serve as performic acid sources, as has been described above.

(81) Regarding the concentrations of the ingredients prior to addition to the mixture, these concentrations may be as follows:

(82) H.sub.2O.sub.2: in some embodiments the concentration of H.sub.2O.sub.2, prior to addition to the mixture in which performic acid is formed, is at least 0.1%. In some embodiments the concentration is at least 0.2%. In some embodiments the concentration is at least 0.25%. In some embodiments the concentration is at least 0.3%. In some embodiments the concentration does not exceed 70%. In some embodiments the concentration does not exceed 50%. In some embodiments the concentration does not exceed 35%. In some embodiments the concentration does not exceed 20%. In some embodiments the H.sub.2O.sub.2 concentration, prior to addition to the mixture in which performic acid is formed, is from 0.1%-70%. In some embodiments the H.sub.2O.sub.2 concentration is from 0.2%-50%. In some embodiments the H.sub.2O.sub.2 concentration is from 0.25-35%. In some embodiments the H.sub.2O.sub.2 concentration is from 0.3-20%. In some embodiments the H.sub.2O.sub.2 concentration is from 3%-15%.

(83) Formic acid, when used: in some embodiments, the formic acid concentration is at least 3 wt. %. In some embodiments, the formic acid concentration is at least 5 wt. %. some embodiments, the formic acid concentration is at least 10 wt. %. In some embodiments, the formic acid concentration is not more than 70 wt. %. In some embodiments, the formic acid concentration is not more than 50 wt. %. In some embodiments, the formic acid concentration is not more than 35 wt. %. In some embodiments, the formic acid concentration is not more than 25 wt. %. Also, when formic acid is used, it has been found that using a 1:1 ratio of formic acid to hydrogen peroxide gives very stable results.

(84) Phosphonic acid, partly neutralized: in some embodiments, the phosphonic acid is partly neutralized before its addition to the mixture in which the performic acid is formed. In some embodiments, the partial neutralization is carried out using KOH. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 1. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 1.5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 1.7. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 2. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 2.5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 3. In some embodiments, the phosphonic acid is partly neutralized to a pH of not less than 3.5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 10. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 9. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 7. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 4.5. In some embodiments, the phosphonic acid is partly neutralized to a pH of not more than 4.0. In some embodiments, the phosphonic acid is first partly neutralized to a pH of 1-10. In some embodiments, the phosphonic acid is partly neutralized to a pH 1.1-9. In some embodiments, the phosphonic acid is partly neutralized to a pH of 1.2-7. In some embodiments, the phosphonic acid is partly neutralized to a pH 1.5-5. In some embodiments, the phosphonic acid is partly neutralized to a pH of 2-4.5. In some embodiments, the concentration of the phosphonic acid, prior to addition to the mixture in which performic acid is formed, is at least 0.1 wt. %. In some embodiments, the concentration is at least 0.2 wt. %. In some embodiment the concentration is at least 0.3 wt. %. In some embodiment the concentration is at least 0.5 wt. %. In some embodiment the concentration is at least 0.75 wt. %. In some embodiments, the concentration of the phosphonic acid, prior to addition to the mixture in which performic acid is formed, is not more than 70 wt. %. In some embodiments, the concentration is not more than 50 wt. %. In some embodiments, the concentration is not more than 35 wt. %. In some embodiments, the concentration is not more than 20 wt. %. In some embodiments, the concentration of the phosphonic acid, before addition to the mixture in which the performic acid is formed, is from 0.1%-70%. In some embodiments the concentration is from 0.2%-50%. In some embodiments the concentration is from 0.3-35%. In some embodiments the concentration is from 0.75%-25%. In some embodiments the concentration is from 0.5-20%. It will also be appreciated that in some cases, solid phosphonic acid, a salt thereof, or mixtures thereof, e.g. in granulated form, may be used. It will also be appreciated that the dissolution of solid phosphonic acid in water is endothermic, as is the dissolution of KOH, whereas the mixing of solutions of KOH and phosphonic or other dissolved acids is exothermic. Hence, persons skilled in the art will readily appreciate ways in which the order of addition of ingredients may be manipulated to achieved desired temperature effects.

(85) Citric acid: in some embodiments, the concentration of citric acid, prior to addition to the mixture in which the performic acid is formed, is at least 0.1 wt. %. In some embodiments the concentration is at least 0.15 wt. %. In some embodiments the concentration is at least 0.2 wt. %. In some embodiments the concentration is at least 0.25 wt. %. In some embodiments the concentration is at least 0.3 wt. %. In some embodiments the concentration is at least 0.5 wt. %. In some embodiments the concentration is not more than 50 wt. %. In some embodiments the concentration is not more than 40 wt. %. In some embodiments the concentration is not more than 30 wt. %. In some embodiments the concentration is not more than 20 wt. %. In some embodiments the concentration is about 15 wt. %. In some embodiments the concentration of the citric acid, before addition to the mixture in which the performic acid is formed, is from 0.1%-50%. In some embodiments the concentration is from 0.15-40%. In some embodiments the concentration is from 0.2-30%. In some embodiments the concentration is from 0.25-20%. In some embodiments the concentration is from 0.3-10%. It will also be appreciated, that as with phosphonic acid, citric acid may be provided in solid form and dissolved directly as needed.

(86) Alkyl polyglycoside surfactant(s): alkyl polyglycoside surfactants for agricultural use are known in the art. In some embodiments, the total concentration of alkyl polyglycoside surfactants in the mixture in which the performic acid is formed, is at least 0.001 wt. %. In some embodiments the concentration is at least 0.01 wt. %. In some embodiments the concentration is at least 0.1 wt. %. In some embodiments the concentration is at least 1 wt. %. It will also be appreciated by persons skilled in the art that other surfactants may be substituted for or used in addition to the alkyl polyglycoside surfactant(s). Such surfactants may include amphoteric surfactants, cationic surfactants, non-ionic surfactants, and anionic surfactants.

