AU766865B2 - Decontaminating and dispersion suppressing foam formulation - Google Patents

Decontaminating and dispersion suppressing foam formulation Download PDF

Info

Publication number
AU766865B2
AU766865B2 AU27898/00A AU2789800A AU766865B2 AU 766865 B2 AU766865 B2 AU 766865B2 AU 27898/00 A AU27898/00 A AU 27898/00A AU 2789800 A AU2789800 A AU 2789800A AU 766865 B2 AU766865 B2 AU 766865B2
Authority
AU
Australia
Prior art keywords
formulation
foam
decontamination
surfactant
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
AU27898/00A
Other versions
AU2789800A (en
Inventor
John G. Bureaux
George R. Cowan
N. Edward Cundasawmy
J. Garfield Purdon
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Royal Canadian Mounted Police
Original Assignee
Royal Canadian Mounted Police
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Royal Canadian Mounted Police filed Critical Royal Canadian Mounted Police
Publication of AU2789800A publication Critical patent/AU2789800A/en
Application granted granted Critical
Publication of AU766865B2 publication Critical patent/AU766865B2/en
Assigned to HER MAJESTY THE QUEEN IN RIGHT OF CANADA AS REPRESENTED BY THE SOLICITOR GENERAL ACTING THROUGH THE COMMISSIONER OF THE ROYAL CANADIAN MOUNTED POLICE reassignment HER MAJESTY THE QUEEN IN RIGHT OF CANADA AS REPRESENTED BY THE SOLICITOR GENERAL ACTING THROUGH THE COMMISSIONER OF THE ROYAL CANADIAN MOUNTED POLICE Alteration of Name(s) in Register under S187 Assignors: BUREAUX, JOHN G.
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42AMMUNITION; BLASTING
    • F42BEXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B33/00Manufacture of ammunition; Dismantling of ammunition; Apparatus therefor
    • F42B33/06Dismantling fuzes, cartridges, projectiles, missiles, rockets or bombs
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42AMMUNITION; BLASTING
    • F42DBLASTING
    • F42D5/00Safety arrangements
    • F42D5/04Rendering explosive charges harmless, e.g. destroying ammunition; Rendering detonation of explosive charges harmless
    • F42D5/045Detonation-wave absorbing or damping means
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/02Chemical warfare substances, e.g. cholinesterase inhibitors
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/06Explosives, propellants or pyrotechnics, e.g. rocket fuel or napalm

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Manufacturing & Machinery (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Detergent Compositions (AREA)
  • Apparatus For Disinfection Or Sterilisation (AREA)

Abstract

A method and foam formulation are provided for enabling both blast suppressing and decontamination, particularly desirable when faced with an explosive device which has been rigged with a contaminant for destructive dissemination. A formulation is foamed to surround the explosive CB contaminant device, preferably encapsulated in a containment structure. The preferred composition of foamer-compatible decontaminant and foamer to foam and surround the device is about 1 % to 3 % /w of hydrated chloroisocyanuric acid salts and more including lithium hypochlorite, about 1 % of a co-solvent selected from the group consisting of polypropylene glycols, polyethylene glycols, and derivatives and mixtures thereof; about 1 % to about 5 % of a surfactant and foam stabilizer; and a buffer system to initially maintain said formulation at a pH from about 11.0 to about 8.5 for a minimum of 30 minutes; and the balance being water.

Description

WO 00/51687 PCT/CA00/00199 1 DECONTAMINATING AND'DISPERSION SUPPRESSING 2 FOAM FORMULATION: 3 4 CROSS-REFERENCE TO RELATED APPLICATION This application claims the benefits under 35 U.S.C. §119(e) of US 6 provisional application 60/122,091, filed February 26, 1999, which is incorporated 7 herein by reference in its entirety.
8 9 FIELD OF THE INVENTION This invention relates to foam formulations having both blast- 11 suppressant and decontamination capabilities.
12 13 BACKGROUND OF THE INVENTION 14 Improvised explosive devices (IEDs) represent an increasingly dangerous threat to society, particularly when they contain a toxic 16 chemical/biological (CB) agent. It is vital that both the blast effects (a compression 17 or pressure wave, heat and shrapnel) and the CB agent and aerosols, released 18 from the initiation of such devices, are contained. Once released, CB agents also 19 present a decontamination problem when deposited on the surfaces of various equipment and vehicles, or spilled on the ground.
21 In the last decade, patents and papers have been published on the 22 use of foam for blast suppression. For example, in US patents 4,541,947 and 23 4,589,341 to Clark et al., an improved method for blast suppression is disclosed 24 which utilizes fire fighting foams confined in a structural barrier surrounding the blast source. Typically, water-detergent based foams are used, having an 26 expansion 50:1- 1000:1. Clark discloses the use of JET-X, from Rockwell Systems WO 00/51687 PCT/CA00/00199 1 Corporation and having 1 6% detergent, containing protein additives and used in 2 the ratio of 1 3 parts by volume for each 100 parts of water. The key to this 3 invention is the methodology for containing a high expansion foam in a desired 4 location.
