MX2008006747A - Solid biocidal compositions and methods of using the same - Google Patents

Abstract

The present invention relates to stable, pH self-adjusting, solid compositions for the preparation of a biocide useful in preventing or inhibiting the growth of living organism in liquids.

Description

SOLID BIOCIDAL COMPOSITIONS AND METHODS FOR USING THE SAME FIELD OF THE INVENTION The present invention relates to solid, stable, self-adjusting, pH compositions for the preparation of biocides useful for preventing or inhibiting the growth of living organisms in liquids. BACKGROUND OF THE INVENTION The mixture of a solution of an ammonium salt and a sodium hypochlorite solution is known to produce the biocidal onocloramine agent. Monohaloamines such as monochloramine have been reported as effective biocides for swimming pool and municipal water treatment applications (J. Beck, et al., Aqua (Oxrod), 1:25 (1986)). To generate monohaloamines, an ammonium halide solution is typically mixed with a hypohalite solution at high pH, thereby generating monohaloamine in situ; and the mixture is then used for the intended application. For example, Barak et al., U.S. Patent Nos. 5,976,386, 6,132,618, and 6,478,973; and US Patent Application Publication Nos. 2003/0121868, 2003/0132173 and 2005/0194324 report processes for employing individual solutions of ammonium halide and sodium hypochlorite that combine to generate a biocide for liquid treatment. Similar biocidal systems have been reported in CK Davis, G. Casini, Pulp and Paper, February 2003 and S. Bharati, K. Ryand, Paper Asia, Vol. 19, No. 7, September 2003. Solution-based systems However, they can impose numerous difficulties to use, store and manage. For example, solutions may be unstable, requiring protection from exposure to environmental conditions and refrigeration. The transport and handling of liquids is also undesirable due to the excess of weight and volume, limiting in this way the application and distribution of the technology. Consequently, there is a current need for simpler and more portable methods for the generation of biocidal agents containing monohaloamines and related compounds. The compositions, systems and methods provided herein are directed to this end. COMPENDIUM OF THE INVENTION The present invention provides solid double agent compositions which comprise: a) a solid hypohalite; b) a source of solid nitrogen; and c) a component that is either: i) a solid pH control material having at least a secondary function such as a diluent, stabilizer, anti-cake-forming agent, binder or blotter; or ii) a combination of a solid pH control material and a solvent, stabilizer, cake counter agent, blotter binder, or combination thereof; wherein the double agent composition forms a biocidal mixture when combined with water. The present invention further provides a system comprising a first single agent solid composition and a second solid single agent composition, wherein the first single agent solid composition comprises: a) a source of solid nitrogen; and b) a pH control material; wherein the second single agent solid composition comprises: a) a solid hypohalite; wherein the first single agent solid composition and the second solid single agent composition together form a biocidal mixture when combined with water. The present invention further provides methods for preparing a biocidal mixture comprising: a) combining a double agent composition described herein with an appropriate amount of water to produce a peak haloamine concentration of from about 10 to about 10,000 ppm; or b) combining the first and second solid single agent compositions of a system described herein with an appropriate amount of water to produce a peak haloamine concentration of from about 10 to about 10,000 ppm. The present invention further provides biocidal mixtures prepared in accordance with the methods described herein. The present invention further provides methods for preventing or inhibiting the growth of living organisms in a liquid comprising: a) preparing a biocidal mixture in accordance with any of the methods described herein; and b) treating the liquid with the biocidal mixture. DETAILED DESCRIPTION Double agent compositions The present invention provides, among others, solid double agent compositions which, when combined with water, form useful biocidal mixtures to prevent or inhibit the growth of living organisms in liquids. The components of the double agent composition can react during combination with water to form reactive biocidal agents including monohaloamines and / or dihaloamines (collectively "haloamines"). The dual agent solid compositions of the invention have numerous advantages over liquid and other biocidal haloamine systems including, for example, improved stability, shelf life, portability, and general ease of use. The double agent solid compositions of the invention are furthermore characterized by their properties of stability and self-adjustment of pH. The solid double agent compositions of the invention contain the following components: a) a solid hypohalite; b) a source of solid nitrogen; and c) a solid pH control material. The compositions optionally may further include one or more of the following solid components: d) a solid blotter); e) a solid stabilizer; f) an agent against cake formation, g) a binder, h) a disintegrator, i) a slider; j) a solid diluent, or combinations thereof. Some of the components can serve multiple or overlapping functions. However, as used herein, the primary function of each component will be dictated by the name of the component. For example, the primary function of solid pH control material will be pH control of the eventual biocidal mixture. In some cases, the solid pH control material may also function as a diluent, stabilizer, blotter, and / or other ingredient, but unless otherwise indicated herein, these secondary functions are optional. In another example, a blotter may also function as a diluent, stabilizer, or other ingredient. Consequently, the primary function of the secant will be to protect the moisture composition, and any dilution or other properties will be considered secondary, and therefore optional, unless otherwise indicated. Thus, "primary function" (as determined by the ingredient name) as used herein refers to the primary purpose for including the ingredient in the composition and also indicates that the ingredient is present in the composition in an amount sufficient or effective to carry out substantially that function. A "secondary frustration" refers to a functional property of an ingredient in addition to the primary function and that the ingredient is present in the composition in a sufficient or effective amount to substantially carry out both primary and secondary functions. An ingredient can have multiple secondary functions. In the case where an ingredient can potentially have multiple primary functions, it will be present in the present compositions to serve only one of those primary functions and the other functions will be considered secondary. For example, if a composition of the invention contains a pH control material and a drying agent, the pH control material will not be composed of the same substance as the drying agent. To further illustrate, if potassium carbonate is used as the pH control material and the composition also contains a separate drying ingredient, the blotter will be different from potassium carbonate. While not wishing to be bound by any theory, it is believed that when the double agent solid composition is dissolved in a predetermined amount of water, the hypohalite component reacts with the solid nitrogen source, and the pH controlled largely by the pH control material, to form haloamines 8v.gr., monohaloamine and / or dihaloamine). Accordingly, compositions containing both a solid hypohalite and a solid nitrogen source are referred to herein as "double agent compositions".