(87) The composition may be used as a disinfectant in and on food commodities, for soil, water, surfaces, equipment, air volumes, plant matter, and feed stocks, including disinfection and sterilization needs in all fields of application.

Example 21—More Compositions, e.g. for Arresting Sprouting in Potatoes

(88) In a manner similar to that of Example 20, various compositions were formed. In some cases, as noted in the table below, one or more ingredients, such as formic acid, were left out of the composition and only added on-site prior to use. In some cases, phosphoric acid was used in addition to or instead of phosphonic acid. Such compositions were found to be stable and efficacious, for example in arresting sprouting of potatoes.

(89) H.sub.2O.sub.2, phosphonic acid, citric acid, formic acid, surfactants: as in Example 19.

(90) Phosphoric acid: in some embodiments, the total concentration of phosphoric acid, prior to addition to the mixture in which the performic acid is formed, is at least 0.1 wt. %. In some embodiments the concentration is at least 0.2 wt. %. In some embodiments the concentration is at least 0.3 wt. %. In some embodiments the concentration is at least 0.5 wt. %. In some embodiments the concentration is not more than 70 wt. %. In some embodiments the concentration is not more than 50 wt. %. In some embodiments the concentration is not more than 35 wt. %. In some embodiments the concentration is not more than 20 wt. %. In some embodiments, the concentration of phosphoric acid, before addition to the mixture in which the performic acid is formed, is from 0.1-70 wt. %. In some embodiments the concentration is from 0.2-50 wt. %. In some embodiments the concentration is from 0.3-35 wt. %. In some embodiments the concentration is from 0.5-20 wt. %. In some embodiments the concentration is around 10 wt. %.

(91) TABLE-US-00016 Formulation option no. 1 2 3 4 5 6 7 8 9 H.sub.2O.sub.2 X X X X X ** ** ** — Phosphonic acid X — X X X X X X X Phosphoric acid — X X — X — — — — Citric acid X X X X X X — ** — Formic acid X X X ** ** X X X X Surfactant X X X X X X X X X

(92) In this table, X=included in the formulation, —=not included, and ** denotes a case in which the other ingredients are first mixed together, and then the indicated ingredient(s) is (are) added to this mixture on-site, not more than a few hours before use and in some cases immediately before use, optionally with heating of the formulation up to 80° C. for up to a few minutes.

(93) In cases where control of insects and microorganisms, at least in part, by means of a controlled atmosphere (i.e. having a higher than normal CO.sub.2 concentration) is desired, for example in storage rooms or silos, potassium bicarbonate may be added as well in order to generate additional CO.sub.2; such a method is particularly effective if application of the formulation will be made in a closed storage space via fogging or in the gas phase. Similarly, is gaseous ozone is used as an oxidizer to form performic acid in the gas phase, excess ozone can be supplied, as ozone itself may also help control pathogens.

(94) Although the use of KOH to control the pH has so far been found to be best, other potassium, ammonium and sodium agents as well as combinations of all of these may be used. For example, potassium metabisulfite or potassium permanganate may be used as a well; these are also known to function as preservatives.

Example 22—Compliance with British/European Standard BS EN 1276: 1997

(95) This is a quantitative suspension test to evaluate the bactericidal activity of chemical disinfectants and antiseptics used in food, industrial, domestic and institutional areas. A mixture (Mixture 1) containing 51.65 wt. % deionized water, 21.4 wt. % of 47% aqueous KOH solution, 11.8 wt. % of 85% formic acid solution, 14.1 wt. % of 70% phosphonic acid solution, 1.0 wt. % Dequest® 2010 (1-hydroxyethylidene-1,1-diphosphonic acid), and 0.05 wt. % alkyl glycoside was prepared. To four parts by weight of Mixture 1 were mixed one part of 50% H.sub.2O.sub.2 solution. For testing, this mixture was further diluted 100-fold in water.

(96) As is known in the art, EN 1276 defines a bactericidal product that has the capability to produce at least a 10.sup.5 reduction in the number of viable cells of the tested organisms, under defined experimental conditions. In the present case, a test suspension of bacteria in a solution of 0.3% bovine albumin (to act as an interfering substance) was added to the diluted product. The mixture was maintained at 20° C.-23° C. for 1 min. (the smallest of the recommended contact times according to the standard, which recommends longer contact times 10 or even 15 minutes), then the bactericidal action of the product was neutralized by the membrane filtration method, and the number of surviving bacteria was determined. Bacteria used were Escherichia coli (ATCC 8739), Staphylococcus aureus (ATCC 6538), Pseudomonas aeruginosa (ATCC 9027), and Enterococcus hirae (ATCC 10541). Each bacterial strain was maintained and counted by the pour plate method in accordance with EN 1276: 1997. Experimental conditions were as follows:

(97) TABLE-US-00017 Test Temperature 20° C. ± 0.5° C. Concentration of test product 1:99 Contact time 1 minute Interfering substance 3.0 g/l bovine albumin - dirty conditions Neutralizing Method Membrane Filtration Temperature of incubation 30° C. ± 1° C.

(98) The Membrane Filtration method was used for assessing the bactericidal effect of the product, and the results are summarized in the table immediately below.