US Patent 4,964,329 assigned to Broken Hill Ltd. describes a foam 6 composition consisting of a mixture of foamable liquid and a particulate additive to 7 be supported as a dispersion in the foam. The dispersion is claimed to be effective 8 in sound attenuation and shock wave attenuation.
9 US Patent 4, 442,018 to P. Rand describes a foaming composition which has decreased solution viscosity for high expansion foam capability and 11 decreased liquid drainage. Such a composition comprises a combination of a water 12 soluble polymer of the polyacrylic acid type, a foam stabilizer of dodecyl alcohol, a 13 surfactant, and a solvent. A key is the combination of the stabilizer and polymer 14 used.
A very interesting US Patent No. 5,434,192 to Thach et al. describes 16 a composition of surfactants and stabilizers consisting of a mixture of modified 17 naturaland synthetic polymer and solvents capable of producing foam viable for 12 18 hours to several days at 75 105 degrees F. Such foam is used to suppress the 19 emission of volatile gases and vapors.
As described in Clark, a blast may be suppressed using foam 21 contained in a barrier. Applicants initially conducted blast tests with a foam product 22 known as aqueous film forming foam (AFFF) initially designed for knocking down 23 fire. The AFFF was contained in nylon dome tents that were deployed around the 24 blast threat. The blast suppression results were very inconsistent; the foam would WO 00/51687 PCT/CA00/00199 1 break down very quickly and varied from a watery form to very light and airy. The 2 lessons learned during this phase included the realization that the physical form of 3 the foam could be varied considerably by the foam-dispensing rate, the percentage 4 of surfactant in the composition and the foam-dispensing nozzle characteristics.
This work led to the development of a containment system described in Applicant's 6 co-pending US application Serial No. 60/069,533, filed December 12, 1997. That 7 system includes a tent-like enclosure that is deployed over an lED and is filled with 8 an air-aspirated aqueous foam material deemed a Dispersal Suppressant Foam 9 (DSF). When the lED was then detonated, the resulting shrapnel was contained within the enclosure. The foam material used comprised a product sold under the 11 trademark of SILVEX as described by US Patent no. 4,770,794 to Cundasawmy, 12 which issued on 13 September 1988.
13 The inclusion of chemical (CW) and biological (BW) warfare agents 14 (collectively CB agents) or radioactive materials into IED's presents an even greater challenge. Not only must the blast be contained, the agents present in the lED must 16 be effectively neutralized within the area of containment to allow personnel access 17 to the site following activation.
18 Generally, decontamination of radioactive particles is not possible 19 due to their nuclear origin, however, removal by encapsulation significantly reduces aerosolization potential. Decontamination of chemical and biological agents usually 21 occurs by oxidation, reduction or hydrolysis. Ideally a broad spectrum 22 decontaminant, which does not produce toxic by-products in its mode of action on 23 .any of the likely contaminants, is of greatest use when the nature of the warfare 24 agent is unknown.
WO 00/51687 PCT/CAOO/00199 1 Ideally, the blast suppression and decontamination should be a result 2 of a single process, increasing the efficiency of the. operation and allowing access 3 to the site as quickly as possible. Further, vital evidence contained within the 4 suppression zone should not be damaged by either the suppressant foam or by the decontaminating agent.
6 In order to provide a single step suppression/decontamination foam, 7 decontaminant must be included as a part of the foam formulation. While foam for 8 blast suppression is currently available, as are decontaminants, it is not merely an 9 obvious step to mix them together for the combined purpose of blast suppression and decontamination.
11 A prior art decontaminant, German Emulsion was designed to 12 be of low corrosivity, dissolve thickeners and penetrate paint to react with 13 embedded agents in a emulsion formulation. It was discovered however, that the 14 emulsion or foam was somewhat unreliable and sometimes did not form at all. Such decontaminant foams would not be suitable for blast suppression for a period of 16 time after generation.
17 Any inclusion of ingredients into a foam formulation must be carefully 18 assessed to determine their effect on the bubble size and uniformity within the 19 foam. Further, the new formulation must possess sufficient stability, as indicated by low liquid drainage rates and an acceptable expansion ratio, to continue to 21 provide optimum blast suppression.
WO 00/51687 PCT/CA00/00199 1 As discussed in US Patent 4,442,018 to Rand, the choice of solvent 2 in a foam formulation can have dramatic effects on the solution viscosity and liquid 3 drainage from the foam. Thus, solvents and co-solvents present in decontamination 4 formulations can act effectively as de-foamers if incompatible with the foam formulation. Particulates or oxidizing components present in decontamination 6 formulations may also have significant detrimental effects on foam characteristics.
