AU2009327415A1 - Formulations of broad spectrum biocides and their use in improved methods for the treatment of ballast water - Google Patents

Abstract

The present invention relates to a method for the treatment of ballast water on board seagoing vessels including the use of formulations of sparingly soluble biocides.

Description

WO 2010/071804 PCT/US2009/068729 FORMULATIONS OF BROAD SPECTRUM BIOCIDES AND THEIR USE IN IMPROVED METHODS FOR THE TREATMENT OF BALLAST WATER TECHNICAL FIELD 5 The invention relates to formulations of sparingly soluble broad spectrum biocides and their use in the treatment of ballast water. In particular, the invention relates to formulations of 2-methyl-1,4-naphthalenedione and their use in 10 improved treatments of ballast water. BACKGROUND ART The introduction of harmful aquatic organisms and pathogens to 15. new environments, including via ships' ballast water, has been identified as one of the four greatest threats to the world's oceans. It is estimated that a foreign marine species is introduced to 20 a new environment somewhere in the world every nine weeks. Human health, ecological and economic impacts can be severe. (Raaymakers (2002)) -Shipping moves over 8 % of the world's commodities and 25 transfers approximately 3 to 5 billion tonnes of ballast water internationally each year. Ballast water is essential to the safe and efficient operation of modern shipping, providing balance and stability to unladen ships. 30 Ballast water is carried by ships to ensure stability, trim and structural integrity. Ships have carried solid ballast, in the form of rocks, sand or metal for thousands of years. In modern times, ships use water as ballast.

WO 2010/071804 PCT/US2009/068729 There are thousands of marine species that may be carried in ships ballast water. Anything that is small enough to pass through a ship's ballast water intake ports and pumps may be 5 carried. This includes various propagules of bacteria and other microbes, small invertebrates and the eggs, cysts and larvae of various species. The problem is compounded by the fact that virtually all 10 marine species have life cycles -that include a planktonic stage or stages. Even species in which the adults are unlikely to be taken on or in ballast water, for example, because they are too large or live attached to the sea bed, may be transferred in ballast water during their planktonic 15 phase. Natural barriers, 'such as temperature and land masses, have prevented many species from dispersing into certain areas. This has resulted in the natural patterns of biogeography 20 observed in the oceans today.. In particular, the pan-global tropical zone has separated the northern and southern temperate and cold waters zone. This has allowed many species to evolve quite independently in these latter zones, resulting in quite different marine biodiversity between the northern 25 and southern hemispheres. The commencement of the use of water as ballast, and the development of larger, faster ships completing their voyages. in even shorter times, combined with rapidly increasing world 30 trade, means that the natural barriers to the dispersal of species across the oceans are being reduced. 2 WO 2010/071804 PCT/US2009/068729 It is estimated that at least 7,000 different species are being carried in ships ballast tanks around the world. When factors are favourable a species introduced by the discharge of ballast water may survive and establish a reproductive 5 population in the new host environment. The introduced species may even become invasive, out competing native species and multiplying into pest proportions. In the USA the European zebra muscle Dreissena polymorpha has 10 infested over 40 % of internal waterways and they have required between US$ 750 million and US$ 1 billion in expenditure on control measures between 1989 and 2000. In southern Australia,- the Asian kelp and Undaria pinnatifida 15 is invading new areas rapidly, displacing the native's seabed communities. In the black sea, the filter feeding North American jellyfish Mnemiopsis leidyi has occasionally reached densities of 1 kg 20 of biomass/m 2 . It has depleted native plants and stocks to such an extent that it has contributed to the collapse of the entire black sea commercial fisheries. In several countries introduced, microscopic, "red-tide" algae 25 (toxic dinoflagellates) have been absorbed by filter-feeding shellfish, such as oysters. When eaten by humans, these contaminated shellfish can cause paralysis and even death. In response to these ecological threats states are introducing 30 mandatory requirements concerning the discharge of ballast water. The threat was recognised in the report of the United Nations Conference on Environment and Development (UNCED). In the