(99) TABLE-US-00018 No. of Initial test Surviving bacteria Test suspension in 0.3% bovine Reduction in Organisms cells/ml (N) albumin (Na) viability (R) E. coli 4.5 × 10.sup.8 Vc 0, 0 >10.sup.5 ATCC 8739 Na <1.5 × 10.sup.2 Staphylococcus 1.1 × 10.sup.8 Vc 0, 0 >10.sup.5 aureus Na <1.5 × 10.sup.2 ATCC 6538 Pseudomonas 3.0 × 10.sup.8 Vc 0, 0 >10.sup.5 aeruginosa Na <1.5 × 10.sup.2 ATCC 9027 Enterococcus 1.0 × 10.sup.8 Vc 0, 0 >10.sup.5 hirae Na <1.5 × 10.sup.2 ATCC 10541 Vc = Viable Count; N = Number of CFU/ml of the bacterial test suspension; NA = Number of colony forming units (cfu)/ml in test mixture; R = Reduction in viability

(100) Validation and verification of the methodology: Validation tests are summarized in the table immediately below. Verification of the methodology for each test organism shows that: (a) the number of cfu/ml of the bacterial test suspension is between 1.5×10 and 5.0×10 cfu/ml (N in the table above); (b) the number of cfu/ml of the bacterial suspension is between 6.0×10.sup.2 and 3.0×10.sup.3 cfu/ml (Nv in the table below); (c) the number of cfu/ml of the neutralizer toxicity control (B in the table below) is equal to, or greater than 0.05 times the number of cfu/ml of the bacterial suspension (Nv in the table below); (d) The number of cfu/ml of the dilution-neutralization control (C in the table below) is equal to, or greater than 0.5 times the number of cfu/ml of the neutralizer toxicity control (B in the table below); (e) the number of cfu/ml of the experimental condition validation (A in the table below) is equal to, or greater than 0.05 times of the number of cfu/ml of the bacterial suspension (Nv in the table below).

(101) TABLE-US-00019 Membrane Bacterial Experimental Filtration test Bacterial Conditions Filtration Neutralization suspension Test Organism suspension Control Control Control (5.4.1.4) E. coli Vc: 311, 252 Vc: 247, 273 Vc: 227, 261 Vc: 258, 284 4.5 × 10.sup.8 ATCC 8739 Nv: 2.8 × 10.sup.3 A: 2.6 × 10.sup.2 B: 2.4 × 10.sup.2 C: 2.7 × 10.sup.2 Staphylococcus Vc: 163, 158 Vc: 123, 145 Vc: 130, 144 Vc: 197, 143 1.1 × 10.sup.8 aureus Nv: 1.6 × 10.sup.3 A: 1.3 × 10.sup.2 B: 1.4 × 10.sup.2 C: 1.7 × 10.sup.3 ATCC 6538 Pseudomonas Vc: 277, 307 Vc: 242, 281 Vc: 266, 303 Vc: 255, 278 3.0 × 10.sup.8 aeruginosa Nv: 2.9 × 10.sup.3 A: 2.6 × 10.sup.2 B: 2.8 × 10.sup.2 C: 2.6 × 10.sup.2 ATCC 9027 Enterococcus Vc: 163, 197 Vc: 117, 156 Vc: 133, 176 Vc: 90, 122 1.0 × 10.sup.8 hirae Nv: 1.8 × 10.sup.3 A: 1.4 × 10.sup.2 B: 1.5 × 10.sup.2 C: 1.1 × 10.sup.2 ATCC 10541 Vc = Viable Count; Nv = Number of CFU/ml of the bacterial suspension; A = Number of CFU/ml of the experimental conditions validation; B = Number of CFU/ml of Neutralizer Toxicity Control; C = Number of CFU/ml of the Dilution - Neutralization Control

(102) According to EN 1276, the tested composition possesses bactericidal activity in one minute at 20° C. under dirty conditions (3.0 g/I bovine albumin) for the tested reference strains.

Example 23—Compliance with British/European Standard BS EN 1650: 1998

(103) This is a quantitative suspension test to evaluate the activity of chemical disinfectants and antiseptics used in food, industrial, domestic and institutional areas against fungi, yeasts and molds. The same composition tested in Example 22 was tested in this case as well.

(104) As is known in the art, EN 1650 specifies a test method and the minimum requirements for anti-fungal, anti-yeast and anti-mold activity of chemical disinfectant and antiseptic products that form a homogeneous, physically stable preparation in hard water and that are used in food, industrial, domestic and institutional areas, excluding areas and situations where disinfection is medically indicated and excluding products used on living tissues except those for hand hygiene in the above-considered areas. In accordance with this standard, fungicidal activity is the capability of a product to produce at least a 10.sup.4 reduction in number of the vegetative yeast cells and mold spores belonging to the reference strains Candida albicans (ATCC 10231), Aspergillus niger (ATCC 16404) and Penicillium w.t. (wild type) under conditions defined by this standard.

(105) A test suspension of yeast cells and/or mold spores in a solution of interfering substance (bovine albumin, 3 g/1) was added to a prepared sample of the product under test diluted in hard water. The mixture was maintained at 20° C.-1° C. for 1 min+10 s (required test conditions). After this contact time, an aliquot was taken; the fungicidal action in this portion was immediately neutralized or suppressed by a validated method. The method of choice was dilution-neutralization. (If a suitable neutralizer could be found, membrane filtration was used.) The number of surviving fungi, yeast cells or mold spores in each sample was determined and the reduction in viable counts was calculated. (Additional and optional exposure times, temperatures, strains and interfering substances are specified in the protocol for the standard, according to which the selection of the contact time to be used is 15 min+/−10 s; the actual 1 minute time used in the present test is listed as the shortest of several optional additional contact times, which range up to 60 min+10s.)

(106) Experimental conditions: test temperature 20° C.+0.5° C.; concentration of test product 1:99, diluted in water; contact time 1 minute; interfering substance 3.0 g/I bovine albumin; neutralizing solution 30 g/I saponin, 30 g/l polysorbate 80, 1 g/I L-histidine, 1 g/I L-cysteine; incubation temperature 30° C.-1° C.