Haloamines include, for example, monohaloamines, dihaloamines, and trihaloamines. Monohaloamines are amines that typically have an N-halogen bond. An example of monohaloamine is monochloramine (NH2C1). Similarly, dihaloamines are characterized by two N-halo linkages and the trihaloamines are characterized by three N-halo linkages. An exemplary dihaloamine is dichloroane (NHC12) and an example of triamloamine is trichloramine (NCI3) - The methods for measuring the concentration of haloamines are rythm in the art and include the methods described in the Examples. Typically, monohaloamines are formed at basic pH (e.g., greater than about pH 8); the dihalohamines are formed from monohaloamines at acidic pH (e.g., at about pH 3-5); and trihaloamines are formed at very acidic pH (e.g., around pH <3). The pH can be controlled by the amount and type of solid pH-control material used in the composition, thus allowing regulation of the type as well as the amount of haloamine generated in the biocidal mixture. The pH control material eventually also eliminates or reduces the need for subsequent pH adjustments or titrations of the biocidal mixture. This feature is one of the numerous advantages of the present invention. The blotter, diluent, stabilizer and other optional components of the compositions of the invention can influence the stability and other properties of the solid compositions. The solid hypohalite component can be a solid hypohalite salt that includes a hypohalite salt of alkali metal or alkaline earth metal. Appropriate solid hypohalites include magnesium, lithium or calcium salts of hypochlorite, hypodromite, or hypoiodite. Examples of solid hypohalites include calcium hypochlorite and lithium hypochlorite. In some embodiments, solid hypohalite is calcium hypochlorite. The solid nitrogen source can be any solid compound having at least one N-H functionality capable of reacting with a hypohalite. For example, the source of solid nitrogen may be an ammonium salt or an organic amine. Suitable ammonium salts are ammonium halides (e.g., ammonium chloride, ammonium bromide, etc. =), ammonium sulfate, ammonium carbonate, and other ammonium salts. Suitable organic amines include, for example, ethylenediamine, ethanolamine, amino acids, and other solid organic amines. In some embodiments, the source of solid nitrogen is ammonium chloride. In additional embodiments, the source of solid nitrogen is ammonium sulfate. The pH control material can be any solid substance capable of maintaining or achieving a desired pH when the composition is mixed with water in order to obtain the desired compounds (e.g., monochloramine and / or dichloramine). In some embodiments, the pH control material is an inorganic salt (e.g., an alkali metal or alkaline earth metal salt) of a hydroxide (e.g., sodium hydroxide), carbonate (e.g. , sodium carbonate, potassium carbonate and the like), acetate (e.g., sodium acetate), phosphate, or another substance capable of maintaining a solution at basic pH. In some embodiments, for example to encourage the formation of monochloramine, the solid pH control material keeps the biocidal mixture at a pH of about 8 to about 13, about 9 to about 12, about 10, or about of 11. In some embodiments, the pH control material is sodium hydroxide or solid carbonate. To encourage the formation of dihaloamines, the pH control material may include a substance capable of maintaining a solution at acidic pH. For example, the pH control material may be an inorganic salt of hydrogen phthalate or monobasic sodium phosphate. In some embodiments, the solid pH control material keeps the biocidal mixture at a pH of about 3 to about 6, about 3 to about 5., or about 4. Sometimes it is desirable that the pH control material have relatively low solubility in water compared to the active agents. For example, lower solubility can delay acidification, thereby allowing monohaloamines to first form at higher pH. The monohaloamines can then serve as precursors to the dihaloamines that are subsequently formed when the pH control material eventually dissolves and the solution reaches the desired acidic pH. Other suitable pH control materials may include inorganic salts of the following substances. Borate, phosphate, propionate, butyrate, or mixtures of these and the like. In some embodiments, the solid pH control material has a secondary function as a diluent, such as when there is sufficient amount of the solid pH control material to dilute and effectively disperse the active 8v.gr., the solid nitrogen source and the solid hypohalite) so that the interaction between the solid assets is minimized, thereby facilitating composition stability and prolonging shelf life. Solid pH control materials that have a secondary function as a diluent include, for example, substances containing carbonate salts, such as sodium carbonate or potassium carbonate, or inorganic salts of hydrogen phthalate. A solid pH control material having a secondary function as a diluent forms at least about 10% by weight of the total composition. In some embodiments, when the pH control material has a secondary function as a diluent, little or no other material is present in the composition that has a primary function as a diluent.; however, materials that have drying, binding, lubricating, anti-cake, or other primary functions may be included. In some embodiments, the solid pH control material has a secondary function as a blotter, meaning that it preferably absorbs or inhibits water vapor from the surrounding environments that serve to protect moisture sensitive components (e.g., the 'assets' of the compositions of the invention and provide stability. Solid pH control materials that have a secondary function as a drying agent include, for example, substances containing carbonate salts, such as potassium carbonate or sodium carbonate. In some embodiments, the solid pH control material may have secondary functions of both diluent and dryer. The double agent compositions of the invention may also include a diluent. The diluent can be any solid substance that serves to disperse and dilute one or more of the reactive (active) components of the solid composition to effectively minimize its interaction in solid form. The diluents are typically inert toward the active. A diluent may also have a secondary function such as a binder, stabilizer, anti-cake-forming agent, or other function. Some thinners can also work as blotters. In some embodiments, the diluent does not have a secondary function as a pH control material. In some embodiments, the diluent does not have a secondary function as a stabilizer. Suitable diluents include inorganic salts (e.g., NaCl, KC1, sodium carbonate, potassium carbonate, calcium sulfates, calcium phosphates, metal aluminosilicates, etc.), as well as powdered cellulose, PCC, and microcrystalline cellulose (e.g., Avicel), and the like.