section on prevention, reduction and control of 3 WO 2010/071804 PCT/US2009/068729 degradation of the marine environment from sea-based activities it is stated: 17.30. States, acting individually, bilaterally, regionally 5 or multilaterally and within the frame work of IMO and other relevant international organizations, whether sub-regional, regional or global, as appropriate, should assess the need for additional measures to address degradation of the marine environment from shipping by considering the adoption of 10 appropriate rules on ballast water discharge to prevent the spread of non-indigenous organisms. In November 1997 the International Maritime Organisation (IMO) adopted resolution A.868 (20) entitled "Guidelines for the 15 control and management of ships ballast water to minimise a transfer of harmful aquatic organisms and pathogens". In a report prepared for the Northeast-Midwest Institute and entitled "Global market analysis of ballast water treatment 20 technology" it was anticipated that after 2008 all international trading vessels that use sea water as ballast are likely to fall under the IMO convention (Tjallingii et al (2001)). 25 In this report it was also anticipated that ballast water exchange (BWE) would remain an option open to ship owners for some time to come. The option for ship owners to choose between on board ballast water treatment (BWT) and ballast water exchange would therefore remain. 30 It was noted in the report that ballast water treatment (BWT) still faces technical challenges before it could provide a sound alternative for BWE. The most important difficulties were recognised as those relating to retrofitting equipment 35 into existing ships, especially where the flow rates are high 4 WO 2010/071804 PCT/US2009/068729 and available space for equipment is limited. The report stated that there was no doubt that a strong demand for an environmentally sound and effective ballast water treatment technology would emerge. 5 Ballast water exchange (BWE) cannot be utilised in near shore voyages and was noted in the report as being dangerous to ships under certain circumstances due to excessive stresses and strains. A technical constraint on the ready adoption of 10 ballast water treatment as opposed to ballast water exchange is the "translation" of existing and field tested "on-shore technology and equipment" to the "on-board environment" with its different characteristics. 15 Any ballast water treatment adopted by the shipping industry must be safe for ship and crew, environmentally acceptable, practicable, economical, and biologically effective. Various options are available for the treatment of ballast water, including: 20 * Mechanical treatment methods such as filtration and separation; e Physical treatment methods such as sterilization by 25 ozone, ultraviolet light, electric currents and heat treatment; and - Chemical treatment methods such as adding biocides to ballast water to kill organisms. 30 Mechanical treatment methods seek to remove organisms from the ballast water. Filtration and separation methods include 5 WO 2010/071804 PCT/US2009/068729 coagulation/flocculation, cyclonic separation, and self cleaning screens. Physical treatment methods seek to kill the organisms in the 5 ballast water. These include the use of ultraviolet light, ozone, heat treatment, oxygen deprivation, high frequency ultrasound, electro-ionization, gas super-saturation, and low frequency sonics. 10 Chemical treatment methods also seek to kill, or at least devitalize, the organisms in the ballast water. These methods include pH adjustment and the use-of biocidal chemicals. For a chemical treatment to be effective a minimum aquacidal 15 concentration must be maintained throughout the volume of the ballast water for a specified period of time. The cost effectiveness of these methods of treatment will be enhanced if the minimum amount of chemical required to achieve the minimum aquacidal concentration throughout the volume of the 20 ballast water is added. Environmental impacts when the treated ballast water is discharged also need to be minimised.