7 It remains the challenge to provide an all-in-one, blast suppression 8 and decontamination foam that combines optimum blast suppression 9 characteristics, such as uniform bubble size, slow drainage, vertical cling, vapor suppression and low toxicity and corrosivity, with optimum broad spectrum 11 decontamination characteristics such as solubilization and emulsification of 12 contaminants, rapid and complete degradation of chemical and biological warfare 13 agents to non-toxic products and low toxicity and corrosivity.
14 o/11/nt 12:55 FAX 613 952 6082 INTELLECTUAL PROPERTY Ihnna S11-04-2001 CA 00000019 1 SUMMARY OF THE INVENTION 2 The present invention discloses the discovery that a foam formulation 3 exists which is suitable for ooth blast suppressing and decontamination, particularly 4 desirable when faced with an explosive device which has been rigged with a contaminant for destructive dissemination. In the known cases of blast 6 suppression, a contaminant can be shown to be substantially contained by a foam, 7 but the used foam becomes heavily contaminated.
8 Accordingly, a serendipitous foam formulation is provided, combining 9 both the advantages of blast suppression and chemical and biological agent decontamination.
11 A foam formulation which is compatible with a decontaminant 12 includes the following compositions: 13 for the surfactant, R(OCH 2
CH
2
),,SO
4 2 where R is an alkyl group 14 having from eight to fourteen carbon atoms, m is an integer from 1 to 3, and M is Na+ or NH 4 in mixture with 16 CH 3
(CH
2
),CH=CHCH
2
SO
3 Na, 17 for the co-solvent, HO(CH 2
(CH
3 )CHO)nH (PPG of MW about 425) 18 where n=5-49 and most preferably 7; and 19 for the foam stabilizer, R-OH where R=Co-C, 4 The decontamination components compatible with the above foamer 21 include hydrated chloroisocyanuric acid salts. Prefereably the chloroisocyanuric 22 acid salt is selected from the group consisting of an alkali metal salt of 23 monochloroisocyanuric acid, dichloroisocyanuric acid, and a combination thereof 6 AMENDED SHEET FP of ae9 Ait 11.Anr. 7 WO 00/51687 PCT/CA00/00199 1 Accordingly, a preferred decontamination formulation suitable also for 2 blast suppression comprises: 3 about 1% to 6% by weight and preferably from about 1% to about 4 3% by weight of hydrated chloroisocyanuric acid salts and more preferably lithium hypochlorite in a ratio of 5 10% of the 6 chloroisocyanuric acid salts; 7 about 1% and optionally up to 8% of a co-solvent selected from 8 the group consisting of polypropylene glycols, polyethylene glycols, 9 and derivatives and mixtures thereof; from about 1% to about 5% of a surfactant; 11 a buffer system to initially maintain said formulation at a pH from 12 about 8.5 to about 11 for a minimum of 30 minutes and preferably 13 initially, from about 10 to about 11; and 14 the balance being water.
In the preferred formulation, the foamer components have a preferred 16 composition of 17 about 15 w/v% of the sodium salt of an ether sulphate of the 18 formula CH 3
(CH
2 11
(OCH
2
CH
2 3 0SO 3 Na; 7.75 w/v% of a sodium 19 .olefin sulphonate of the formula CH 3
(CH
2 )nCH=CHCH 2
SO
3 Na where n=10 to 12, comprising a total of 22.75 w/v% surfactant; 21 about 10 25 w/v% of polypropylene glycol co-solvent of the 22 formula H(OCH(CH 3
)CH
2 )nOH where n 5 to 9; 23 about 1 2.5 w/v% of an alcohol CH 3
(CH
2 )nOH where n 8 to 16 24 to act as a foam stabilizer; and optionally about 0.3% by weight of the above corrosion inhibitors; and the balance being water.
Accordingly, a novel method of handling explosive devices is now available, In a broad aspect, a method for dispersal suppression of an explosive CB contamination device comprises the steps of: surrounding the explosive contamination device with a containment structure; and filling the containment structure with an aerated foam comprisingboth, i) a high expansion foamer; and ii) afoamer-compatible decontamination formulation effective on chemical and biological agents without significantly and adversely affecting the formation of foam, wherein before filling the containment structure, further comprising the steps of: preparing a foamer from a surfactant, a co-solvent selected from the group consisting of polypropylene glycol, polyethylene glycol, and derivatives and mixtures thereof, and a foam stabilizer, S preparing the decontamination formulation from a chloroisocyanuric acid salt, and a buffer to maintain said formulation at a pH from about 11 to about preparing a mixture of the foamer and decontamination formulation in water; and foaming the mixture.