A blotter can be any solid hygroscopic material that preferably absorbs and inhibits water vapor from the surrounding environment, serving to protect the moisture sensitive components of the compositions. Suitable solid dryers include activated alumina, silica gel, calcium chloride, zinc chloride, calcium sulfate (e.g., anhydrous calcium sulfate), calcium oxide, potassium carbonate, montmorillonite clay, and the like . In some embodiments, the blotter contains anhydrous calcium sulfate (e.g., Drierite® from W. A. Hammond Company, Xenia, Ohio) or potassium carbonate. Other suitable blotters are provided, for example, in A. P. Cohen, "Desiccants" in Kira-Othmer Encylopedia of Chemical Technology, 4 a Ed., Vol. 7 p. 1031-1055, Wiley, New York, 1993. In some embodiments, the blotter does not have a secondary function as a solid pH control material. Example dries that do not necessarily have a secondary function as solid pH control materials include alumina, silica gel, calcium chloride, zinc chloride, calcium sulfate (e.g., anhydrous calcium sulfate), calcium, montorillonite clay, and the like. The double agent compositions of the invention may further include a binder. Suitable binders may include, for example, inorganic salts, wax binders, microcrystalline cellulose and the like. The double agent compositions of the invention may further include a disintegrant. Suitable disintegrants may include, for example, sodium chloride, sodium sulfate, ammonium chloride, ammonium sulfate, microcrystalline cellulose, and the like. The double agent compositions of the invention may further include a glidant. Suitable glidants include, for example, magnesium stearate, calcium stearate, talc, colloidal silicas (e.g., Aerosol 200), carnauba wax, hydrogenated vegetable oils, mineral oil, polyethylene glycols, and the like. Generally, the double agent compositions of the invention may contain various ratios and amounts of the components so that the biocidal monohaloamine and / or dihaloamine agent is generated during the dissolution of the composition in water. Accordingly, the double agent compositions of the invention can be formulated such that the molar ratio of N in the solid nitrogen source to halogen in the solid hypohalite (N / X ratio) is about 2: 1 to about 0.5. :1; about 2: 1 to about 0.8: 1, about 1.5: 1 to about 0.9: 1, about 2: 1 to about 1: 1, or about 1.1: 1. The amount of solid nitrogen source individually present in the double agent compositions of the invention can be, for example, about 1 to about 23, about 2 to about 15, about 5 to about 10, or about of 8% by weight. The amount of solid hypohalite individually present in the double agent compositions of the invention can be, for example, from about 1 to about 27, about 2 to about 20, about 5 to about 15, or about 12. % in weigh. The solid hypohalite and solid nitrogen source can be considered the active ingredients of the double agent compositions of the invention and these two ingredients together also referred to herein as "active agents" or "active agents". Accordingly, the double agent compositions of the invention can be prepared so that the active ingredients form about 50% or less of the total weight of the composition. For example, k assets can make around 5 to about 505, about 5 to about 30%, about 10 to about 30%, about 15 to about 25%, or about 20% of the weight total of the composition. Compositions containing 1 to about 5% of the active ingredients are also contemplated by the invention. Usually, the amount of pH control material can vary widely depending on the material used. For example, the compositions of the invention may contain from about 0.5 to about 25, from about 1 to about 15, or from about 1 to about 105 by weight of pH control material containing a relatively strong base (v. .gr., hydroxide). In other embodiments, the compositions of the invention may contain from about 20 to about 90, about 60 to about 90, or about 80% by weight of pH control material containing a relatively weak base (v. ., carbonate). In additional embodiments, the pH control material may be present in compositions of the invention in amounts of about 50 to about 95, about 70 to about 90, about 75 to about 85.; around 20 to around 80, around 20 to around 75, around 20 to around 30, around 55 to around 67, around 40 to around 95, around 40 to around 80, around 40 to around 60, around 50 to around 70, around 30 to around 90, around 1 to around 5, around 1 to around 3, around 80, around 60, around 25, or about 2.5% by weight. In some embodiments, the dual agent compositions contain an additional pH control material (ie, one second). Appropriate amounts include 0 to about 55, 0 to about 40, or about 20 to about 40% by weight. For double agent compositions containing a dryer, any suitable amount can be used. In some embodiments, double agent compositions contain 15 to about 80, about 15 to about 75, about 15 to about 30, about 15 to about 25, about 20 to about 80, about 18 to about 40, about 18 to about 30, about 50, or about 20% by weight of drying. In some embodiments, the blotter may also function as a pH control material. An example of double-function drier and pH control material is potassium carbonate.

For compositions containing other solid additives, the appropriate amount will depend on the properties and amounts of the other components. For example, when the pH control material contains a strongly reactive substance such as a strong base (e.g., hydroxide), larger amounts of the solid additives such as stabilizer and / or diluent can be employed. In compositions employing less reactive substances such as the pH control material (eg, carbonates), the pH control material can have the same diluting effect as a diluent, so that less (or no) diluent or others Additives may be needed. Accordingly, the double agent compositions of the invention may contain from about 0 to about 55, about 0 to about 40, about 1 to about 83, about 10 to about 90, about 20 about of 90, about 20 to about 40, about 50 to about 90, about 60 to about 90, about 70 to about 90, or about 80% by weight of other solid additives such as diluent, binder, stabilizer, and / or agent against cake formation. For double agent compositions containing a stabilizer, the appropriate amount will depend on the properties and the amounts of the other components. In some embodiments, the double agent compositions contain about 40 to about 75% by weight, about 50 to about 60% by weight, or about 55% by weight of stabilizer. Anti-cake forming agents can be present in the double agent compositions of the invention in amounts of from about 0.1 to about 50, about 0.1 to about 10 and about 0.1 to about 5% by weight. Other components such as disintegrants and glidants may be individually present in the double agent compositions of the invention, 1 such as dual agent compositions suitable for preparing tablets or sticks, in an amount of from about 0.2 to about 5% by weight, about 0.5 to about 2% by weight, about 0.5 to about 0.5 to about 1% by weight, or about 1% by weight. The solid double agent compositions of the invention can be provided as free flowing powders or in compacted form such as tablets or sticks. The double agent compositions can also be packaged in such a manner as to minimize exposure to air, particularly moisture, and can be stored in a hermetically sealed package. Certain exemplary double agent compositions in accordance with the present invention consist essentially of e.g., more than about 95% total weight): a) a solid hypohalite; b) an ammonium salt; and c) a solid pH control material. Here, the solid pH control material may have a secondary function as a diluent, stabilizer, anti-caking, binder, or drying agent, substantially avoiding the need for these ingredients as separate components of the composition. In some embodiments, the solid pH control material is an inorganic carbonate salt such as sodium carbonate or potassium carbonate. Additional related double agent agent compositions Al, A2, A3 and A4 are provided in the Table Below (percentages are given as% by weight). For each of the exemplary double agent compositions, the N / X ratio is about 1.5: 1 to about 0.8: 1. Table A An exemplary double agent composition that employs a secant contains: a) about 5 to about 30% by weight of the solid hypohalite and the source of solid nitrogen, together with; b) about 20 to about 8i0% by weight of a solid pH control material having at least a secondary function (such as a diluent); and c) about 15 to about 75% by weight of drying agent. In some embodiments, the above dual agent composition employing a secant contains: a) about 15 to about 25% by weight of solid hypohalite and solid nitrogen source, together with; b) about 55 to about 67% by weight of a solid pH control material having at least a secondary function (such as a diluent); and c) about 18 to about 30% by weight of drying. In additional embodiments, the above dual agent composition employing a blotter contains: a) about 20% by weight of solid hypohalite and solid nitrogen source, together with; b) about 60% by weight of a solid pH control material having at least a secondary function (such as a diluent); and c) about 20% by weight of drying