Menadione (2-Methyl-1,4-naphthalenedione, Vitamin K3) is a quinone derivative of naphthalene with a predicted 25 solubility in water (pH 7, 25 *C) (calculated using Advanced Chemistry Development Software V9.04) of less than 400 jmol/L. Despite this low solubility, menadione was determined to be effective in devitalizing a broad range of harmful aquatic organisms and pathogens that may be present in ballast water 30 (Cutler et al (2001)). The low solubility of menadione has been perceived as a limitation in its use in the treatment of ballast water on 6 WO 2010/071804 PCT/US2009/068729 board ships. As noted above, to be effective the active ingredient must be present at a concentration effective to devitalize the harmful aquatic organisms and pathogens throughout a large, enclosed volume of water. To solve this 5 problem one may resort to using suitable organic solvents in which the quinone is soluble to promote the dispersion of the compound in the water to be treated. The solubility of menadione in various solvent combinations has been determined by Song et al (2007). 10 As a consequence of this perceived limitation, water-soluble derivatives of menadione have been considered for use in the treatment of ballast water. Menadione sodium bisulfite (MSB) is one such water-soluble derivative of menadione, and by 15 contrast with menadione, is relatively stable to photodegradation (Song et al (2008)). Other water-soluble derivatives of menadione that have been considered for use include the nicotinamide salt of menadione bisulphite (MNB) (Manzotti and Monteleone (2004)). 20 As stated in Manzotti and Monteleone (2004): [An] object is to provide a method for treatment preferably of either fresh or salt water in water basins of any size, waters 25 in conduits for civil and industrial use, and ballast water, said method using highly water soluble compounds in order to allow the desired concentration be obtained through the use of the least amount as possible of said compounds. 30 As further stated in Manzotti and Monteleone (2004): ... with those biocides which dissolve poorly in the water pool, the inhibition of the target organisms only takes place in a restricted area surrounding the biocide particle whereas a 35 substantial survival of said organisms is to be expected in 7 WO 2010/071804 PCT/US2009/068729 the great part of the bulk of treated water. This is extremely important whenever water of water basins of any size, water from civil and industrial conduits and ballast water should be treated because of the huge quantity of liquid to be 5 effectively disinfested. The improved rate of biodegradation of MNB relative to that of menadione and MSB was presented in Manzotti and Monteleone (2004) as a particular advantage favoring the use of this 10 water soluble menadione derivative over menadione. It is an object of the invention to provide an improved method of ballast water treatment. 15 It is an object of the invention to provide formulations of 2 methyl-1,4-naphthalenedione that are particularly useful in the treatment of ballast water. These objects are to be read disjunctively with the object of 20 to at least provide a useful choice. DISCLOSURE OF INVENTION In a first aspect the invention provides a flowable 25 concentrate formulation of a sparingly soluble biocide for use in the treatment of ballast water. Preferably, the sparingly soluble biocide is 2-methyl-1,4 naphthalenedione. 30 Preferably, the flowable concentrate is a wettable powder or a suspension concentrate. 8 WO 2010/071804 PCT/US2009/068729 In a first embodiment, the flowable concentrate is a suspension concentrate. Preferably, the flowable concentrate is a'suspension concentrate with a particle size distribution substantially equivalent to that provided in Figure 1. More 5 preferably, the suspension concentrate comprises 40 to 85 % of the sparingly soluble biocide and 7 to 9 % of a starch or dihydric alcohol. In a second embodiment, the flowable concentrate is a wettable 10 powder. Preferably, the wettable powder comprises greater than 50% by weight of the sparingly soluble biocide. More preferably, the wettable powder comprises at least 80% by weight of the sparingly soluble biocide. 15 In an option, the formulation further comprises at least one biocidal quaternary ammonium and/or phosponium compound and at least one anionic surfactant in a molar ratio of from 5 to 1000. Preferably, the formulation further comprises at least one biocidal quaternary ammonium and/or phosponium compound 20 and at least one anionic surfactant in a molar ratio of from 11 to 1000. More preferably, the formulation further comprises at least one biocidal quaternary ammonium and/or phosponium compound and at least one anionic surfactant in a molar ratio of from 20 to 1000. 25 In an embodiment of the first aspect the invention provides a suspension concentrate formulation consisting of: Ingredient concentration (% w/w) Function 2-methyl-1, 4- 44-1 Active naphthalenedione 1,2-Propanediol 8.0 Formulant TENSIOFIX SC 1.5 Formulant TENSIOFIX" XD23 0.5 Formulant SAG 30 ~ 0.5 Antifoam 9 WO 2010/071804 PCT/US2009/068729 PROXEL GXL 0.1 Preservative Xanthan 'gum 0.05 Formulant Water 45.25 Carrier In an embodiment of the first aspect the invention provides a wettable powder formulation consisting of: Ingredient Concentration (% w/w) Function 2-methyl-1,4 80.0 Active naphthalenedione Pure-Dent B700 8.0 Formulant STEPSPERSE DF-200 7.0 Formulant STEPSPERSE DF-500 3.0 Formulant STEPWETm DF-90 1.0 Formulant HiSil 233 1.0 Formulant 5 In a second aspect the invention provides a method of treating ballast water in a tank of a seagoing vessel comprising the steps of: 10 1. Adding an effective amount of a flowable concentrate formulation of a sparingly soluble biocide to the tank; 2. Maintaining the ballast water in the tank for a time and at a temperature sufficient to devitalize harmful aquatic 15 organisms and pathogens that may be present in the ballast water; and then 3. Expelling the ballast water from the tank to the exterior of the vessel. 