*0le o* o*oeo WO 00/51687 PCT/CA00/00199 1 In a novel combination, a system is provided for dispersal 2 suppression of an explosive CB contamination device comprising: 3 a containment structure for surrounding the explosive 4 contamination device; and aerated foam contained within the structure being formed from a 6 decontamination formulation in water comprising a surfactant, a 7 foam stabilizer, a solvent selected from the group consisting of 8 polypropylene glycol, polyethylene glycol, and derivatives and 9 mixtures thereof, chloroisocyanuric acid salts, and a buffer to maintain said formulation at a pH from about 11 to about 11 In the preferred use for surrounding an explosive device, the foam 12 formulation in water comprises about 0.4 4 weight of a surfactant; about 0.03 13 0.5 weight of a foam stabilizer; and about 0.10 9.5 weight of a co-solvent; 14 about 3 6 of the chloroisocyanuric acid salts; the buffer and the balance being water. Preferably, and still effective for decontamination and foaming capability is 16 a formulation 0.6 weight of the surfactant; about 0.03 weight of the foam 17 stabilizer; about 0.75 weight of the co-solvent; and about 3% of the 18 chloroisocyanuric acid salts.
19 BRIEF DESCRIPTION OF THE DRAWINGS Figures 1 -4 relate to Example 2. Figure 1 illustrates the concentration values of methyl salicylate (mustard simulant) in the test chambers, after two baseline shots (no enclosures) and three test device shots (enclosure with foam placement of a tent over the device followed by the injection of DSF). The percentage of agent capture and containment exceeded Figure 2 illustrates the concentration gradient that was measured in the test chamber over a thirty minute duration NOTE: These are the same shots as in Figure 1, Baseline shots not shown as the scale was too large. This is still within acceptable limits but has prompted an effort to make further improvements to the foam mitigating capacity; Figure 3 illustrates the comparison between unmitigated Baseline shots and Test shots of Example 2. Simulant formed a fine aerosol that behaved like that of a biological agent. The percentage of agent captured was in the order of Figure 4 shows the over pressure readings collected by a pressure transducer placed at 1.5 meters. The Baseline shots were between 6 and 7 Pounds per Square- nch (psi) or 0.42 to 0.49 kgf/cm 2 The Test shot readings were almost negligible. The enclosure did not tear, all contents remained in the tent; Figures 5 11 relate to Example 3. Figure 5 depicts the concentrations of simulant in the test chambers of Example 3 after an unmitigated baseline shot and a contained shot. As well, the lethal level of Sarin for a one minute exposure is displayed. A High level of simulant capture is noted; *e o Figure 6 illustrates the over pressure measurements at the noted distances from the device for both an unmitigated and contained shot. The findings indicated over pressure containment in the order of Figure 7 represents the air concentrations of simulant as measured by DAAMS Tube Samplers in an outdoor trial as noted in Fig. 8. This simulated a device being initiated outside of a structure. The.data recorded during the Test Device shot indicated containment greater than Figure 8 illustrates the Range DAAMS Tube Sampler Setup; Figure 9 illustrates the over pressures recorded on two tests, an unmitigated test and a contained test. The readings recorded on the contained shot were barely measurable <1psi or <0.07 kfg/cm 2 Figure 10 depicts one baseline unmitigated shot, and three contained test shots with different explosive amounts as noted. Samplers set as noted in Fig. 8.
Containment realized in excess of 9 5 and Figure 11 shows the over pressure values measured at 1.5 meters from the test device unmitigated and three contained shots, each with different explosive S: loads as noted. Over pressure values were diminished by greater than Figures 12 19d relate to Example 4. Figure 12 represents a total ion chromatogram created from Hapsite data after simulant dispersal showing a single organic chemical with a predominant mass 115 fragment, consistent with diethyl malonate; go o*°o WO 00/51687 PCT/CA00/00199 1 Figure 13 shows the results of the mass spectral data analysis 2 indicating that the chemical in Fig. 12 is indeed diethyl malonate with a probability 3 of 97.5%; 4 Figure 14 shows total ion chromatograms of Hapsite T M readings following vehicle contamination with mustard, prior to application of the foam 6 formulation; 7 Figure 15 shows mass spectral identification of the sample in Fig. 14, 8 containing a predominant mass 109 fragment, as being mustard (bis (2-chloroethyl) 9 sulphide); Figure 16 shows total ion chromatograms of Hapsite data from air 11 samples acquired after vehicle decontamination showing the absence of mustard 12 vapor; 13 Figure 17 shows total ion chromatograms of two separate air samples 14 of tent head-space air, taken at 20 seconds and at one minute during the 5 minute sampling period, following activation of the device; 16 Figure 18a shows the total ion chromatogram of the mustard sample, 17 sampled by Hapsite, from the head-space air of the bottle containing mustard, used 18 for.vehicle contamination trials; 19 Figure 18b shows the total ion chromatograms from the mustard headspace air sample of Fig. 18a, showing additional solvent components; 21 Figures 19a-19d show mass spectral library identification 22 chromatograms used to identify the constituents in the mustard head-space air 23 sample of Fig. 18a; WO 00/51687 PCT/CA00/00199 1 Figures 20 23 relate to Example 5. Figure 20 shows a total ion 2 chromatogram of an air sample acquired by Hapsite during the Example 5 simulant 3 dispersal trial showing the sample to contain a high concentration of a single 4 component, subsequently identified as DEM; Figure 21 shows a total ion chromatogram of a head-space air sample 6 above a bottle of mustard agent acquired by Hapsite showing a total ion and mass 7 109 reconstructed ion chromatogram identifying the substance as mustard; 8 Figure 22 shows a total ion chromatogram of the tent head-space air 9 sample acquired by Hapsite 10 minutes after detonation in the simulant trial showing a small amount of simulant and dichloroethyl acetate; 11 Figure 23 shows a total ion chromatogram of the tent-head-space air 12 sample acquired by Hapsite after detonation in the mustard trial, not to be mustard, 13 but to be 1,2-dichloroethane instead; 14 Figure 24 is a table illustrating the effectiveness of several decontaminant formulations against selected G-type nerve gases GB, GA and GD 16 and mustard gas, HD; 17 Figure 25 is a table illustrating the effectiveness of a foam formulation 18 containing 9% active ingredient (FS) and one containing 3% active ingredient (Mild) 19 against the nerve agent VX; and Figure 26 is a graph illustrating the effectiveness of the foaming agent 21 by itself to effect decontamination of radioactive dusts from the exterior surface of 22 an armored vehicle.