agent. A further exemplary double agent composition employing a pH control material having at least a secondary function as a diluent and at least a secondary function as a drying agent contains: a) from about 5 to about 30% by weight of the solid hypohalite and the solid nitrogen source, together with, b) about 40 to about 95% by weight of a pH control material having at least a secondary function as a diluent and at least a secondary function as a blotter; and c) 0 to 55% by weight of an additional solid pH control material, a blotter, a stabilizer, or combination thereof. A further exemplary double agent composition employing a pH control material having at least a secondary function as a diluent and at least a secondary function as a drier contains: a) from about 10 to about 30% by weight of the solid hypohalite and solid nitrogen source, together with; b) about 40 to about 80% by weight of a pH control material having at least a secondary function as a diluent and at least a secondary function as a drying agent; and c) 0 to about 40% by weight of an additional solid pH control material, a blotter, an additional stabilizer, or combination thereof. In some embodiments, the above double agent composition having at least a secondary function as a diluent and at least a secondary function as a drier contains: a) about 20% by weight of the solid hypohalite and solid nitrogen source , With; b) about 40 to about 60% by weight of a pH control material having at least a secondary function as a diluent and at least a secondary function as a drying agent; and c) about 20 to about 40% by weight of an additional solid pH control material, an additional secant, a stabilizer, or combination thereof. In some embodiments, the solid pH control material that has at least a secondary function as a solvent and at least a secondary function as a blotter in the above dual agent compositions contains potassium carbonate. The solid pH control material may additionally have a secondary function as a material against cake formation. In some embodiments, the additional solid pH control material contains sodium carbonate. In some embodiments, the secant contains calcium sulfate. In some embodiments, the stabilizer contains sodium chloride. An exemplary dual agent composition employing a blotter and a diluent, stabilizer, anti-cake-forming agent, binder or combination thereof and optionally in the form of a tablet or stick, contains: a) about 5 to about 30% by weight of the solid hypohalite and the solid nitrogen source, together with; b) the combination of about 1 to about % by weight of solid pH control material and about 1 to about 79% by weight of diluent, stabilizer, anti-cake-forming agent, binder, or combination thereof; c) about 15 to about 50% by weight of drying agent; and d) about 0.2 to about 5% by weight of disintegrant, glidant, or combination thereof. In some embodiments, the above dual agent composition employing a blotter and a diluent, stabilizer, anti-cake-forming agent, binder or combination thereof and optionally in the form of a tablet or stick contains: a) about 15 g. to about 25% by weight of the solid hypohalite and the source of nitrogenosolid, together with; b) the combination of about 1 to about 3% by weight of solid pH control material and about 45 to about 55% by weight of diluent, stabilizer, anti-cake-forming agent, binder, or combination thereof same, c) about 15 to about 25% by weight of drying agent; and d) about 0.5 to about 3% by weight of disintegrant, glidant, or combination thereof. In some embodiments, the above dual agent composition employing a blotter and a diluent, stabilizer, anti-caking agent, binder or combination thereof and optionally in the form of a tablet or stick contains: a) about 20 % by weight of the solid hypohalite and the source of nitrogenosolid, together with; b) the combination of from about 1 to about 3% by weight of solid pH control material and around 50 to about 60% by weight of solvent, stabilizer, anti-cake-forming agent, binder, or combination thereof; c) about 20% by weight of drying agent; and d) about 0.5 to about 3% by weight of disintegrant, glidant, or combination thereof. In some embodiments, the above double agent composition employing a blotter and a diluent, stabilizer, anti-cake-forming agent, binder or combination thereof and optionally in the form of a tablet or stick contains: a) about 20 % by weight of the solid hypohalite and the solid nitrogen source, together with; b) the combination of about 2.5% by weight of solid pH control material and about 56.5% by weight of diluent, stabilizer, anti-cake-forming agent, binder, or combination thereof; c) about 20% by weight of drying agent; and d) about 1% by weight of disintegrant, glidant, or combination thereof. In some embodiments related to the above dual agent compositions employing a blotter and a diluent, the diluent contains microcrystalline cellulose or PCC, which may also serve as a binder. In additional embodiments related to the above dual agent compositions, the anti-cake forming agent contains silica. In additional embodiments related to the above dual agent compositions, the composition contains a combination of diluent and anti-cake-forming agent. In additional embodiments related to the above dual agent compositions, a glidant such as magnesium stearate is present. In still further embodiments related to the above dual agent compositions, the secant contains anhydrous calcium sulfate. In still further embodiments related to the above dual agent compositions, the pH control material is an inorganic hydroxide salt, such as NaOH. Certain exemplary double agent compositions employing a stabilizer may contain: a) from about 5 to about 30% by weight of solid hypohalite and solid nitrogen source, together with; b) about 20 to about 80% by weight of solid pH control material having at least a secondary function as a diluent, anti-cake, binder, or blotting agent; and c) about 40 to about 75% by weight of stabilizer. Additional exemplary double agent compositions employing a stabilizer may contain: a) from about 10 to about 30% by weight of solid hypohalite and solid nitrogen source, together with; b) about 20 to about 30% by weight of solid pH control material having at least a secondary function as a diluent, anti-cake, binder or blotting agent; and c) about 50 to about 60% by weight of stabilizer. Additional exemplary double agent compositions employing a stabilizer may contain: a) about 20% by weight of solid hypohalite and solid nitrogen source, together with; b) about 25% by weight of solid pH control material having at least a secondary function as a diluent, cake counter, binder or blotting agent; and c) about 55% by weight of stabilizer. In some embodiments, the stabilizer in the above dual agent compositions contains sodium chloride. In additional embodiments, the exemplary double agent compositions above containing stabilizer further employ sodium carbonate as the component of pH control material. It is also understood that the present invention further encompasses mixtures of two or more of the double agent compositions described herein. In some embodiments, the mixtures may be composed of two different double agent compositions in any weight ratio such as around 10:90, around 20:80, around 25:75, around 30:70, about 40. : 60, or around 50:50. In some embodiments, the mixture is comprised of a first double agent composition that mainly generates onohaloamines in water and a second double agent composition that mainly generates dihaloamines in water. The present invention also encompasses systems containing a combination of two or more of the double agent compositions described hereinbefore. The double agent compositions of the system are typically separated from one another, each in the form of a powder, tablet, bar, or the like. For example, the system may contain a first double agent composition that generates monohaloamines in water and a second double agent composition that generates dihaloamines in water. An example system is a device that contains two or more tablets or bars, each containing a different double agent composition. Systems Containing Single Agent Compositions The present invention further provides systems having a single simple agent composition containing the solid nitrogen source (as described above for double agent compositions) and a second solid single agent composition containing the solid hypohalite (as described above for double agent compositions). The two single agent compositions of the system are separated from one another and can form a biocidal mixture when combined together in water. In some embodiments, the system comprises a first solid single agent composition containing: a) a source of solid nitrogen, b) a solid pH control material; and a second solid single agent composition containing > . a) a solid hypohalite. The term "simple agent composition" is intended to refer to compositions of the invention that contain any one of the solid nitrogen source or solid hypohalite, but not both.In some embodiments, the amount of solid nitrogen source in the first Single solid agent composition is about 10 to about 85, about 60 to about 70, or about 80% by weight.