20 Preferably, the sparingly soluble biocide is the compound 2 methyl-1,4-naphthalenedione. In a first embodiment, the flowable concentrate is a 25 suspension concentrate. Preferably, the flowable concentrate 10 WO 2010/071804 PCT/US2009/068729 is a suspension concentrate with a particle size distribution substantially equivalent to that provided in Figure 1. More preferably, the suspension concentrate comprises 40 to 85 % of the sparingly soluble biocide and 7 to 9 % of a starch or 5 dihydric alcohol. In a second embodiment, the flowable concentrate is a wettable powder. Preferably, the wettable powder comprises greater than 50% by weight of the sparingly soluble biocide. More 10 preferably, the wettable powder comprises at least 80% by weight of the sparingly soluble biocide. In an option, the formulation further comprises at least one biocidal quaternary ammonium and/or phosponium compound and at 15 least one anionic surfactant in a molar ratio of from 5 to 1000. Preferably, the formulation further comprises at least one biocidal quaternary ammonium and/or phosponium compound and at least one anionic surfactant in a molar ratio of from 11 to 1000. More preferably, the formulation further 20 comprises at least one biocidal quaternary ammonium and/6r phosponium compound and at least one anionic surfactant in a molar ratio of from 20 to 1000. Preferably, the effective amount is sufficient to provide an 25 initial concentration of the sparingly soluble biocide in the ballast water of at least 800 ppb. More preferably, the effective amount is sufficient to provide an initial concentration of the sparingly soluble biocide in the ballast water of at least 1.6 ppm. Most preferably, the effective 30 amount is sufficient to provide an initial concentration of the sparingly soluble biocide in the ballast water of at least 5 ppm. 11 WO 2010/071804 PCT/US2009/068729 Preferably, the time sufficient to devitalize harmful aquatic organisms and pathogens is less than 48 hours. More preferably, the time sufficient to devitalize harmful aquatic organisms and pathogens is less than 24 hours. 5 In a third aspect the invention provides a suspension concentrate formulation of a sparingly soluble biocide packaged with directions for use in the treatment of ballast water in a tank of a seagoing vessel where the sparingly 10 soluble biocide has a median particle size of 2.0 to 3.5 ym and a maximum particle size of 9.0 pm. Preferably, the suspension concentrate formulation is a suspension concentrate formulation of the compound 2-methyl 15 1, 4 -naphthalenedione. In a fourth aspect the invention provides a wettable powder formulation of a sparingly soluble biocide packaged with directions for use in the treatment of ballast water in a tank 20 of a seagoing vessel where the wettable powder comprises at least 80% by weight of the sparingly soluble biocide. Preferably, the suspension concentrate formulation is a suspension concentrate formulation of the compound 2-methyl 25 1,4-naphthalenedione. In a fifth aspect the invention provides a seagoing vessel containing ballast water to which a flowable concentrate formulation of a sparingly soluble biocide of the first aspect 30 of the invention has been added. In the description and claims the following acronyms, terms and phrases have the meaning provided: 12 WO 2010/071804 PCT/US2009/068729 "Benthic" means normally living at the soil-water interface at the bottom of a sea or lake. 5 "Biocide" means an active ingredient to which the devitalization of a population of organisms or pathogens is attributed. "Devitalisation" means the depriving of strength and vigour of 10 a population of organisms or pathogens so that substantially no viable individuals remain and "devitalize" has a corresponding meaning. "Flowable concentrate" means a concentrated formulation of 15 active ingredient(s) in a liquid or solid form that is capable of being poured from a container. "Harmful aquatic organisms and pathogens" means the plurality of species recognized by the International Maritime 20 Organization (IMO)-to present a threat to marine ecology. "Pelagic" means normally living in the middle depths and surface waters a sea or lake. 25 "Population" means a collection of individuals of the same species. "ppb" means parts per billion (109) on a per weight basis. 