Classifications

• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N61/00—Biocides, pest repellants or attractants, or plant growth regulators containing substances of unknown or undetermined composition, e.g. substances characterised only by the mode of action

Definitions

• the present invention relates to a microbiocidal formulation for dissolution in water as a diluent to form a microbiocidal solution, said formulation containing an alkalinity neutralising agent to neutralise the total alkalinity present in the water used as the diluent.
• Typical of such donors are sodium and calcium hypochlorite, chloramines, iodophors and sodium dichloroisocyanurate (NaDCC) . While the effectiveness of all of these donors as a source of microbiocidally effective agent, e.g. hypochlorous acid, has been shown in various laboratory trials at different concentrations of the agent against a wide range of micro-organisms, it has been found that, in the field, the microbiocidal efficiency was not as expected from the laboratory trials.
• microbiocidally effective agent e.g. hypochlorous acid
• the invention provides a microbiocidal formulation suitable, following dissolution in a diluent to form a microbiocidal solution for microbiocidal treatment of an environment, the formulation comprising sufficient diluent alkalinity neutralising agent so that, following dissolution in the diluent, an alkalinity of no more than 100, preferably no more than 50 mg/1 bicarbonate alkalinity is observed in the microbiocidal solution; sufficient pH neutralising agent so that, following dissolution in the diluent, a pH of 5.0-8.0, preferably 6.0-6.8, is observed in the microbiocidal solution and a microbiocidally effective amount of an alkalinity sensitive microbiocidal agent; the formulation being adapted to release the microbiocidally effective amount of the alkalinity sensitive microbiocidal agent over a microbiocidally effective period of time.
• the alkalinity sensitive microbiocidal agent is a source of available halogen.
• the formulation is adapted to release available halogen, in use, from an organic source/precursor of hypohalous acid and/or hypohalite.
• the organic source/precursor compound releases, in aqueous solution, hypohalous acid and/or hypohalite in a microbiocidally effective amount over the microbiocidally effective period of time, by adaption of the formulation for the control of the pH.
• the alkalinity neutralising agent is comestibly acceptable.
• the organic source/precursor compound is a halogenated isocyanuric compound or a salt thereof. More preferably, the source/precursor compound of the microbiocidally effective hypohalous acid and/or hypohalite is selected from sodium dihaloisocyanurate, potassium dihaloisocyanurate or trihaloisocyanuric acid, preferably sodium dichloroisocyanurate .
• the microbiocidally effective amount of the hypohalous acid is released from 1 to 5000 ppm of the solid source/precursor compound and the microbiologically effective period of time is in the range of 10 seconds to 48 hours .
• the micro-organism is selected from E. coli or Pseudomonas or is a resistant micro-organism, more preferably a pasteurisation resistant micro-organism, still more preferably a thermoduric or thermophilic organism, most preferably, a species of micro-organism selected from Bacillus, Micrococcus, Microbacterium, Clostridium, Listeria, Alcaliigenes, Arthrobacter, Lactobacillus , Serratia or any other spore forming species.
• the environment comprises an external surface or a lumen of an apparatus used in the production, preparation or processing of food or beverages.
• the environment comprises process liquid or liquid for human or animal consumption.
• the alkalinity neutralising agent is a comestibly acceptable acid or its salt or a mixture thereof, preferably a comestibly acceptable organic acid. More preferably, the alkalinity neutralising agent is succinic acid or a salt thereof.
• the alkalinity neutralising agent is citric acid or a salt thereof.
• the microbiocidal formulation is in powder, granulate or tablet form.
• alkalinity affects the microbiocidal activity of the hypohalous acid and/or its hypohalite salts by neutralising the hypohalous acids themselves and by affecting the pH of the microbiocidal formulation in the environment .
• Tests were conducted to compare laboratory trials using distilled water or water of a known alkalinity as the diluent. These comparisons provided new and very surprising results with regard to the efficiency of the microbiocidal agent when dissolved in high alkalinity water as the diluent.
• Alkalinity is the sum of all titratable bases and is a measure of the acid neutralising capacity (ANC) .