(107) Results are shown in the table immediately below.

(108) TABLE-US-00020 Validation Test Dilution Neutralizer Neutralization toxicity or control or Test procedure at Test Fungal Experimental filtration filtration test Fungal test concentration % organism suspension condition control control suspension (v/v) Candida Vc: 88.92 Vc: 85.93 Vc: 94.100 Vc: 80.83 10.sup.−5: 180.200 Vc 0.0 albicans Nv: 9.0 × 10.sup.2 A: 9.0 × 10.sup.2 B: 1.0 × 10.sup.2 C: 8.0 × 10.sup.2 10.sup.−6: 10.9 Na <1.5 × 10.sup.2 ATCC N: 1.9 × 1.0.sup.7 R >10.sup.4 10231 Aspergillius Vc: 154.162 Vc: 142.151 Vc: 150.165 Vc: 140.150 10.sup.−5: 280.300 Vc 0.0 niger Nv: 1.6 × 10.sup.3 A: 1.5 × 10.sup.2 B: 1.6 × 10.sup.2 C: 1.5 × 10.sup.2 10.sup.−6: 50.60 Na <1.5 × 10.sup.2 ATCC N: 2.9 × 10.sup.7 R >10.sup.4 16404 Penecillium Vc: 123.262 Vc: 101.93 Vc: 89.112 Vc: 107.107 10.sup.−5: 177.169 Vc 0.0 wild type Nv: 1.2 × 10.sup.3 A: 1.0 × 10.sup.2 B: 1.1 × 10.sup.2 C: 1.0 × 10.sup.2 10.sup.−6: 21.22 Na <1.5 × 10.sup.2 N: 1.7 × 10.sup.7 R >10.sup.4 VC = viable count; R = reduction in viability; Nv = number of cfu/ml of the fungal suspension; N = number of cfu/ml of the fungal test suspension; Na = number of cfu/ml in the test mixture; A = number of cfu/ml of the experimental condition validation; B = number of cfu/ml of the neutralizer toxicity validation or of the filtration control; C = number of cfu/ml of the dilution − neutralization test control or of the membrane filtration test control

(109) Thus according to EN 1650 the tested formulation possesses satisfactory fungicidal activity in 1 minute at 20° C. under dirty conditions (3 g/I bovine albumin) for the tested reference strains. In comparison, a commercial solution of peracetic acid (PAA, considered to be a very effective disinfectant and sterilizer) at 300 ppm (which is actually 100 ppm higher than the maximum permitted under the standard), tested against A. niger and

(110) Penicillium under the same test conditions, did not meet the standard. In fact, the formulation in accordance with the present invention was 10-100 times more effective than PAA in killing A. niger and Penicillium.

Example 24—Stability of Performic Acid Composition

(111) Aqueous solutions of 50% H.sub.2O.sub.2 and 42% citric acid were mixed in a 3:2 ratio, yielding a mixture with 30 wt. % H.sub.2O.sub.2 and 16.8 wt. % citric acid. This was then mixed in a 1:1 ratio with Mixture 1 from Example 22. The resulting mixture was tested for stability by measuring the concentrations of H.sub.2O.sub.2 and formic acid over time. The loss of H.sub.2O.sub.2 over three months of storage at room temperature was about 0.5%, i.e. the H.sub.2O.sub.2 concentration was nearly unchanged over this period.

Example 25—Soil Treatment

(112) Solutions were prepared according to the table below and used in amounts of 10.7 ml to treat 100 g of soil of pH 8 by mixing therein until a paste was obtained; except for trial 1, the soil was pre-wetted with 10.7 ml of water. Samples of soil were then taken for titration at the intervals shown. In the first table, units are wt. % unless noted otherwise.

(113) TABLE-US-00021 H2O2 H3PO4 HEDP Ag Stab Citric acid Benzoic acid EtOH Glycerol Trial 1 7 1.0 0.05 0.06 1000 ppm 1000 ppm 1 0 Trial 2 7 1.0 0.05 0.06 1000 ppm 1000 ppm 1 0 Trial 3 7 1.0 0.5 0.06 1000 ppm 1000 ppm 1 0 Trial 4 7 3.5 0.3 0.06 1000 ppm 1000 ppm 1 0 Trial 5 7 2.0 1.0 0.06 1000 ppm 1000 ppm 1 0 Trial 6 7 3.5 1.0 0.06 1000 ppm 1000 ppm 1 0 Trial 7 7 3.5 1.5 0.06 1000 ppm 1000 ppm 1 0 Trial 8 7 3.5 1.0 0.06 1000 ppm 1000 ppm 0 2 Trial 9 7 3.5 1.0 0.06 1000 ppm 1000 ppm 0 3 Trial 10 7 2.0 1.0 0.06 1000 ppm 1000 ppm 0 3 Time—minutes 0 5 10 20 30 Peroxide 0.73 0.20 0.08 0.01 0.004 titration—% 0.66 0.15 0.11 0.06 0.010 0.66 0.16 0.04 0.01 0.002 0.66 0.20 0.10 0.09 0.060 0.66 0.21 0.18 0.17 0.110 0.66 0.30 0.22 0.17 0.130 0.66 0.23 0.21 0.17 0.150 0.66 0.32 0.24 0.18 0.120 0.66 0.30 0.26 0.18 0.140 0.66 0.21 0.13 0.04 0.017

Example 26—Tests on Different Edible Materials and Substrates in Different Conditions

(114) The series of tables that follow below summarize numerous experiments that were conducted in accordance with embodiments of the invention. The following paragraphs explain the significance of the small letters that appear in the table.