30 "ppm" means parts per million (106) on a per weight basis. "Suspension concentrate" means a flowable concentrate that is a stable suspension of active ingredient(s) in water. 13 WO 2010/071804 PCT/US2009/068729 "Sparingly soluble" means having a solubility in water (pH 7, 25 *C) of less than 500 pmol/L. 5 "Treatment of ballast water" means the devitalization of harmful aquatic organisms and pathogens that may be present in the water and "treating of ballast water" has a corresponding meaning. 10 "Viable" means capable of growth and reproduction. "Wettable powder" means a formulation that forms a suspension of active ingredient(s) on addition to water. 15 Unless stated otherwise percentages (%) used to define formulations and mixtures are calculated on a per weight basis. Exemplary embodiments of the invention will now be described 20 - in detail with reference to the Figures of the accompanying drawings pages. BRIEF DESCRIPTION OF DRAWINGS 25 Figure 1. Particle size distribution of the suspension concentrate designated SEAKLEEN' 500SC. DETAILED DESCRIPTION 30 The inventor has determined that contrary to the assertions made in the prior art, formulations of menadione (2-methyl 1,4-naphthalenedione) can be used effectively in the treatment of ballast water. Indeed, the limited solubility of the active ingredient may be of particular advantage where the 14 WO 2010/071804 PCT/US2009/068729 harmful aquatic organisms and pathogens reside in the sediments that accumulate and are retained in the ballast water tanks of seagoing vessels. 5 The formulations are prepared as a flowable concentrate of the sparingly soluble biocide. The flowable concentrate may be in the form of a wettable powder or suspension concentrate, although the latter is particularly preferred due to the convenience with which an effective amount of the active 10 ingredient may be delivered into the ballast water tank. A flowable concentrate formulation of a sparingly soluble biocide that provides a suspension with a median particle size of 2.0 to 3.5 pm and a maximum particle size of 9.0 ym when 15 added to the ballast water in a tank of a seagoing vessel is believed to be optimal to devitalize the harmful aquatic organisms and pathogens both suspended in the ballast water and residing in the residula sediment. Over time a portion of the sparingly soluble biocide is anticipated to concentrate in 20 the sediment augmenting the efficacy of the ballast water treatment. The efficacy of the treatment may be further augmented by the addition of a biocidal quaternary ammonium and/or phosphonium 25 compound. The use of such compounds in combination with an anionic surfactant in a manner that prevents foaming is described in Sweeny et al (2008). Biocidal quaternary ammonium and/or phosphonium compounds such 30 as alkyldimethyl-benzylammonium chloride or tributyl tetradecylphosphonium clhloride may be used. Anionic surfactants may be selected from the group consisting of 15 WO 2010/071804 PCT/US2009/068729 diamylsulfosuccinate, dihexyl sulfosuccinate, dioctyl sulfosuccinate, ditridecyl sulfosuccinate, and their salts. In use it is recognized that the formulations may be dispensed 5 directly into the ballast water enclosed in the tank while the ship is in transit. Alternatively, the formulations could be dispensed into the ballast water tank prior to the tank being filled with ballast water. A further option is for metered delivery of the formulations into the flow of ballast water as 10 it is pumped into the tanks. It will be apparent to those skilled in the art that formulants with undesirable environmental impacts, such as ethoxylated-alkyl phenols, should be excluded from the 15 formulations. For example, linear alcohols or ethylene oxide/propylene oxide block polymers are preferred for use as surfactants in addition to the biocidal quaternary ammonium and/or phosphonium compounds. 20 It will also be apparent from the results presented that efficacy of the method of the invention is enhanced by maintaining the ballast water in total darkness for a sufficient period of time prior to expelling the ballast water from the tank to the exterior of the vessel. The 25 susceptibility of menadione to photo-degradation makes the sparingly soluble biocide particularly suitable for the treatment of ballast water. 16 WO 2010/071804 PCT/US2009/068729 EXAMPLES Preparation of SEAKLEEN"" 80OWP 5 Batches of a wettable powder formulation of 2-methyl-1,4 naphthalenedione were prepared. The ingredients listed in Tables la or lb were mixed at the concentrations indicated and blended in a Brinkman Hammer Mill (1 x 2.0 mm, 2 x 0.75 mm) to provide the wettable powder. 10 Ingredient Concentration (% w/w) Function 2-methyl-1,4 naphthalenedione 80.0 Active Pure-Dent B700 8.0 Formulant STEPSPERSE" DF-200 7.0 Formulant STEPSPERSE" DF-500 3.0 Formulant