• Water total alkalinity is mainly a sum of carbonate, bicarbonate and hydroxide levels but may also include contributions from borates, phosphates, silicates or other bases, if these are present. Bicarbonates are the main contributors to "field" water total alkalinity.
• Alkalinity of water is pH related but is not pH dependant, for example, water can have a pH of 6.4 and an alkalinity of 320 mg/1 and, conversely, water can have a pH of 8.0 and an alkalinity of 95 mg/1.
• ANC means "acid neutralising capacity” . This term is now coming into use to replace the classical expression “total alkalinity” , although the latter remains the most widely used term in the field of applied water chemistry. Outside the field of applied water chemistry, total alkalinity as a concept separate from pH is not at all well understood.
• Figure 2 shows a simplified pH distribution curves for the FAC species, based on reasonably ignoring the significant Cl 2 contribution when the pH is greater than 3 (it is not now necessary to specify the Cl 2 concentration) .
• Figure 3 shows the pH dependence of these two FAC species, in which the respective percentages are on a molar basis .
• a chlorine donor compound is often referred to as having say 500mg of available chlorine per gram. This describes the total amount of chlorine available but describes neither the form, its activity, nor its availability at a given time, all of which will affect the microbiocidal effectiveness of the solution.
• Lubricating agents are commonly used in the tabletting process e.g. adipic acid or succinic acid. However, their sole disclosed function to date has been as a lubricating agent or as the replacement of an existing lubricating agent.
• any comestibly acceptable acid or a salt thereof can be introduced to perform this function such as, for example, any comestibly acceptable acid or a salt thereof.
• the level of a suitable lubricating agent should be adjusted to accommodate or neutralise the impact of the total alkalinity or ANC value of the diluent water on the microbiocidal effectiveness of any given microbiocidal solution.
• the lubricating component has been taken into account when calculating the adjustment that would be required to a "conventional" microbiocidal formulation to neutralise the total alkalinity or ANC of any given diluent water.
• total alkalinity is pH related but not pH dependant and the use of a comestible acid to neutralise the alkalinity had the additional benefit of achieving an optimum pH for the dissociation of the chlorine donor NaDCC.
• a comestible acid (or a salt thereof) was selected for further tests.
• the object of the present invention was to neutralise (reduce or eliminate) the ANC of the diluent water
• the dosed water achieved the target dosed pH of 5.0- 8.0, preferably, 6.0-6.8 and the target dosed ANC of no more than 100 mg/1 bicarbonate alkalinity, preferably no more than 50 mg/1 bicarbonate alkalinity.
• An NaDCC based tablet was prepared containing, along with various components customarily employed to facilitate tabletting and to promote dissolution of the tablet by means of effervescence, a comestible agent present in a specifically adjusted amount to achieve a desired target pH and FAC (free available chlorine) value in the dosed water when the tablet was completely dissolved in the diluent water.
• Dissolution requires that all the tablet components are uniformly distributed in the diluent, that the solution is fully diluted to the required dilution for its use as a microbiocidal agent and that following partial or virtually complete loss of the excess dissolved carbon dioxide introduced by the effervescence.
• the comestible acid may be a comestible agent additional to "conventional" tabletting agents and/or effervescence agents, but the amount of comestible agent must be specifically determined to attain the desired pH and FAC value, following loss of excess dissolved carbon dioxide to a contiguous gaseous phase.
• the amount of comestible agent required to produce the desired pH and FAC value in the dosed water is determined by a calculation which takes account of the following factors :
• ANC acid neutralising capacity
• NaDCC the chemical species derived from the carbonate and bicarbonate salts, the chemical species derived from any lubricating agents (including comestible acids incorporated for that purpose) in the formulation, and the chemical species derived from the comestible acid which is to serve as the pH- and FAC-adjusting species as defined hereinabove;
• the desired final FAC or hypochlorous acid or hypochlorite ion concentration may be prescribed [but are not essentially prescribed] as a fraction of the total concentration of chlorine (Cl ⁇ ) introduced into the diluent water, at its desired dilution, by the NaDCC component of the formulation (Cl ⁇ , expressed as mol per unit volume, is twice the number of mols of NaDCC added to the unit volume of the diluent) .