In some embodiments, the amount of pH control material in the first solid single agent composition is about 1 to about 5, 15 to about 5 90, about 30 to about 40, or about 20% by weight. In some embodiments, the amount of solid hypohalite in the second solid single agent composition is about 10 to about 100, about 80 to about 100, or about 100% by weight. The first solid single agent composition may optionally further contain a drying agent, a stabilizer, an anti-caking agent, a binder, a disintegrant, a glidant, a diluent, or any combination thereof. In some embodiments, the first solid single agent composition also contains a blotter. In some embodiments, the first solid single agent composition further contains a diluent, anti-cake-forming agent, or combination thereof. The second solid single agent composition may additionally optionally contain a solid pH control material, a drying agent, a stabilizer, an anti-caking agent, a binder, a disintegrant, a glidant, a diluent, or any combination thereof. . In some embodiments, the second solid single agent composition further contains a pH control material. In some embodiments, the second solid single agent composition also contains a blotter. In some embodiments, the second solid single agent composition further contains a diluent, anti-caking agent, or combination thereof. Appropriate amounts of blotter in single agent solid compositions include 0 to about 85, 0 to about 60, about 15 to about 30, about 20 to about 80, about 20, and about 50% over. weight. Other components such as stabilizers, anti-caking agents, binders, disintegrants, glidants, diluents, and the like may be present in the solid compositions of single agent of the invention in an amount of from 0 to about 65% by weight. Solid pH control materials, blotters, stabilizers, cake-forming agents, binders, disintegrants, glidants, and diluents that are suitable for the systems of single agent compositions of the invention are described above in connection with the agent compositions. double. Consequently, these ingredients may have one or more secondary functions as described above. In some embodiments with respect to the above system, the first solid single agent composition contains: a) about 10 to about 80% by weight of solid nitrogen source, b) about 1 to about 90% by weight of material of solid pH control; c) about 0 to about 60% by weight of drying agent; and d) about 0 to about 60% by weight of solid diluent, binder, anti-cake-forming agent or combination thereof. In some embodiments in connection with the above system, the first solid single agent composition contains: a) about 10 to about 80% by weight of solid nitrogen source, b) about 20 to about 90% by weight of solid pH control material; c) about 0 to about 60% by weight of drying, and d) about 0 to about 60% by weight of solid diluent, binder, anti-cake-forming agent or combination thereof. In some embodiments in connection with the above system, the first solid single agent composition contains: a) about 10 to about 40% by weight of solid nitrogen source, b) about 50 to about 70% by weight of solid pH control material, c) about 10 to about 30% by weight of drying, and d) about 0 to about 605 by weight of solid diluent, binder, anti-cake-forming agent or combination thereof. In some embodiments, the first solid single agent composition contains: a) about 20% by weight of solid nitrogen source, b) about 60% by weight of solid pH control material; and c) about 20% by weight of drying agent. In some embodiments, the first solid single agent composition contains: a) from about 33 to about 50% by weight of solid nitrogen source; and b) about 50 to about 67% by weight of solid pH control material. In some embodiments, the second solid single agent composition contains: a) from about 10 to about 100% by weight of solid hypohalite; b) about 0 to about 90% by weight of drying agent; c) about 0 to about 60% by weight of solid pH control material; and d) about 0 to about 605 by weight of solid diluent, binder, anti-cake-forming agent, or combination thereof. In some embodiments, the second solid single agent composition contains: a) from about 20 to about 80% by weight of solid hypohalite; b) about 20 to about 80% by weight of drying agent; c) about 0 to about 60% by weight of solid pH control material; and d) about 0 to about 60% by weight of solid diluent, binder, anti-cake-forming agent, or combination thereof. In some embodiments, the second solid single agent composition contains. a) about 50% by weight of solid hypohalite; and b) about 50% by weight of drying agent. In some embodiments, the second single agent solid composition contains about 100% solid hypohalite. In some embodiments of the above systems, the source of solid nitrogen is an ammonium salt. In some embodiments of the above systems, the pH control material is an inorganic carbonate salt or inorganic hydroxide salt. In still further embodiments of the above systems, the secant contains anhydrous calcium sulfate. In some embodiments of the above systems, the molar ratio of N in the solid nitrogen source of the first solid single agent composition to halogen in the solid hypohalite of the second solid single agent composition (N / X ratio) is about from 2.1 to around 0.5: 2, around 2: 1 to around 0.8: 1, around 1.5: 1 to around 0.9: 1, around 1.2: 1 to around 1: 1, or around 1.1: 1. In some embodiments of the above systems, one or both of the first and second solid single agent compositions may further comprise a diluent, stabilizer, cake counter, blotter, binder, disintegrant, or slip agent. In some embodiments of the above systems, one or more of the first and second single agent compositions are in the form of a tablet or bar. In some embodiments one or both of the first and second solid single agent compositions is hermetically sealed in a package. Methods of Use The compositions and systems described herein are useful for preparing biocidal mixtures that can be used to prevent or inhibit the growth of living organisms in liquids. The biocidal mixture can be prepared by combining a composition of the invention, or the first and second compositions of a system of the invention, with an appropriate amount of water. As discussed above, the active ingredients react to form monohaloamines and / or dihaloamines, depending on the pH control material used, which are among the biocidal agents of the resulting biocidal mixture. Accordingly, the term "biocidal mixture" refers to an aqueous mixture containing a composition of the invention, or both first and second compositions of a system of the invention, wherein the mixture also contains monohaloamines (e.g., chloramine) and / or dihaloamines (e.g., dicloramine). The amount of water that is combined with the compositions of the invention to form the biocidal mixtures may vary, but is typically sufficient to at least partially dissolve the active ones so that the formation of one or more haloamines may occur. In some modalities, the amount of water combined with the compositions described herein results in a peak hyaloamine concentration of about 10 to about 10,000, about 100 to about 10,000, about 500 to about 5000, about 500 to about of 3000, or around 600 to about 2000 ppm. In some embodiments, the biocidal mixture has a haloamine concentration of about 4 of 100 to about 5000 ppm, about 500 to about 5000 ppm, or about 600 to about 2000 ppm. In additional embodiments, the weight ratio of water to the total of the first and second solid compositions of systems of the invention is about 1000: 1 to about 5: 1, about 500: 1 to about 10: 1, about from 200.1 to around 10: 1; around 175: 1 to around 40.1, or around 90: 1 to around 70: 1. In some embodiments, the weight ratio of water to solid composition is about 1000.1 to about 5: 1, about 500: 1 to about 10: 1, about 200.1 to about 10: 1; around 175: 1 to around 40.1, or around 90: 1 to around 70: 1. For single agent systems of the invention, the mode of addition of the first and second single or single agent compositions to water can be concurrent or consecutive. For consecutive addition, the two