STEPWET

m DF-90 1.0 Formulant HiSil 233 1.0 Formulant Table la. Formulation designated SEAKLEEN 8boWP. Ingredient Concentration (% w/w) Function 2-methyl-1,4 naphthalenedione 80.0 Active Paragon Clay 8.0 Formulant STEPSPERSE" DF-200 7.0 Formulant STEPSPERSE" DF-500 3.0 Formulant STEPWET" DF-90 1.0 Formulant HiSil 233 1.0 Formulant 15 Table lb. Formulation designated SEAKLEEN" 800WP. Suspensibility of the wettable powder formulations was evaluated over a 3 month period at an elevated temperature of 50~*C. The results for each formulation are presented in 20 Tables 2a and 2b. 17 WO 2010/071804 PCT/US2009/068729 Con entration Suspensibility (%) Initial 1 month 3 month 1000 ppm 90.7 79.9 79.9 2000 ppm 94.3 75.8 81.6 Table 2a. Suspensibility of the wettable powder formulation designated SEAKLEEN" 800WP (Table la). 5 Concentration Suspensibility (%) Initial 1 month 3 month 1000 ppm 90.7 79.9 79.9 2000 ppm 94.3 75.8 81.6 Table 2b. Suspensibility of the wettable powder formulation designated SEAKLEEN" 800WP (Table lb). 10 The formulations were determined to have a measured activity (%) of 95.5 +5.5 relative to the theoretical activity (mean of 2 batches). Preparation of SEAKLEEN m 500SC 15 Batches of a suspension concentrate (SC) formulation of 2 methyl-1,4-naphthalenedione were prepared. The ingredients listed in Tables 2a or 2b were blended to provide the suspension concentrate. 20 Ingredient Concentration (% w/w) Function 2-methyl-1,4 naphthalenedione 44.1 Active 1,2-Propanediol 8.0 Formulant TENSIOFIX SC 1.5 Formulant TENSIOFIX" XD23 0.5 Formulant SAG 30 0.5 Antifoam PROXEL" GXL 0.1 Preservative Xanthan gum 0.05 Formulant Water 45.25 Carrier Table 3. Formulation designated SEAKLEEN' 500SC. 18 WO 2010/071804 PCT/US2009/068729 Characteristic Determination Purity (% w/w) 44 ±0.2 Density (g/ml) 1.146 ±0.02 pH 6.42 +0.01 Suspensibility 95.2 ±1.0 Table 4. Characteristics of the formulation designated SEAKLEEN" 500SC (Table 3) (mean of 2 batches). 5 Laboratory testing of the efficacy of formulations The SEAKLEEN" formulations were evaluated for use in the treatment of ballast water. Efficacy of the SEAKLEEN" formulations (the compound 2-methyl-1,4-naphthalenedione as 10 active ingredient) was determined with or without the inclusion of the water soluble menadione sodium bisulfite (MSB). Assays were performed using an average initial count of 247 15 Mytilus galloprovincialis larvae per 10 ml sample. The results of the assays employing different light conditions for the aging of te.st solutions and bioassay are presented in Tables 5 to 9. Concentration (ppb) % Mortality Total darkness Constant light 500 100* 100* 200 0 7.3 100 0 1.6 50 0 0 Control 0 0 20 Table 5. Efficacy of a mixture of 80% MSB and 20% SEAKLEEN"' 800WP against Mytilus galloprovincialis larvae following aging of the test solutions for 48 hours in total darkness and conducting the bioassay under the light conditions indicated. *p 50.,05 25 19 WO 2010/071804 PCT/US2009/068729 Concentration (ppb) % Mortality 500 100* 200 4.3 100 1.6 50 0 Control 0 Table 6. Efficacy of a mixture of 80% MSB and 20% SEAKLEEN 800WP against Mytilus galloprovincialis larvae following aging of the test solutions for 48 hours and conducting the bioassay under constant light. *p S 0.05 5 Concentration (ppb) % Mortality 500 100* 200 25.3* 100 1.7 50 0 Control 0 Table 7. Efficacy of the formulation SEAKLEEN 800WP against Mytilus galloprovincialis larvae following aging of the test solutions for 48 10 hours and conducting the bioassay in total darkness. *p 0.05 Concentration (ppb) % Mortality 500 94.4* 200 3.7* 100 0 50 0 Control 0 Table 8. Efficacy of the formulation SEAKLEEN" 800WP against Mytilus 15 galloprovincialis larvae following aging of the test solutions for 48 hours in total darkness and conducting the bioassay under constant light. *p 5 0.05 20 WO 2010/071804 PCT/US2009/068729 Concentration (ppb) % Mortality 500 69.9* 200 8.0* 100 0 50 0 Control 0 Table 9. Efficacy of the formulation SEAKLEEN m 800WP against Mytilus galloprovincialis larvae following aging of the test solutions for 48 hours and conducting the bioassay under constant light. *p 5 0.05 5 Notably the formulation of SEAKLEEN m BOOWP demonstrated the highest efficacy at 200 ppm against the test organism Mytilus galloprovincialis larvae when both the aging of the test solutions and conducting of the bioassay were performed under 10 total darkness. Efficacy of SEAKLEEN T M 800WP was reduced by either aging the test solutions or conducting the bioassay under constant light. These results indicate the suitability of SEAKLEEN" 800WP for 15 use in