• the "degree of saturation with respect to carbon dioxide” is the concentration of free carbon dioxide in a water, in this case, the dosed and fully diluted water, expressed as a fraction of the concentration of free carbon dioxide which would be present if the water was at equilibrium with a contiguous gaseous phase for which the partial pressure of carbon dioxide is known or prescribed;
• the concentration of "free” carbon dioxide can be interpreted as the concentration of C0 2 per se [as opposed to the concentration of "dissolved” carbon dioxide which embraces the dissolved molecular species C0 2 , in addition to carbonic acid (H 2 C0 3 ) and its dissociation products, the bicarbonate (HC0 3 ⁇ ) and carbonate ions (CO, " ) ]
• chlorine is a commonly used halogen in commercial microbiocides, namely, sodium hypochlorite; a commercial NaDCC based product, Agrisept R Tabs; and a test product, the same formulation as Agrisept Tabs, but containing, in addition, an agent to neutralise the diluent alkalinity.
• Table 1 shows, using this predictive computer programme, the impact of altering the diluent's ANC, whilst maintaining all other factors constant.
• the formulation comprises (excluding the alkalinity reducing agent) 2.21g NaDCC, 1.13g adipic acid, 1.036g sodium bicarbonate and 0.044g sodium carbonate.
• the diluent water pH is 7.5 and its volume is 11.
• the target dosed pH and FAC to total Cl ratio are 6.0 and 0.5, respectively.
• Table 2 shows, using the predictive computer programme, the impact of altering the diluent volume, whilst maintaining all other factors constant.
• the formulation comprises (excluding the alkalinity neutralising agent) 2.21g NaDCC, 1.13g adipic acid, 1.036g sodium bicarbonate and 0.044g sodium carbonate.
• the diluent water pH is 7.5 and its volume is 101.
• the target dosed pH and FAC to total Cl ratio are 6.0 and 0.5, respectively.
• Table 3 shows the impact of altering the amount of adipic acid (the conventional lubricating agent) , whilst maintaining all other factors constant.
• the composition of the formulation is as set out above for Tables 1 and 2.
• the diluent water volume is 11, its pH is 7.5 and its total alkalinity is 400 mg/1.
• the target dosed pH and FAC to total Cl ratio are 6.0 and 0.5, respectively.
• microbiocidal efficiency of halogen-based microbiocides in particular, and, more generally, of any microbiocide whose activity in solution is influenced or degraded by the ANC value of the diluent water is as follows:
• microbiocidal formulation of the present invention is particularly applicable to neutralising the medium and major negative impacts set out hereinabove and is most particularly applicable to neutralising the major negative impacts set out hereinabove.
• a microbiocidal formulation of the present invention has the following preferred composition:
• a 1% aqueous solution of sodium dichloroisocyanurate has a pH within the range of 5.5-7.0.
• an alkalinity reducing agent such as succinic acid ensures that the alkalinity, which is primarily bicarbonate alkalinity, is neutralised. This ensures that the nominal amount of the hypochlorous acid and/or the hypochlorite salt present in the sodium dichloroisocyanurate solution, is actually available.
• the final pH will of course determine the relative amounts of hypochlorous acid and hypochlorite salt present .
• adipic acid ensures a stable formula suitable for tabletting and the incorporation of the effervescent excipients ensure the effective and rapid release of hypochlorous acid and/or hypochlorite salt into solution, from the source.
• microbiocidal formulation of the present invention will be equally suitable for use in powder, granulate or tablet form, each of which allows accurate quantification of the microbiocidally inactive source and of the excipient quantities, in a given volume of water or any other suitable solvent .
• the studies set out in the remaining Examples were carried out with tablets of the microbiocidal formulation of the invention having the following composition: -
• the alkalinity reducing agent can be integrally incorporated in the microbiocidal formulation.