(115) Composition preparation: compositions (solutions) containing performic acid were prepared as discussed in the preceding examples; in some cases the compositions included one or more of the following groups: Emulsifiers, chelating agents, lubricants, corrosion inhibitors, anti foaming agents, inorganic additives, organic additives, modifiers, promoters, synergists, activators, solvents, essential oils, other ingredients, pH regulators, bases, acids, wetting agents, surfactants, stabilizers, catalysts, oxidizers, and performic Acid sources.

(116) 1a=pre-preparation of the composition at the manufacturing site;

(117) 1 b=preparation by mixing on site

(118) Method of Application: As long as the compositions are in a liquid phase they may be applied them by immersing the substance to be treated in the compositions, and/or spraying the substance with the compositions, and/or creating a fog made of micro droplets using ultrasonic air pressure/liquid fogger and/or electric ultrasonic resonance, with or without heating, with or without ozone gas and/or ozonated water. The gas phase is introduced with a hot fogger with or without ozone gas.

(119) 2a Dipping; 2b pressure wash; 2c Spray; 2d Fog; 2e Gas; 2f mixing (when disinfecting water)

(120) Formula concentrations as H.sub.2O.sub.2 and or Ozone and or Peracetic Acid (PAA) content in the undiluted concentrated form: Oxidizing levels are measured rapidly on site with a certified field kit. As of today there is no certified field kit to measure the performic acid (PFA) levels, so the inventor developed a standard measuring constant that correlates to the oxidation rate: using a Reflectoquant Colorimeter (Merck), the concentration of H.sub.2O.sub.2 and/or PAA was measured; a correlation constant was calculated to enable computation of the PFA concentration. As a parallel control titration of the solutions as described by Swern at al. (Organic Peroxides 1 (1970) p. 501) was conducted in a laboratory.

(121) 3a 35%-70%; 3b 20%-35%; 3c 10%-20%; 3d 0.1%-10%

(122) Aims of Treatment:

(123) 4a Cleaning, Sanitizing, Disinfection, Sterilization—treatments are designed to dissolve and remove dirt and to act against microorganisms, including, among others, fungi, algae, mold, yeast, gram negative and gram positive bacteria, bacteriophages, viruses, amoebas, spores, protozoa, etc.; 4b Sprout arresting in potatoes—As well as for onion, garlic, sweet potato, radish in storage as well as elimination of emerging weeds; 4c Pre-harvest—The pre-harvest treatments are applications that aim to control pathogen attack through the soil and at the field—usually bush, and or orchard-trees, and/or greenhouse during the growing period; 4d Post-harvest—Post harvest treatments address the application of the composition on the substance itself, such as but not limited to fruits, vegetables, milk, milk products, meat, meat products, egg, and egg products—includes fertile egg for chicks produce, and or fish and or fish produce etc. Regarding fertile eggs that go through the hatching process, the disinfection treatments yielded 3-7% more hatched chicks; 4e Herbicide; 4f Insecticide, Miticide/acaricide, Nematocide; 4 g Rodenticide; 4h Elimination of cut-end blackening, inducing whitening—such as but not limited to cut corn, celery, lettuce, French fries and all fresh cut produce, including chilled ready to eat salads and other chilled meals; 4i Improve storability and prolong shelf life—this addresses in a more specific category produce that is kept under long storage periods (weeks and months) that suffers losses during the storage period and later on: as the physiological age progresses, the produce becomes more prone to any stress, with the outcome being a very short shelf life; 4j Improve yield—this addresses seeds yield, orchard yield, soil yield after treatments, chick yield from fertilized eggs, etc.

(124) Performance

(125) 5a 2%-4% losses; 5b 0%-2% losses; 5c higher yield 0.1%-60%; 5d Cleaning, Sanitizing, Disinfection, Sterilization efficacy

(126) Temperature

(127) 6a warmed solution 25-90° C.; 6b ambient solution 20-25° C.; 6c cooled solution 0.1−20° C.

(128) Contact time/application time: contact time is the time the composition is in contact with the treated matter; application time is the time required for the solution to be applied to the matter. For example, a fruit is sprayed for 5 seconds (application time) and the solution is washed after 40 seconds of contact with the sprayed composition (contact time).

(129) 7a seconds; 7b minutes; 7c hours; 7d days

(130) Intervals: How often are the compositions applied?

(131) 8a once; 8b a few times; 8c once a day; 8d once a week; 8e every two weeks; 8f once a month

(132) Method/Place of Post-Harvest Treatments

(133) 9a at the entry to the long storage and or to the packing house; 9b during storage before sorting line treatment; 9c on sorting line treatment; 9d during storage after sorting line treatment; 9e right before packing