the treatment of ballast water enclosed in tanks that is to be expelled to the exterior of the ship following treatment. Shipboard testing of the efficacy of formulations 20 The efficacy of the formulation SEAKLEEN m 800WP was evaluated in a shipboard trial. The trial was conducted aboard the tanker Seabulk Mariner as-detailed in the publication of Wright et al (2009) . The disclosures of this publication are 25 incorporated in their entirety. Briefly, the formulation, SEAKLEEN" 800WP was mixed as a slurry and the seawater in ballast water tanks was treated at a rate equivalent to a nominal concentration of 2-methyl-1,4 21 WO 2010/071804 PCT/US2009/068729 naphthalenedione of 0.8 (tank 5S) or 1.6 (tank 5P) mg/L. Untreated water in a third tank partially filled at the commencement of the ballasting operation and completely filled at the end of the ballasting operation was used as a control 5 (untreated). Water samples were collected from the tanks containing treated seawater at 2 hours, 15 hours, 48 hours, 49.5 hours and 52.5 hours after treatment. The third, fourth and fifth samples 10 were collected during and following the flow-through ballast water exchange that commenced just prior to collection of the third set of samples. The fifth set of samples were collected following a nominal 300% flow-through exchange. Collection of samples of treated ballast water was immediately followed by 15 samples of control, untreated, ballast water. Following a target dose of 0.8 mg/L of 2-methyl-1,4 naphthalenedione the third set of samples (48 hours) were determined to contain a concentration of 0.49 mg/L. Following 20 a target'dose of 1.6 mg/L of 2-methyl-1,4-naphthalenedione the third set of samples (48 hours) were determined to contain a concentration of 1.32 mg/L. The mortality of zooplankton (including benthic species) in these treated ballast water samples is presented in Table 10. 25 As stated by Wright et al (2009): Following 48 h exposure to SEAKLEEN" in both the high-dose tank [1.6 mg/L and the low-dose tank [0.8 mg/LI no surviving 30 zooplankton were found. With reference to the publication of Raikow et al (2006) the publication of Wright et al (2009) states: 22 WO 2010/071804 PCT/US2009/068729 While SEAKLEEN' shows good efficacy against pelagic organisms, it is less effective against some benthic vegetative stages and eggs. 5 It should be noted that in the studies of Raikow et al (2006) menadione sodium bisulfite (MSB), and not the formulations used in the present invention, was employed as the biocide. The advantageous properties of the flowable concentrate formulations would not therefore have been realised in the 10 studies of Raikow et al (2006). Acknowledging the observed inefficiencies in achieving complete ballast water exchange, the retention in the ballast water tanks of an undischarged residue of the biocide in the 15 sediment may therefore be desirable to the long-term efficacy of ballast water treatments employing the use of sparingly soluble broad spectrum biocides. Although the invention has been described by way of exemplary 20 embodiments it should be appreciated that variations and modifications may be made without departing from the scope of the invention. Furthermore where known equivalents exist to specific features, such equivalents are incorporated as if specifically referred to in this specification. 25 In particular, the ingredients of the formulations are identified by trade names. It will be recognized that ingredients that are functionally equivalent to these trade name products may be substituted at the same concentration for 30 those specifically referenced. 23 WO 2010/071804 PCT/US20091068729 v~ 0~ It +1 +1 +1 +1 C0 D C0 0 rn 0 M -3 V)0 CD 0) 0 0D 0 0 CD +1 - d)) 0 - _ _ _ _ 4) * . 0 44) :1 C 0 0 0 C0 0 0D 040 CD CD 0 CD C 0j aa -0) 4- 4J 0 U v ) 0 0 -CO 44 c 0 w - )\I $ m 0 0 0 0- 0 1 0 '0 .1)+

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0_ Y_ 0 (N 00 o0 0.- CI-i -40 N w I- 0 0 H :: o.' 0r '- 0 440 V-4 0 0 +1 01r 0 (N _ 0-4 0n -4 0 > 0 on -4 Vt 0) H 0 4 0 A-A 0 0 r 4. -4 0 X 4) o 0 > . 0 -' 0 Q4 > ~ 0 0 00 u w 240 .~ WO 2010/071804 PCT/US2009/068729 REFERENCES American Society for Testing and Materials (2003) Standard guide for -conducting acute toxicity tests on test materials with fishes, macroinvertebrates, and amphibians, E 729-96. In Annual Book of ASTM 5 Standards, Section II, Vol 11.05. Philadelphia, PA, pp 1-22. APHA, AWWA, and WEF (2005), Standard Methods for the Examination of Water and Wastewater, 21st ed., American Public Health Association, Washington, DC. 10 Bailey SA. (2005) Sediments as a dispersal vector of aquatic invertebrates: An estimation of propagule pressure associated with 'no ballast on board' vessels, PhD thesis, University of Windsor, Windsor, ON, Canada.