compositions can be added to water in any order. In some embodiments, the first single agent solid composition containing the nitrogen source is added before the second single agent solid composition. In other embodiments, the second single agent solid composition containing solid hypohalite is added before the second single agent solid composition. As used herein, the term "water" refers to any water-based liquid. Accordingly, the term "water" includes substantially pure water as well as aqueous mixtures, solutions and suspensions. The biocidal mixture can be used for the treatment of liquid to prevent or inhibit the growth of living organisms in the liquid. Accordingly, the present invention provides methods for preventing or inhibiting the growth of living organisms in a liquid by preparing a biocidal mixture as described above and treating the liquid with the biocidal mixture. The treatment typically includes combining the biocidal mixture directly with the liquid to be treated. The combination can be carried out batchwise or by continuous flow mixing. The combination of the biocidal and liquid mixture can be carried out so that the final combined liquids result in a maximum haloamine concentration of about 4 to about 20 ppm. Suitable liquids for treatment include any liquid that contains or may contain undesirable living organisms such as protozoan bacteria, microscopic multicellular organisms, algae, fungi, and the like. In addition to pool water and drinking water, the treatment methods of the invention may also be applicable to liquids generated by various industrial processes including pulp and paper milling process. Pulp and paper mills frequently suffer from icrobiological growth, which results from free floating (planktonic) cells, biofilms and silt. Accordingly, the biocidal mixtures of the invention are effective for treatment of mill water, waste water, and other aqueous effluents, and can be combined with other oxidizing and non-oxidizing biocides to control the growth of living organisms. Unless stated otherwise, all percentage values are calculated by weight. The term "contains" as used herein in connection with the compositions of the invention is intended to refer to compositions that include the aforementioned components and optionally include additional components. The term "consists essentially of" as used herein in connection with the compositions of the invention is intended to refer to compositions that are primarily composed of the aforementioned components, and any other components not mentioned that make less than about 5% by weight. % by weight of the total composition. Any composition mentioned herein that contains certain mentioned components is also intended to include compositions consisting essentially of the aforementioned components. In order that the invention described herein be understood more efficiently, examples are provided below. It should be understood that these examples are for illustrative purposes only and should not be considered as limiting the invention in any way. EXAMPLES Conventional laboratory practice was used for sample preparation and for various tests. Typically, 5.8 g of sample was added to 491.6 g of water, or 0.58 g of sample in 49.16 g of water. The solution was stirred to complete the dissolution. 30 mL of this solution was poured through a Corning syringe filter of 0.45 um. The filtrate was then analyzed. The main tests were the Hach (for free and total chloros) and UV. The Hach values (eg, MCA levels) were calculated as the difference between two tests: total and chlorine-free, which were determined using a portable UV meter (Pocket Colori Ether IIMR Hack) and the supplied pre-packs by Hach. The UV spectra were obtained in a digital UV spectrophotometer. Monochloramine gives a maximum at 245 nm, and dicloramine at 206 and 295 nm (T. W. Trofe, G. W. In an, J. D. Johnson, Environ.Sci. Technol. 14, 544 1980)). Example 1: Comparative and Example Compositions Calcium hypochlorite and ammonium chloride, both in powder form, were combined with solid NaOH (pH control material) according to Table 1 below (Ex. Le and Id). One of the solid compositions further contained 80% by weight of a diluent (85% by weight of lactose and 15% by weight of pregelatinized starch) and compressed into a tablet form. The comparative solutions 82200 ppm) were also prepared (eg, la and Ib). The level of onocloramide (MCA) was measured for each experiment after either combining the appropriate solutions (eg la and Ib) or dissolving the solid compositions in water (eg le and Id). The level of monochloramine (MCA) was measured, using a Pockiet Colorimeter IIMR Hack, as the different from total chlorine and lire that is reported below in Table 1 as Hach value. The example provided a slightly lower Hach value immediately after dissolution in water which may be due to the instability of the solid mixture evidenced by the observation that after one day, the Hach value was more than 30% lower. The tablet (eg Id) gave a Hach value similar to the solution fomrulations. Table 1: Comparison of solution and solid formulations (2200 ppm; pH 10) 49. 16 mL of water. pH 9.22 Id NH4C1 Ca (OCl) tablet Yes 790 55 mg 53.5 mg dry, with ppm NaOH 10.8 mg) and binder (467.7 mg, 85% lactose, 15% pregel starch). Dissolved in 49.16 mL of water. pH > 9 Example 2: Additional example compositions Additional double agent compositions containing various diluents and other components were also tested. Each composition was pressed to a tablet before dissolution in water. MCA levels were measured as described in Example Id and reported in Schedule 2 below. Each of the compositions contained 80% by weight of diluent and / or other additives (475 mg), 18% by weight of active (calcium hypochlorite 50.6 mg, ammonium chloride 55.0 mg), and 2% NaOH (13 mg ). Each tablet was then dissolved in 50 L of water. Each of the compositions produced acceptable levels of MCA, the presence of which was confirmed by UV at 245 nm. Table 2. Diluent / additives variation In addition, variations in the level of diluent / additives were tested. From the accumulated data, a level of diluent / additives of > 60% by weight was needed for these particular formulations. Even better results were obtained at 80% by weight. The above compositions formed strong tablets (and could function as powder mixtures); however, they did not have long term shelf stability that is believed to be caused by the reaction between the hypochlorite and the diluent / additives. A formula as in Example 2d decreased in Hach value by 50% in 11 days. More stable formulations were explored below. Example 3: Additional Double Agent Example Compositions Solid powder compositions containing inorganic salt diluents and additives (lacking oxidizable functional groups) were tested. Tables 3-1 and 3-2 below provide data in connection with the stability of compositions containing about 20% by weight of ammonium sulfate and calcium hypochlorite (1.8: 1.0 molar ratio, total weight of 105.6 mg), and 80% by weight of sodium carbonate (474.4 mg) together dissolved in 50 ml of water. The pH remained above 11.0 and no NaOH was used. Each of the 5 samples of CF-3-1 was sealed separately in a vial, which remained unopened until it was erased for pH and Hach value. Under the experimental conditions, the formulation appeared stable. Table 3-1. Biocide composition of MCA with sodium carbonate (condition is sealed, strict preparation and storage) In contrast to the results in Table 3-1, samples prepared using commercial raw materials under less stringent conditions (eg, single samples were repeatedly opened for testing), resulted in more variability and less stability. Consequently, the compositions appeared to benefit from fresh (not aged) starting materials and air protection. The effect was also made to optimize the level of MCA formed (and the Hach value). This was done by varying the molar ratio of ammonium sulfate and calcium hypochlorite. The result (again for powders) is shown in Table 3-2. Table 3-2. Hach value as a function of molar ratio of ammonium sulfate and calcium hypochlorite.