23
L
WO 00/51687 PCT/CA00/00199 1 DESCRIPTION OF THE PREFERRED EMBODIMENTS 2 In the present invention, a blast suppressing decontamination foam 3 formulation and means for its use are provided for incorporating the known active 4 decontamination ingredient, hypochlorite, in a uniquely buffered solution designed to be incorporated into a blast suppressing foam to be used to suppress the blast 6 shock wave, contain shrapnel and toxic vapors following detonation of iED's and 7 decontaminate chemical and warfare agents contained therein.
8 9 Generally Incorporation of known decontaminant solutions into existing blast 11 suppressing foam formulations requires careful testing and optimization to ensure 12. that neither of the component formulations suffers adverse effects with respect to 13 their intended purpose.
14 Particularly, incorporation of solvents and particulates into foam formulations may adversely effect those characteristics required for blast 16 suppression, those characteristics being slow liquid drainage rates, high expansion 17 ratios and optimum bubble size.
18 Further the addition of foam agents and solvents into decontaminant 19 solutions should not alter the effective pH ranges of the active ingredients and stabilizers, nor should it result in the production of toxic by-products or cause false 21 positive or negative readings on monitoring equipment.
22 Formulations which are suitable for the suppression of blasts are 23 discussed in co-pending US provisional patent application 60/120,874, filed 19 WO 00/51687 PCT/CA00/00199 1 February 1999, and replaced by a regular application filed on or about 18 February 2 2000, which is incorporated herein by reference in its entirety.
3 In co-pending application 60/120,874, it was determined that a 4 suitable foamer concentrate comprising a surfactants 40-80%/w; a foam stabilizer 3-7 a polyalkyleneglycol solvent 10-30%/w; and water balance 6 to 100%.
7 The surfactants was a mixture of two surfactants. The use of the 8 term surfactant herein is defined as individual or a mixture of surfactants as set 9 forth in the context.
11 Foam Formulations 12 As suggested, a foam formulation generally comprises a surfactant, 13 a co-solvent and a stabilizer.
14 The surfactant is capable of acting as an emulsifier and forms a foam, over a wide range of pH, when aerated. Ideally the surfactant should be soluble in 16 fresh or seawater and is chosen to be compatible with other ingredients in the foam 17 formulation. The surfactant may be a single ingredient or a mixture of two or more 18 surfactants such as Cedepal® TD-407, a sodium alkyl ether sulfate, and Bioterge@ 19 AS-90, an alpha olefin sulphonate.
The co-solvent acts as a coupling agent for solubilizing the surfactant 21 and as solubilizer for chemical warfare agents that are not water soluble. The term 22 co-solvent is used herein to define organic-based chemicals that solubilize CB 23 agents, e.g. from alkyd-coated (painted) surfaces. One such co-solvent is S26-02-2 001 CA 000000199 1 polypropylene glycol (PPG425). The PPG425 still permits good foaming 2 characteristics over a wide range of pH in both fresh and seawater.
3 The stabilizer acts to increase foam stability. Long chain, often water 4 insoluble, polar compounds with straight chain hydrocarbon groups of approximately the same length as the hydrophobic group of the surfactant, such as 6 long chain fatty acids, act as foam stabilizers. One such stabilizer is dodecanol 7 :Lorol® 70:30 which is a blend of C12-14 aliphatic alcohols in tne ratio of 70:30.
8 Another is Alfol® 1412, a mixture of 1-dodecanol and 1-tetradecanol.
9 Briefly, the foamer consists of a surfactant, a co-solvent and a foam stabilizer. Optionally, in addition, corrosion inhibitors can be added in very small 11 quantities.