• the alkalinity reducing agent can be present in a coating on a powder, granulate or tablet embodiment of the microbiocidal formulation and, in that event, the alkalinity reducing agent is released into solution, to reduce the alkalinity level, before the microbiocidally active agent is released into solution. It will be appreciated that there is no need for a tabletting or lubricating agent in a powder or granulate formulation.
• the desired pH of the final solution in the case of sodium dichloroisocyanurate as the microbiocidally inactive source, is in the range 5.0-8.0, preferably 6.0-6.8.
• the dissociation of hypochlorous acid into the hypochlorite ion is pH dependent. Thus, at pH 6.0 , 97.3% of the hypochlorous acid is undissociated and, at pH 7.0 , 78.1% of the hypochlorous acid is undissociated.
• anhydrous form of the microbiocidally inactive source be employed in the present microbiocidal formulations.
• Hard water with a hardness of 342mg/l, is prepared by dissolving 304mg CaCl 2 and 139mg MgCl 2 .6H 2 0 in 1 litre deionised water.
• Hard water, with an alkalinity of lOOmg/l, 200mg/l or 300mg/l is prepared by dissolving 200mg, 400mg or 600mg NaHC0 3 , with 304mg CaCl 2 and 139mg MgCl 2 .6H 2 0 in 1 litre deionised water.
• the microbiocidal formulation of the invention comprises one 9.42g tablet of Example 1 dissolved in sufficient hard water of 0, lOOmg/l, 200mg/l or 300mg/l added alkalinity, to yield 25 ppm of available chlorine.
• the comparative formulation has the following composition: Ingredient Weight
• One tablet (5g) of the comparative formulation is dissolved in sufficient hard water of 0, lOOmg/l, 200mg/l or 300mg/l added alkalinity, to yield 25 ppm available chlorine.
• the pH was measured at 10 °C and the results are shown in Table 5.
• added alkalinity affects the pH of both the comparative formulation solution and the formulation of the invention solution. Specifically, when the added alkalinity is greater than lOOmg/l, the pH of the comparative formulation solution is outside the desired 6.0-6.8 pH range. In contrast, even when the added alkalinity is 300mg/l, the pH of the formulation of the invention solution is still within the desired 6.0-6.8 pH range.
• the lumen of the milking system is pre- rinsed at the end of the morning milking process, with cold water, followed by a wash sequence involving circulation of 45 litres of a detergent solution containing 0.5% (227g/45 litres (0.5lb/l0gal) ) of an approved caustic detergent, for 10 minutes, which detergent solution is then recovered in the wash trough for reuse in the second daily wash. It is suggested not to post-rinse the caustic solution residue from the lumen until immediately before the next milking, since it is believed that successful cleaning and microbiocidal action on the lumen of the milking system depends on prolonged contact of this caustic residue with the lumen surfaces.
• a hot wash at regular intervals is an essential part of the routine to remove built up milk deposits, inter alia . In order to get optimum results from cold cleaning, the following instructions are widely acceptable : -
• the total bacterial counts and the psychotrophic counts for each of week 1 and week 2 show a superior performance for the microbiocidal formulation of the present invention.
• Example 2 A laboratory comparison was carried out to determine the microbiocidal efficacy of the test formulation as described in Example 1, of the comparative formulation (5g tablets) as described in Example 2 and of a sodium hypochlorite solution (Merck) , supplied by Lennox Chemicals, Dublin, Ireland.
• the objective was to establish that the formulation of the present invention was more effective as a microbiocide than a conventional sodium hypochlorite solution and a conventional tableted formulation, as per Example 2, in "field" water.
• the general format of the testing schedule is derived from BS3286:1960. The tests were carried out using 0.1% milk as an organic load. The milk used was unpasteurised milk with an approximate somatic cell count of 300 x 10 3 .
• test organisms were Staphylococcus aureus , isolated from a clinical case of mastitis in dairy cows, and Bacillus subtilis, a control culture obtained from ATCC. Contact times for the three products were 5 mins, 10 mins, 6 hrs and 24 hrs.
• the concentrations of the three products were 25 ppm (mg/1) of available chlorine.