In further experiments, the sodium carbonate in the compositions of Table 3-1 was replaced with sodium acetate, also acting as well as diluting as well as pH controlling agent. The data is provided below in Table 3-3. These compositions were more difficult to handle because the sodium acetate was hygroscopic. Table 3-3. Biocide composition of MCA with sodium acetate Example 4: Double Agent Powder Mixtures Containing Sequents Four powder compositions were prepared as shown in Table 4-1. The first composition (4a) consisted of four components: ammonium sulfate, calcium hypochlorite, sodium carbonate and Drierite. The second composition (4b) was the same as the first one but contained ammonium chloride instead of ammonium sulfate. The level of ammonium chloride was not optimized in sample 4b, and this was probably the reason for the lower Hach values. The third composition (4c) contained 10% sodium chloride, which was found to have some stabilizing action. The fourth composition (4d) used NaOH and precipitated calcium carbonate (PCC) instead of sodium carbonate. In all four cases, the Hach values remained stable for six weeks. Table 4-1. MCA biocide compositions with anhydrous Ca sulfate In addition to the basic formulation with the four chemicals (example 4a), talc or PCC (up to at least 20%) was added without damaging the stability. It was found that insoluble anhydrous calcium sulfate (US Gypsum Company (USG), Chicago, Illinois) was less effective than Drierite as a drying agent.The insoluble anhydride appeared to have a more limited capacity for water absorption and was shown to be effective for only up to about two weeks (Four 4-2) Table 4-2 Biocide compositions of MCA with anhydrous Ca sulfate (USG) Another suitable blotter was found to be potassium carbonate (Table 4-3). Note that potassium carbonate has the notorious advantage of serving five functions at once: diluent, against cake formation, pH control, stabilizer, and drying. Table 4-3. Biocide compositions of MCA with potassium carbonate Instead of Drierite and potassium carbonate, previously dried calcium oxide and Montmnorillonite K10 clay were also found to give good stable powder compositions (Table 4-4). The previously dried silica gel gave more moderate results. In all cases, prior drying of the blotter was found to be beneficial. A typical pre-drying process involved heating in air for 3 hours at high temperatures 8v.gr., above 200 ° C.

Table 4-4. Compositions biocides of MCA with sodium carbonate and other siccatives Example 5: Double Agent Powder Compositions Containing a Stabilizer Two tables are shown for example compositions containing a stabilizer. In accordance with Table 5-1, the compositions contained ammonium sulfate and calcium hypochlorite (as the active component), and sodium carbonate (as well as diluent as pH control material), and sodium chloride (as a stabilizer) . The formulation was shown to be stable. Table 5-1, Biocide compositions of MCA with a stabilizer As shown in Example 5b (see Table 5-2), the level of sodium chloride was lower than in the compositions of Table 5-1, but a stabilizing effect was still observed (although to a lesser degree) . A mixture of sodium chloride and sodium sulfate also resulted in a stabilizing effect (eg 5c) but to a lesser extent than the composition of Table 5-1. Table 5-2. MCA biocide compositions with a stabilizer Example 6: Single Agent Composition Systems The data for a simple agent example system having two separate compositions (one containing the ammonium salt - Part A, and the other containing the hypochlorite - Part B) is shown in the Table 6-1. The two compositions were poured simultaneously into water and dissolved at room temperature. Time study 8 in accordance with Hach values) indicated that the compositions were stable. Table 6-1. Mixture of single agent powder for MCA biocide If Parbe B is kept substantially free of moisture, a stable formulation can be made without drying. An example is shown in Table 6-2. Table 6-2. Simple agent powder mix for MCA biocide Ex. Formulation Time pH Hach elapsed 6b Part A: 0.464 g (NH4) 2S04 0.5 h 11.4 790 3.5 g of Na2C03 14 d 11.3 790 Part B: 0.696 g of Ca (OCl) 2 42 d 11.2 790 Both added to 491.6 g of water for Test Example 7: Tablet Formulations An example of the double agent tablet composition is provided in Table 7-1. All the ingredients were formed into a single tablet. The shelf life was determined to be about 1 month. Table 7-1. Solid MCA biocide in a single tablet formulation The simple agent composition system can be made in the form of tablets as well. An example is given in Table 7-2. This system is more stable.

Table 7-2. Solid MCA biocide in a two tablet formulation Example 8: DCA Generator Powder Composition The data for a pl axis composition that generated dichloramma (DCA) during dissolution in water is given below in Table 8-1. The pH control material that was used was potassium hydrogen phthalate (KHP) which slowly dissolved in water and was buffered in solution at pH 4.3 allowing sufficient time for the initial formation of MCA at higher pH and then the subsequent conversion to DCA as the pH was reduced to 4.3. The presence of DCA was detected as shown by UV and Hach. The compositions also showed prolonged term stability. Table 8-1. Composition of double agent in solid powder to generate DCA biocide An additional pH control system that can be used to generate DCA is monobasic sodium phosphate (Table 8-2). The total Hach value is lower, but the formulation is stable. Table 8-2. Composition of double agent in solid powder to generate DCA biocide Various modifications of the invention, in addition to those described herein, will appear to those skilled in the art from the foregoing description. These modifications are also intended to be within the scope of the appended claims. Each reference, including all patents, patent applications, and journal literature, cited in the present application is hereby incorporated by reference in its entirety.