12 Generally, suitable surfactants include a composition of either the 13 formula [R(OCH 2
CH
2 where R is an alkyl group having from eight to 14 eighteen carbon atoms, n is an integer from 1 to 10; X is selected from the group of SO2", SO 4 2
CO
3 2 and PO40 3 M is an alkali metal, alkaline earth metal, 16 ammonium or amine derivative; a is the valence of M and b is the valence of 17 [R(OCH 2
CH
2 or the formula tR-CH=CH(CH 2 )e-XMb where 1: is an alkyl group 18 having from eight to eighteen carbon atoms; m is an integer from 0 to 3: X is 19 selected from the group of SO 3
SO,
2 C0 3 and POI. M is an alkali metal, alkaline earth metal, ammonium or amine derivative, a is the valence of M and b is 21 the valence of [R-CH=CH(CH),-X] or a mixture thereof.
22 A suitable foam stabilizer is an alkyl alcohol, R-OH. where R is an 23 alkyl group having from eight to sixteen carbons.
16 AMENDED SHEET 04/11/o ,12:55 FAX 613 952 6082 INTELLECTUAL PROPERTY g0U05 11-04-2001 CA 00000019.
1 Combined, one such suitable foamer is Silv-Ex'T made by Ansul Fire 2 Protection described in US Patent 4,770,794 issued to Cundasawmy et al.
3. September 13, 1988. More specifically, the Silv-Ex formulation consists of a 4 surfactant comprising: 20% by weight of a surfactant C 1 oH 2 1
(OCH
2
CH
2 )2.
3
SO
4 'Na* and 20% by weight of C 4 H29(OCH 2
CH
2 3
SO
4 -NH4; a co-solvent of 20% by weight 6 of diethylene glycol monobutyl ether; and a stabilizer of 5% by weight of C 12
HOH.
7 The balance is water. Optionally, the formulation contains a further 0.5% of 8 corrosion inhibitors.
9 Altematively, foamers which do not contain diethylene glycol monobutyl ether as the co-solvent are preferable, as residuals of Ihis low molecular 11 weight constituent can be detected by some conventional decontamination 12 monitoring equipment (such as Graseby lonics T M Chemical Agent Monitor or CAM) 13 and are thus interpreted falsely as positive detection of residual contaminant.
14 Accordingly, a suitable non-residual foamer (or NR-foamer) consists of a composition of alkyl ether sulphate salt, an alpha olefin sulfonate, a co-solvent, 16 an alkyl alcohol, and water. More specifically the surfactant, co-solvent and foam 17 stabilizer are in mixture in water, the component formulas being: 18 for the surfactant, R(OCH 2
CH
2 )mSO 4 2 where R is an alkyl group 19 having from eight to fourteen carbon atoms, m is an integer from 1 to 3, and M is Na+ or NH4 in mixture with 21 CH 3
(CH
2
),CH=CHCH
2
SO
3 Na, 22 for the co-solvent, HO(CH 2
(CH
3 )CHO),H (PPG of MW about 425) 23 where n=5-49 and most preferably 7; and 17 AMENDED SHEET Fmofan asyeit I,.Ap r. 19:57
W
1 2 3 4 6 7 8 9 11 12 13 14 16 17 18 19 21 22 23 24 00/51687 PCT/CA00/00199 Accordingly, one preferred composition of the NR-foam formulation consists of about 30% weight/volume of the sodium salt of an ether sulphate of the formula CH3(CH 2 )11(OCH 2
CH
2 3
OSO
3 Na; 15.5 w/v% of a sodium olefin sulphonate of the formula CH3(CH 2 )nCH=CHCH 2
SO
3 Na where n=10 to 12; about 20 w/v% of polypropylene glycol co-solvent of the formula
H(OCH(CH
3
)CH
2 )nOH where n 5 to 9; about 5 w/v of an alcohol CH 3
(CH
2 )nOH where n 8 to 16; and optionally about 0.3% by weight of optional corrosion inhibitors such as sodium tolyltriazole, ammonium dimolybdate and sodium pentahydrate silicate; and the balance being water, with additional water being added to dissolve other components.
Further, this NR-foamer is capable of generating foam of uniform bubble size, is capable of coating vertical surfaces, is compatible with water, gray water and seawater as the main solvent, and is readily removed following decontamination by rinsing with water.
This particular NR-foamer is subject to soft thixotropic gelling at temperatures below about 10°C, which could be troublesome if shipped or used in adverse weather at this concentration.
It has been determined that to lower the thixotropic gelling point of the surfactant, to be useful in a wider range of environments, one approach is to WO 00/51687 PCT/CAOO/00199 1 provide an alcohol stabilizer component which comprises more C 12 than C 14 It has 2 been found that, even more significantly, diluting the surfactant 1:1 with water for 3 storage and transport further lowers the gelling point.