• the tests were carried out at 10 °C. Dilutions in all cases were made in a diluent comprising water with an alkalinity of 300 mg/1 expressed as calcium carbonate (CaC0 3 ) equivalent and a hardness of 342mg/l expressed as calcium carbonate (CaC0 3 ) .
• the pH of the water was checked before and after addition of trial product .
• Inactivation of the products under test was carried out by placing 1ml of reactant mix, after the appropriate contact time, in 9mls of sterile inactivation fluid. The inactivation will neutralise the effect of the disinfectant.
• the inactivation fluid comprises lecithin - soya (3g) , Tween 80 (30ml) , sodium thiosulphate (5g) , L-histidine (lg) , phosphate buffer (0.25N; 10ml), and purified water - made up to 1 litre.
• the inactivation fluid was sterilised at 121°C for 15 minutes.
• the "field" diluent comprises NaHC0 3 (600mg) , CaCl 2 (304mg) and MgCl 2 .6H 2 0 (1339mg) , which is made up to 1,000ml with deionised water.
• Organism Bacillus subtilis
• Organism Staphylococcus aureus
• Example 1 A laboratory comparison of the efficiency of a test formulation as described in Example 1 against the conventional microbiocide, sodium hypochlorite, at two different concentrations, under control conditions. The objective was to establish that the formulation of the present invention was more effective as a microbiocide at a very low concentration, 25 ppm, when compared to sodium hypochlorite and that, even if the concentration was increased, by a factor of 10, to 250 ppm, the formulation of the present invention was much more efficient in "field" water.
• Example 4 The testing procedure of Example 4 was followed, with the following amendments.
• the test organisms were Bacillus subtilis, Salmonella typhimurium (phage type 104) , Listeria monocytogenes and Clostridium butyricum.
• the concentrations were 25 ppm and 250 ppm for each of hypochlorite and formulation of the present invention.
• the organic load was 0.1% milk (25 ppm) or 5% yeast (250 ppm) .
• Organism Salmonella typhimurium phage type 104
• Organism Clostridium butyricum
• Organism Bacillus subtilis
• the trial was carried out simultaneously on both products at two different concentrations, 25 ppm and 250 ppm.
• the results of the trial clearly demonstrate that, at 250 ppm, the formulation of the present invention is microbiocidally superior to the conventional hypochlorite. At 25 ppm, the difference is smaller but, in most cases, the formulation of the present invention is still superior.
• composition Sod. Dichloroisocyanurate...25% (w/w) 800mg
• the general format of the testing schedule is derived from BS3286:1960 and the testing procedure of Example 4 was followed, with the following amendments.
• the tests were carried out using 0.1% milk as an organic load.
• the test organism was Bacillus subtilis BGA, a control culture obtained from ATCC.
• the contact time for each of the formulations was 5 mins, 10 mins, 1 hour and 6 hours.
• the concentration of each formulation was 100 ppm (mg/1) available chlorine in a volume of 5 litres of diluent water. All tests were carried out at 10 °C.
• the diluent water had a total alkalinity of 400mg/l expressed as calcium carbonate (CaC0 3 ) equivalent and a hardness of 342mg/l expressed as calcium carbonate (CaC0 3 ) .
• the pH of the water was measured before and after the addition of the various formulations .
• the inactivated fluids were cultured onto Colombia Blood Agar using standard laboratory practices. Incubation was for 18 hours at 37°C.
• the concentration of the inoculum was 1.25 x 10 6 orgs/ml.
• the "field" diluent comprises NaHC0 3 (750mg) , CaCl 2 (304mg) and MgCl 2 .6H 2 0 (1339mg) , which is made up to 1,000ml with deionised water.
• Test Formulation B is superior to Test Formulation A in suppre'ssing growth of Bacillus subtilis BGA under the conditions described.
• the residual resistance of the organism is due to various factors limiting the formulation's microbiocidal activity, specifically, its spore form, the high concentration of the inoculum organism used and the high total alkalinity of the diluent.
• microbiocidal formulation of the present invention has applicability in a milking apparatus at the end of a post-milking apparatus washing procedure (as exemplified in Example 3) ; in any pre- pasteurisation holding system; and in any post-pasteurisation apparatus against post-pasteurisation contaminant microorganisms .