(134) TABLE-US-00022 Fruit/ Solution Application Formula Aim of Temp- Contact method of Vegetable preparation method concentration treatment erature time interval treatment performance Apple 1a, b 2a-e 3c 4a, b, c, d, i, j 5b, c, d 6b, c 7a, b, c 8b 9a-e Avocado 1a, b 2a-e 3b 4a, b, c, d, i, j 5b, c, d 6b, c 7a, b 8b 9a-e Citrus- 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b 8b 9a-e Mandarin Citrus- 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b 8b 9a-e Oranges Citrus- 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b 8b 9a-e Mineola Citrus- 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b 8b 9a-e Grapefruits Citrus- 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b 8b 9a-e lemon Date 1a, b 2c, d, e 3c, d 4a, c, d, i, j 5b, c, d 6b 7a, b 8a 9c Kiwi 1a, b 2a, c, d, e 3c, d 4a, c, d, i, j 5b, c, d 6b 7a, b 8b 9a, d, e Lychee 1a, b 2a, c, d, e 3c, d 4a, c, d, i, j 5b, c, d 6b 7a, b 8b 9a, d, e Mango 1a, b 2a-e 3b, c, d 4a, c, d, i, j 5b, c, d 6a, b 7a, b 8b 9a-e Peach 1a, b 2a, c, d, e 3c, d 4a, c, d, i, j 5b, c, d 6a 7a, b 8b 9a, b, d, e Pear 1a, b 2a, c, d, e 3c, d 4a, c, d, i, j 5b, c, d 6b 7a, b 8b 9a, d, e Persimmon 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6b 7a, b 8b 9a-e Pomegranate 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b 7a, b 8b 9a-e Pepper 1a, b 2a-e 3c, d 4a, c, d, i, j 5b, c, d 6a, b 7a, b 8a 9a Asparagus 1a, b 2a, c, d, e 3c, d 4a, b, c, d, h, i, j 5b, c, d 6b, c 7a, b, c 8b 9a-e Banana 1a, b 2a, c, d, e 3c, d 4a, c, d, h, i, j 5b, c, d 6b, c 7a, b 8b 9a-e Broccoli 1a, b 2a, c, d, e 3c, d 4a, c, d, h, i, j 5b, c, d 6b, c 7a, b, c 8a 9a-e Cabbage 1a, b 2a-e 3c, d 4a, c, d, h, i 5b, c, d 6b, c 7a, b, c 8b 9a-e Carrot 1a, b 2a-e 3c, d 4a, b, c, d, h, i, j 5b, c, d 6b, c 7a, b, c 8a 9a-e Cauliflower 1a, b 2a, c, d, e 3c, d 4a, c, d, h, i 5b, c, d 6b, c 7a, b, c 8a 9a-e Celery 1a, b 2a-e 3c, d 4a, b, c, d, h, i, j 5b, c, d 6b, c 7a, b, c 8b 9a-e Corn 1a, b 2a-e 3a-d 4a, c, d, h, i 5b, c, d 6b, c 7a, b, 8a 9a Kohlrabi 1a, b 2a-e 3c, d 4a, b, c, d, h, i, j 5b, c, d 6b, c 7a, b, 8b 9a Cucumber 1a, b 2a-e 3c, d 4a, c, d, h, i 5b, c, d 6b, c 7a, b, 8a 9a Eggplant 1a, b 2a-e 3c, d 4a, c, d, h, i 5b, c, d 6a, b 7a, b, 8a 9a Garlic 1a, b 2d, e 3c, d 4a, c, d, h, i, j 5b, c, d 6b, c 7a, b, 8b 9a Lettuce 1a, b 2a-e 3c, d 4a, b, c, d, h, i, j 5b, c, d 6b, c 7a, b, 8a 9a, b, c, e Onion 1a, b 2d, e 3a-d 4a, c, d, h, i, j 5b, c, d 6b, c 7a, b, c 8b 9a-e Peanuts 1a, b 2a-e 3a-d 4a, c, d, h, i 5b, c, d 6b 7a, b, c 8a 9a Potato 1a, b 2a-e 3a-d 4a, b, c, d, h, i, j 5b, c, d 6b, c 7a, b, c 8b 9a-e Strawberry 1a, b 2a, c, d, e 3c, d 4a, c, d, h, i 5b, c, d 6b, c 7a, b, 8b 9a Sweet 1a, b 2a-e 3c, d 4a, c, d, h, i 5b, c, d 6a, b, 7a, b, 8a 9a pepper Sweet potato 1a, b 2a-e 3d 4a, b, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, c 8b 9a-e Tomato 1a, b 2a-e 3d 4a, c, d, h, i 5b, c, d 6b 7a, b, 8b 9a-e Water melon 1a, b 2a-e 3c, d 4a, c, d, h, i 5b, c, d 6b 7a, b, 8a 9a Grapes 1a, b 2a-e 3c, d 4a, c, d, h, i 5b, c, d 6b 7a, b, 8a 9a

(135) TABLE-US-00023 Field Solution Application Formula Aim of Contact method of Pathogen preparation method concentration treatment temperature time interval treatment performance Phytoph- 1a, b 2a-e 3a-d 4a, c, d, f, h, i, j, 5b, c, d 6a, b, c 7a, b, 8b 9a-e thora Scab 1a, b 2a-e 3a-d 4a, c, d, f, h, i, j, 5b, c, d 6a, b, c 7a, b, 8b 9a-e Silver Scurf 1a, b 2a-e 3a-d 4a, c, d, f, h, i, j, 5b, c, d 6a, b, c 7a, b, 8b 9a-e Penecillium Butrytice Alternaria Aspergillus Candida Rizopus

(136) TABLE-US-00024 Seed or Solution Application Formula Aim of Contact method of grain preparation method concentration treatment temperature time interval treatment performance Flower 1a, b 2a, c, d, e 3c, d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a-e bulbs Barley 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Oats 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Potato 1a, b 2a, c, d, e 3a-d 4a, b, c, d, 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e f, h, i, j Wheat 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Soybeans 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Corn 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Tomato 1a, b 2a, c, d, e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Onion 1a, b 2a, c, d, e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Garlic 1a, b 2a, c, d, e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Rice 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Pepper 1a, b 2a, c, d, e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Melons 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Cucumber 1a, b 2a, c, d, e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Cotton 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a, d, e Vegetative 1a, b 2a, c, d, e 3c, d 4a, c, d, i, h, j 5b, c, d 6b, c 7a, b, 8a, b 9a, d, e propagation Flower 1a, b 2a, c, d, e 3c, d 4a, c, d, i, h, j 5b, c, d 6b, c 7a, b, 8a, b 9a, d, e seedling Ornamental 1a, b 2a, c, d, e 3c, d 4a, c, d, i, h, j 5b, c, d 6b, c 7a, b, 8a, b 9a, d, e plant seedling