4 Accordingly, a more dilute NR-foamer consists of: about 15 w/v% of the sodium salt of an ether sulphate of the 6 formula CH 3
(CH
2 )11(OCH 2
CH
2 3
OSO
3 Na; 7.75 w/v% of a sodium 7 olefin sulphonate of the formula CH 3
(CH
2 )nCH=CHCH 2
SO
3 Na 8 where n=10 to 12, comprising a total of 22.75 w/v% surfactant; 9 about 10 25 w/v% of polypropylene glycol co-solvent of the formula H(OCH(CH 3
)CH
2 )nOH where n 5 to 9; .11 about 1 2.5 w/v% of an alcohol CH 3
(CH
2 )nOH where n 8 to 16 12 to act as a foam stabilizer; and optionally 13 about 0.3% by weight of the above corrosion inhibitors; and 14 the balance being water.
Accordingly, to provide the required concentration of foamer 16 ingredients in the final foam formulation, twice the volume of this diluted foam 17 formulation must be added to the decontaminant and buffer solutions to provide the 18 preferred blast suppressing/decontamination foam formulation.
19 Decontamination Formulation 21 More detail on the decontamination formulation is disclosed in a co- 22 pending US provisional patent application 60/120,971, filed 19 February 1999, and 23 which was replaced by a regular application filed 14 February 2000, and which is 24 incorporated herein by reference in its entirety.
WO 00/51687 PCT/CAOO/00199 1 Used as a decontaminating formulation alone, and as disclosed in co- 2 pending application 60/120,971, the decontamination formulation comprises an 3 active decontamination agent in a buffer system designed to optimize the initial 4 reaction pH above 8.5 and more preferably in the range of 10 to 11 for favoring hydrolysis of G-agents, and oxidation of VX and HD agents.
Active Inqredient The decontamination formulation of the present invention contains as an active ingredient, sodium dichloroisocyanurate. Other chloroisocyanuric acids, their alkali metal salts or a combination of acids including trichloroisocyanuric acid are also suitable for use as the active ingredient. As an example, alkali metal salts of monochloroisocyanuric or dichloroisocyanuric acid or a combination of any of the above salts with cyanuric acid may be used.
The decontamination formulation contains from about 1% to about and preferably from about 3% to about by weight, of the hydrated dichloroisocyanuric acid salt when used for decontamination alone. When used simultaneously as a blast suppressant, the formulation contains from about 1% to about 6% by weight, of the hydrated dichloroisocyanuric acid salt and preferably from about 3% to about 6% by weight, of the hydrated dichloroisocyanuric acid salt.
The formulation may additionally comprise lithium hypochlorite to enhance the activity of the dichloroisocyanuric acid salt.
WO 00/51687 PCTf/CA00/00199 1 Buffer 2 The decontamination formulation of the present invention further 3 comprises a buffer that temporarily maintains an initial pH in the range of 10 to 11 4 sufficient to enable hydrolysis of G-agents and favor oxidation of the V and mustard agents so as to produce non-toxic products. An initial pH in the range of 10 to 11 6 is sufficient to provide adequate hypochlorite ions for decontamination.
7 Subsequently, it is desirable that the buffer fail, allowing the pH to decrease 8 eventually to a more neutral pH to enable more efficient destruction of the BW 9 agents.
As the buffer fails and the pH drops to a more neutral pH, 11 hypochlorous acid becomes more prevalent as hypochlorite ions react with 12 available hydrogen ions. Hypochlorous acid is the more active species with respect 13 to the destruction of BW agents as neutral species are able to enter the BX agent 14 cell more easily. Should a BW agent survive the initial decontamination, the BW agent and decontamination formulation may continue to co-reside over time, 16 perhaps after rinsing, and, as the pH falls, BW agent decontamination continues 17 at an even more effective pH. Further, from an environmental standpoint, a more 18 neutral final pH of the decontamination formulation is less hazardous.
19 It is important to maintain the initial moderately high pH over a prescribed duration (such as a NATO designated duration of 30 minutes for a 21 military decontamination), to provide sufficient hypochlorite ions to effect 22 decontamination favoring hydrolysis of G-agents, favoring oxidation of VX agent 23 which avoids the formation of toxic hydrolysis byproducts, and favoring oxidation 24 of HD agents and avoiding HD reformation. Accordingly, the buffer must be WO 00/51687 PCT/CA00/00199 1 capable of buffering the release of HCI due to hydrolysis of the chloroisocyanuric 2 salts by water. Most preferably, the pH is maintained above 8.5 during the duration 3 available for decontamination.
4 It has been determined that the most suitable buffering system is an inorganic buffering system, adjusted to an initial pH in the range of 10 to 11.
6 Sodium salts, such as a mixture of sodium tetraborate decahydrate and anydrous 7 sodium carbonate, are preferable since quaternary ammonium compounds result 8 in depletion of hypochlorite through reaction with the hydrolysis product of 9 hypochlorite, chloride ion.