• microbiocidal formulations of the present invention provide effective water treatment by giving effective microbiocidal effect without exceeding the WHO recommended limits. It will also be appreciated that the microbiocidal formulation of the present invention, although exemplified in respect of a milking apparatus, has general applicability in any apparatus used in the production, preparation or processing of food or beverages and, indeed, in the treatment of water for human or animal consumption or of process liquids .
• a microbiocidal formulation of the above-mentioned composition is useful, following dissolution in five litres of a diluent having a pH of 7.5, a total alkalinity of lOOmg/l as calcium carbonate and a total carbonic carbon of 2.1mmol/l (calculated) so as to achieve, following dissolution in the diluent, a pH of 6.0 and a FAC to total Cl ratio of 1.0.
• Succinic acid 2.619g
• a microbiocidal formulation of the above-mentioned composition is useful, following dissolution in five litres of a diluent having a pH of 7.5, a total alkalinity of 400mg/l as calcium carbonate and a total carbonic carbon of 8.5mmol/l (calculated) so as to achieve, following dissolution in the diluent, a pH of 6.0 and a FAC to total Cl ratio of 1.0.
• a microbiocidal formulation of the above-mentioned composition is useful, following dissolution in five litres of a diluent having a pH of 7.5, a total alkalinity of 50mg/l as calcium carbonate and a total carbonic carbon of l.lmmol/1 (calculated) so as to achieve, following dissolution in the diluent, a pH of 6.0 and a FAC to total Cl ratio of 1.0.
• Succinic acid 13.589g
• a microbiocidal formulation of the above-mentioned composition is useful, following dissolution in twenty- five litres of a diluent having a pH of 7.5, a total alkalinity of 400mg/l as calcium carbonate and a total carbonic carbon of 8.5mmol/l (calculated) so as to achieve, following dissolution in the diluent, a pH of 6.0 and a FAC to total Cl ratio of 1.0.
• a microbiocidal formulation of the above-mentioned composition is useful, following dissolution in twenty- five litres of a diluent having a pH of 7.5, a total alkalinity of lOOmg/l as calcium carbonate and a total carbonic carbon of 2.1mmol/l (calculated) so as to achieve, following dissolution in the diluent, a pH of 6.0 and a FAC to total Cl ratio of 1.0.
• Succinic acid 0.428g
• a microbiocidal formulation of the above-mentioned composition is useful, following dissolution in one litres of a diluent having a pH of 7.5, a total alkalinity of 400mg/l as calcium carbonate and a total carbonic carbon of 8.5mmol/l (calculated) so as to achieve, following dissolution in the diluent, a pH of 6.0 and a FAC to total Cl ratio of 1.0.
• a microbiocidal formulation of the above-mentioned composition is useful, following dissolution in one litres of a diluent having a pH of 7.5, a total alkalinity of lOOmg/l as calcium carbonate and a total carbonic carbon of 2.1mmol/l (calculated) so as to achieve, following dissolution in the diluent, a pH of 6.0 and a FAC to total Cl ratio of 1.0.
• Example 13 is an example of a microbiocidal formulation, in which the total alkalinity of the diluent water plays a very minor role, in that it is necessary to merely add 0.017g succinic acid to the adipic acid already present in the microbiocidal formulation, in order to achieve a target dosed pH of 6.0.
• the total alkalinity of the diluent water plays a minor role, in that it is necessary to add 0.2-0.6, preferably, 0.218-0.561g succinic acid to the adipic acid already present in the microbiocidal formulation, in order to achieve a target dosed pH of 6.0.
• the total alkalinity of the diluent water plays a medium role, in that it is necessary to add 2.619g succinic acid to the adipic acid already present in the microbiocidal formulation, in order to achieve a target dosed pH of 6.0.
• the total alkalinity of the diluent water plays a major role, in that it is necessary to add 3-15g, preferably, 3.303-13.589g succinic acid to the adipic acid already present in the microbiocidal formulation, in order to achieve a target dosed pH of 6.0.

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