(137) TABLE-US-00025 Solution Application Formula Aim of Contact method of preparation method concentration treatment temperature time interval treatment performance For soil 1a, b 2a-e 3a-d 4a, b, c, d, e, f, 5b, c, d 6a, b, c 7a, b, c, d 8a, b N/A disinfection g, i, j For 1a, b 2a-e 3a-d 4a, b, c, d, e, f, 5b, c, d 6a, b, c 7a, b, c, d 8a, b N/A disinfection g, i, j of substrate for sowing As herbicide 1a, b 2a-e 3a-d 4a, b, c, d, i, j 5b, c, d 6a, b, c 7a, b, c, d 8a, b, N/A As insecticide 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c, d 8a, b, 9a, d, e As 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c, d 8a, b 9a, d, e rodenticide

(138) TABLE-US-00026 Micro- Solution Application Formula Aim of Contact method of organism preparation method concentration treatment temperature time interval treatment performance Gram positive 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e bacteria Gram 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e negative bacteria Fungi 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e Algae 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e Virus 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e Yeast 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e Mold 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e Spores 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e Bacteriophage 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e protozoa 1a, b 2a-e 3a-d 4a, c, d, h, i, j 5b, c, d 6a, b, c 7a, b, 8a, b 9a-e

(139) TABLE-US-00027 Type of Solution Application Formula Aim of Contact method of water preparation method concentration treatment temperature time interval treatment performance General 1a, b 2e, f 3a-d 4a, b, c, i, j 5d 6a, b, c 7a, b, c 8a, b 9a-e Recirculated 1a, b 2e, f 3a-d 4a, b, c, i, j 5d 6a, b, c 7a, b, c 8a, b 9a-e Drinking 1a, b 2e, f 3a-d 4a, b ,c, i, j 5d 6a, b, c 7a, b, c 8a, b 9a-e water

(140) TABLE-US-00028 Solution Application Formula Aim of Contact method of Foliage preparation method concentration treatment temperature time interval treatment performance Foliage 1a, b 2a-e 3a-d 4a, c, d, f, i, j 5b, c, d 6a, b, c 7a, b, c 8a 9a-e freshness Stem cleaning 1a, b 2a-e 3a-d 4a, c, d, f, h, i, j 5b, c, d 6a, b, c 7a, b, 8a 9a-e Stem 1a, b 2a-e 3a-d 4a, c, d, f, h, i, j 5b, c, d 6a, b, c 7a, b, 8a 9a-e freshness Field foliage 1a, b 2a-e 3a-d 4a, c, d, f, i, j 5b, c, d 6a, b, c 7a, b, c, d 8a, b N/A

(141) TABLE-US-00029 General Solution Application Formula Aim of Contact method of foods preparation method concentration treatment temperature time interval treatment performance Fish 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a-e Eggs (to eat) 1a, b 2a, c, d, e 3a-d 4a, c, d, i, h, j 5b, c, d 6a ,b, c 7a, b, c 8a, b 9a-e Meat 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a-e Milk 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b 9a-e Milk products 1a, b 2a-e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c 8a ,b 9a-e Eggs (to 1a, b 2a, c, d, e 3a-d 4a, c, d, i, j 5b, c, d 6a, b, c 7a, b, c, d 8a, b, c 9a-e hatch)

(142) TABLE-US-00030 Disinfecting surfaces, spaces, equipment & Solution Application Formula Aim of Contact method of systems preparation method concentration treatment temperature time interval treatment performance Food industry 1a, b 2a-e 3a-d 4a, f, g, 5d 6a, b, c 7a, b, c 8a, b, c 9a-e Hospitals 1a, b 2a-e 3a-d 4a, f, g, 5d 6a, b, c 7a, b, c 8a, b, c N/A Hotels 1a, b 2a-e 3a-d 4a, f, g, 5d 6a, b, c 7a, b, c 8a, b, c N/A Public places 1a, b 2a-e 3a-d 4a, f, g, 5d 6a, b, c 7a, b, c 8a, b, c N/A Production 1a, b 2a-e 3a-d 4a, f, g, 5d 6a, b, c 7a, b, c 8a, b, c 9a-e halls Buses 1a, b 2a-e 3a-d 4a, f, g, 5d 6a, b, c 7a, b, c 8a, b, c NA Airplanes 1a, b 2a-e 3a-d 4a, f, g, 5d 6a, b, c 7a, b, c 8a, b, c N/A Trains 1a, b 2a-e 3a-d 4a, f, g, 5d 6a, b, c 7a, b, c 8a, b, c N/A Spaces 1a, b 2a-e 3a-d 4a, f, g, i, j 5b, c, d 6a, b, c 7a, b, c 8a, b, c 9a-e

Example 27—Compliance with British/European Standard BS EN 1276:2009

(143) This is a quantitative suspension test to evaluate the bactericidal activity of chemical disinfectants and antiseptics used in food, industrial, domestic and institutional areas. A first and a second mixture were mixed together in a ratio of 40 wt. % first mixture and 60 wt. % second mixture, along with phosphonic acid. The first mixture contained 80 wt. % of a 94 v.1.%) aqueous formic acid solution and 20 wt. .sup.10o of a 99 wt. o propionic acid solution. The second mixture was a 50 v\1.% hydrogen peroxide solution. For testing, this mixture was further diluted 1000-fold in water; the resulting dilute solution (which contained about 800 ppm of phosphonic acid) had a pH of approximately 2.5.