Claims (35)

1. CLAIMS 1. A solid double agent composition comprising. a) a solid hypohalite; b) a source of solid nitrogen; and c) a component that is either > . i) a solid pH control material having at least a secondary function such as a diluent, stabilizer, anti-cake-forming agent, binder or blotter; or ii) a combination of a pH control material and a diluent, stabilizer, anti-cake-forming agent, binder, siccative, or combination thereof; wherein the double agent composition forms a biocidal mixture when combined with water.
2. 2. The composition according to claim 1, wherein the solid hypohalite is calcium hypochlorite.
3. 3. The composition according to claim 1, wherein the source of solid nitrogen is an ammonium salt or organic amine. Four . The composition according to claim 1, wherein the solid pH control material or the solid pH control material having at least a secondary function keeps the biocidal mixture at a pH of about 8 to about 13. 5. The composition according to claim 1, wherein the solid pH cdontrol material having at least a secondary function is an inorganic salt of carbonate, phosphate, acetate, hydrogen phthalate, or hydroxide. 6. The composition according to claim 1, wherein the solid pH control material has no secondary function as a diluent or stabilizer. 7. The composition according to claim 1, wherein the molar ratio of N in the source of solid nitrogen to halogen in the solid hypohalite is about 2: 1 to about 0.5: 1. 8. The composition according to claim 1, wherein the solid hypohalite and the solid nitrogen source together comprise about 5 to about 30% by weight of the total composition. 9. The composition according to claim 1, further comprising a secant. 10. The composition according to claim 1, further comprising a stabilizer. 11. The composition according to claim 10, wherein the stabilizer is sodium chloride. 12. The composition according to claim 1, further comprising a diluent, anti-cake-forming agent, or combination thereof. 13. The composition according to claim 12, wherein the diluent, anti-cake-forming agent, or combination thereof comprises an inorganic salt. 14. The composition according to claim 1, which consists essentially of: a) a solid hypohalite; b) an ammonium salt; and c) a solid pH control material having at least a secondary function such as a diluent, stabilizer, anti-cake-forming agent, binder or blotter. 15. The composition according to claim 14, wherein the solid hypohalite and the ammonium salt together comprise about 5 to about 30% by weight of the total composition. 16. The composition according to claim 14, wherein the solid pH control material comprises from about 20 to about 90% by weight of the total composition. 17. The composition according to claim 14, wherein the pH control material comprises an inorganic carbonate salt. 18. The composition according to claim 1, comprising: a) about 5 to about 305 by weight of the solid hypohalite and the source of solid nitrogen, together; b) about 20 to about 80% by weight of the solid pH control material having at least a secondary function; and c) about 15 to about 75% by weight of drying agent. 19. The composition according to claim 1, comprising. a) around 5 to about 30% by weight of the solid hypohalite and the solid nitrogen source, together; b) about 40 to about 95% by weight of the pH control material having at least a secondary function as a diluent and at least a secondary function as a drying agent; and c) 0 to about 55% by weight of an additional pH control material, a blotter, a stabilizer, or combination thereof. 20. The composition according to claim 1, comprising: a) about 5 to about 30% by weight of the solid hypohalite and the source of solid nitrogen, together; b) the combination of from about 1 to about 5% by weight of the solid pH control material, and from about 1 to about 79% by weight of diluent, stabilizer, anti-cake-forming agent, binder, or combination thereof the same; c) about 15 to about 50% by weight of drying agent; and d) about 0.2 to about 5% by weight of disintegrant, glidant, or combination thereof. 21. The composition according to claim 1, comprising. a) about 5 to about 30% by weight of solid hypohalite and solid nitrogen source, together; b) about 20 to about 80% by weight of solid pH control material having at least a secondary function as a diluent, cake counter, binder, or blotting agent; and c) about 40 to about 75% by weight of stabilizer. 22. The composition according to claim 21, wherein the stabilizer comprises sodium chloride. 23. A system comprising a first solid single agent composition and a second solid single agent composition separated from the first solid single agent composition, wherein the first solid single agent composition comprises: a) a source of solid nitrogen , b) a pH control material; and wherein the second solid simple agent composition comprises: a) a solid hypohalite; wherein the first solid single agent composition and the second solid single agent composition together form a biocidal mixture when combined with water. 24. The system according to claim 23, wherein the first solid single agent composition comprises. a) about 10 to about 80% by weight of the solid nitrogen source, b) about 1 to about 90% by weight of the solid pH control material; and c) about 0 to about 60% by weight of a secant, d) about 0 to about 60% by weight of a solid diluent, binder, anti-cake-forming agent or combination thereof. 25. The system according to claim 23, wherein the second solid simple agent composition comprises. a) around 10 to about 100% by weight of the solid hypohalite; and b) about 0 to about 90% by weight of the secant, c) about 0 to about 60% by weight of a solid pH control material; and d) about 0 to about 605 by weight of a solid diluent, binder, anti-cake-forming agent, or combination thereof. 26. The system according to claim 23, wherein the source of solid nitrogen is an ammonium salt. 27. The system according to claim 23, wherein the pH control material comprises an inorganic salt of carbonate or inorganic salt of hydroxide. 28. The system according to claim 23, wherein the first solid single agent composition further comprises a drier. 29. The system according to claim 28, wherein the secant comprises anhydrous calcium sulfate. 30. A method for preparing a biocidal mixture comprising combining the composition according to claim 1 with an appropriate amount of water to produce a peak haloamine concentration of about 10 to about 10,000 ppm. 31. The method according to claim 30, wherein the weight ratio of water to composition is about 1000: 1 to about 5: 1. 32. A method for preparing a biocidal mixture comprising combining the first and second solid single agent compositions of the system according to claim 23, with an amount of water appropriate to produce a peak haloamine concentration of about 10 to about of 10,000 ppm. 33. The method according to claim 32, wherein the weight ratio of water to the total of the first and second solid single agent compositions is about 1000: 1 to about 5: 1. 34.- A method for preventing or inhibiting the growth of living organisms in a liquid comprising: a) preparing a biocidal mixture according to claim 30, and b) treating the liquid with the biocidal mixture. 35.- A method to prevent or inhibit the growth of living organisms in a liquid, which comprises. a) preparing a biocidal mixture according to claim 32; and b) treating the liquid with the biocidal mixture.