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Claims (1)

1. 2-methyl-1,4-naphthalenedione, 8% 1,2-Propanediol, 30 1.5% TENSIOFIXm SC, 0.5% TENSIOFIX" XD23, 0.5% SAG 30, 0.1% PROXELO GXL, 0.05% Xanthan gum and 45% water. 33 WO 2010/071804 PCT/US2009/068729 15) A method of treating ballast water in a tank of a seagoing vessel comprising the steps of: * Adding an effective amount of a flowable 5 concentrate formulation. of a sparingly soluble biocide to the tank; * Maintaining the ballast water in the tank for a time and at a temperature sufficient to devitalize 10 harmful aquatic organisms and pathogens that may be present in the ballast water; and then * Expelling the ballast water from the tank to the exterior of the vessel. .15 16) The method of claim 15 where the sparingly soluble biocide is the compound. 2-methyl-1, 4-naphthalenedione 17) The method of claim 16 where the flowable concentrate 20 is a suspension concentrate. 18) The method of claim 17 where the flowable concentrate is a suspension concentrate with a particle size distribution substantially equivalent to that provided 25 in Figure 1. 19) The method of claim 18 where the suspension concentrate comprises 40 to 85 % of the sparingly soluble biocide and 7 to 9.% of a starch or dihydric 30 alcohol. 20) The method of claim 15 where the flowable concentrate is a wettable powder. 34 WO 2010/071804 PCT/US2009/068729 21) The method of claim 20 where the wettable powder comprises greater than 50% by weight of the sparingly soluble biocide. 5 22) The method of claim 21 where the wettable powder comprises at least.80% by weight of the sparingly soluble biocide. 23) The method of claim 15 where the formulation further 10 comprises at least one biocidal quaternary ammonium and/or phosponium compound and at least one anionic - surfactant in a molar ratio of from 5 to 1000. 24) The method of claim 15 where the formulation further 15 comprises at least one biocidal quaternary ammonium and/or phosponium compound and at least one anionic surfactant in a molar ratio of from 11 to 1000. 25) The method of claim 15 where the formulation further 20 comprises at least one biocidal quaternary ammonium and/or phosponium compound and at least one anionic surfactant in a molar ratio of from 20 to 1000. 26) The method of claim 15 where the effective amount is 25 sufficient to provide an initial. concentration of the sparingly soluble biocide in the ballast water of at least 800 ppb. 27) The method of claim 26 where the effective amount is 30 sufficient to provide an initial concentration of the sparingly soluble biocide in the ballast water of at least 1.6 ppm. 28) The method of claim 27 where the effective amount is 35 sufficient to provide an initial concentration of the 35 WO 2010/071804 PCT/US2009/068729 sparingly soluble biocide in the ballast water of at least 5 ppm. 29) The method of claim 15 where the time sufficient to 5 devitalize harmful aquatic organisms and pathogens is less than 48 hours. 30) The method of claim 29 where the time sufficient to devitalize harmful aquatic organisms and pathogens is 10 less than 24 hours. 31) A suspension concentrate formulation of a sparingly soluble biocide packaged with directions for use in the treatment of ballast water in a tank of a seagoing 15 vessel where the sparingly soluble biocide has a median particle size of 2.0 to 3.5 pm and a maximum particle size of 9.0 ym. 32) The suspension concentrate of claim 31 where the 20 sparingly soluble biocide is the compound 2-methyl 1,4-naphthalenedione. 33) A wettable powder formulation of a sparingly soluble biocide packaged with directions for use in the 25 treatment of ballast water in a tank of a seagoing vessel where the wettable powder comprises at least 80% by weight of the sparingly soluble biocide. 34) The wettable powder formulation of claim 33 where the 30 sparingly soluble biocide is the compound 2-methyl 1,4-naphthalenedione. 35) A seagoing vessel containing ballast water to which a flowable concentrate formulation of a sparingly 36 WO 2010/071804 PCT/US2009/068729 soluble biocide of any one of claims 1 to 14 has been added. 37