(144) As is known in the art, EN 1276 defines a bactericidal product that has the capability to produce at least a 10.sup.5 reduction in the number of viable cells of the tested organisms, under defined experimental conditions. En the present case, a test suspension of bacteria (Listeria monocytogenes, ATCC 19115) in a solution of 3 g/l bovine albumin (to act as an interfering substance), was added to the diluted product. The mixture was maintained at 20° C.±0.5° C. for 1 min. or 5 min., then the bactericidal action of the product was neutralized by addition/dilution (solution containing 6 g/l sodium thiosulfate, 30 g/l polysorbate 80 and 3 g/l lecithin), and the number of surviving bacteria was determined. Each bacterial strain was maintained and counted by the pour plate method in accordance with EN 1276:1997. The results were as follows (Ve.sub.ccc viable count, N.sub.ccc number of cfu/ml of the bacterial suspension, Na=number of cfu in the test mixture, R=reduction in viability):

(145) TABLE-US-00031 Initial test No. of Surviving suspension bacteria in 0.3% Reduction in Contact time cells/ml (N) bovine albumin (Na) viability (R) 1 minute 2.2 × 10.sup.8 Vc 0, 0 >10.sup.5 Na <1.4 × 10.sup.2 5 minutes 2.2 × 10.sup.8 Vc 0, 0 >10.sup.5 Na <1.4 × 10.sup.2

(146) Validation and verification of the methodology: the validation tests are summarized in the table immediately belmN.

(147) TABLE-US-00032 Experimental Neutralization Dilution Contact Bacterial Conditions toxicity Neutralization Bacterial test time suspension Control Control Control suspension 1 minute Vc: 158, 149 Vc: 67, 79 Vc: 49, 68 Vc: 46, 68 10.sup.−6: 234, 232 Nv: 1.5 × 10.sup.3 A: 7.3 × 10.sup.2 B: 6.8 × 10.sup.1 C: 4.6 × 10.sup.1 10.sup.−7: 20, 24 5 minutes Vc: 120, 122 Vc: 54, 76 Vc: 35, 50 Vc: 54, 62 N: 2.2 × 10.sup.8 Nv: 1.2 × 10.sup.3 A: 6.5 × 10.sup.2 B: 4.3 × 10.sup.1 C: 5.8 × 10.sup.1 Vc = Viable Count; Nv = Number of CFU/ml of the bacterial suspension; A = Number of CFU/ml of the experimental conditions validation; B = Number of CFU/ml of Neutralization Toxicity Control; C = Number of CFU/ml of the Dilulion-Neutralization Control

(148) These results show that this composition conforms to the requirements of EN 1276 for the evaluation of bactericidal activity in 1 minute and 5 minutes at 20° C., under dirty conditions (3 gll bovine albumin) for reference strain Listeria monocytogenes.

Example 28—Compliance with British/European Standard BS EN 13697:2001

(149) This is a quantitative non-porous surface test to evaluate the bactericidal and/or fungicidal activity of chemical disinfectants used in food, industrial, domestic and institutional areas. The composition used was the same composition described in Example 22; as in Example 22, for testing it was diluted 100-fold.

(150) As is known in the art, EN JJ. § 5!-7. specifies a test method for testing the efficacy of materials against microorganisms on surfaces. A test suspension of fungi in solution under dirty conditions is inoculated onto a stainless steel surface and dried. The prepared sample of the product is applied in a manner which covers the dried film. The surface is maintained at a specified temperature for the defined contact time. The surface is transferred to the neutralization medium. The number of surviving organisms which can be recovered from the surface is determined. Dilution-neutralization is also utilized in parallel in some of the samples.

(151) The fungal strain was maintained and counted by the pour plate method in accordance with EN 13697:2001. Experimental conditions: test temperature, 22° C.±1° C.; contact times I minute and 5 minutes; hard water (distilled, not demineralized water), per total volume of !000 ml: 0.12 g of anhydrous MgCh, 0.28 g of anhydrous CaCh, and 0.28 g of NaHCO.sub.3 were added; interfering substance: 3.0 g/l bovine albumin—dirty conditions; neutralizer: 6 g/l sodium thiosulphate+30 g/l polysorbate 80+ lecithin 3 g/1; temperature of incubation 30° C. ct, 1° C.; test surface: stainless steel discs (2 cm diameter); test procedure: dilution-neutralization method was used to assess the fungicidal effect of the product, and the results are summarized in the table below.

(152) TABLE-US-00033 Fungal test Water suspension Validation test control Test results N NT NC Nc 1 min 5 min 10.sup.−5; >300, >300 10.sup.−2: >300, >300 10.sup.−2: >300, >300 10.sup.−2: 25, 27 10.sup.−0: 0, 0 10.sup.−0: 0, 0 10.sup.−6: 40, 46 10.sup.−3: 35, 37 10.sup.−3: 68, 63 10.sup.−3: 2, 3 10.sup.−1: 0, 0 10.sup.−1: 0, 0 N: 6.33 10.sup.−4: 2, 5 10.sup.−4: 8, 5 10.sup.−4: 0, 0 10.sup.−2: 0, 0 10.sup.−2: 0, 0 NT: 5.56 NT: 5.82 10.sup.−5: 0, 0 Nd <0.1 Nd <0.1 Nc: 4.41 Nts: 0 Nts: 0 Nts: 22 ME: >4.40 ME: >4.40 N = Log.sub.10 number of cfu per 0.05 ml of the test suspension; NT = Log.sub.10; number of cfu per test surface of the neutralization test; NC = Log.sub.10 number of cfu per test surface of the neutralization control; Nc = Log.sub.10, number of cfu per test surface in the water control; Nd = Log.sub.10 number of cfu per test surface in the disinfectant test; Nts = number of cfu remaining on the test surface; ME = microbicidal effect.

(153) Thus in accordance with EN 13697, the product, KEF 1, possesses fungicidal activity on surfaces in 1 min and in 5 min at 22° C. under dirty conditions (3 g/l bovine albumin) for reference strain of Aspergillus brasiliensis.

(154) It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed. Although the foregoing invention has been described in some detail for purposes of illustration, it will be readily apparent to one skilled in the art that changes and modifications may be made without departing from the scope of the invention described herein.