11 Augmented Active Ingredients 12 The decontamination formulation may further optionally include 13 lithium hypochlorite to augment the active hypochlorite content of the solution over 14 a short term, thus providing a higher level of active species in the initial stages after the addition of water. Preferably, lithium hypochlorite is present in amounts in the 16 range of from about 5 to about 10% by weight of the active ingredient 17 dichloroisocyanuric acid salt and taking into account that commercially available 18 lithium hypochlorite is normally only available as 30% pure. Alternatively, small 19 amounts of Super Tropical Bleach (STB) or High Test Hypochlorite (HTH), below their solubilisation limits so that no solid or slurry results, could serve the same 21 function as the addition of lithium hypochlorite.
22 The decontamination formulation of the present invention may further 23 optionally include inorganic/organic bromide to increase the reactivity of the WO 00/51687 PCT/CA00/00199 1 chloroisocyanuric acid and generate low levels of hypobromite and bromine 2 chloride.
3 4 Blast suppressing-decbntamination foam formulation Therefore, in the present invention, a foamer compatible 6 decontamination formulation is mixed with foamer to provide a preferred foam 7 formulation capable of simultaneous blast suppression and decontamination 8 comprising; 9 from about 1% to 6% by weight and preferably from about 1% to about 3% by weight of hydrated chloroisocyanuric acid salts and 11 more preferably lithium hypochlorite in a ratio of 5 10% of the 12 chloroisocyanuric acid salts; 13 about 1% and optionally up to 8% of a co-solvent selected from 14 the group consisting of polypropylene glycols, polyethylene glycols, and derivatives and mixtures thereof; 16 from about 1% to about 5% of a surfactant; 17 a buffer system to initially maintain said formulation at a pH from 18 about 8.5 to about 11 for a minimum of 30 minutes and preferably 19 initially, from about 10 to about 11; and the balance being water.
21 It was tested and determined that the addition of 3% active ingredient 22 and buffer into the foamer had substantially no adverse effects on blast suppression 23 effectiveness, the expansion ratios of the foam or on its liquid drainage rates. It was WO 00/51687 PCT/CA00/00199 1 further determined that the foamer did not affect the ability of the active ingredient 2 to effect total decontamination of CB agents.
3 Should the lED have already detonated, then clean up may be 4 required by a decontaminant with minimal or no blast suppression capability. For example, a 6% active ingredient formulation can be used. In such an instance, 6 additional co-solvent can added to raise the total co-solvent (foamer and added co- 7 solvent) to about 8% for more effectively solubilizing penetrated CB agents from 8 surfaces.
9 The combined foamer and decontamination formulation can now be applied to IED's which contain a contaminant which would require both blast 11 suppression and decontamination capabilities.
12 As described in more detail in co-pending provisional application 13 60/120,874 disclosing blast suppressing foam formulations and also in co-pending 14 provisional application 60/069,533, filed Dec. 12, 1997 and its replacement regular application (both of which are incorporated herein in its entirety), an explosive device 16 including explosive contamination device, is surrounded by an encapsulating foam 17 containment structure. The foamer and decontamination formulation are mixed in 18 water and foamed to fill the containment structure, thereby surrounding the lED.
19 4 WO 00/51687 1 Examples Example 1 2 DECONTAMINATION EFFECTIVENESS EVALUATIONS PCT/CAOO/00199 3 s j In the process of foam formulation optimization, the three most promising formulations, 1, #3 and #4 in Table 1, incorporating the PPG425 co-solvent, were prepared and evaluated for their agent simulant solubilisation capabilities (ability to dissolve and solubilize compounds simulating real agents).
Table 1. Percentage Composition of Components in New Formulations.
Candidate Foam Ingredients #1 #2 #3 #4 Alkyl Ether Sulfate (FA-406) 30 NIL NIL NIL Alkyl Ether Sulfate (TD-407) 26 26 26 26 NIL a- olefin Sulfonate (AS-90) NIL 15.5 NIL NIL 15.5 a- olefin Sulfonate (Stepantan AS 12) NIL NIL 15.5 NIL NIL Sulfosuccinate (Aerosol OT) NIL NIL NIL 50 NIL Lauryl Alcohol 5.0 5.0 5.0 5.0 Co-Solvent 20.0 20.0 20.0 20.0 20.0 Citric Acid to pH Water QS to 100% It was assessed that all three formulations were equal in their effectiveness in reducing the capacity factors or retention times of test simulants on an HPLC assessment column.
Further work demonstrated that all three formulations met their requirements for limited inhibition of decontamination reaction times with formulation #3 being the preferred formulation. All subsequent testing and field tests were performed using formulation #3.
WO 00/51687 PCT/CA00/00199 1 The decontaminating solution was then prepared by combining two 2 solutions as follows: 3 1) A buffer solution consisting of: 4 a) sodium tetraborate decahydrate, used at a concentration in the decontamination solution so as to 6 produce 0.004167 mol/L after being mixed with the surfactant 7 solution; and 8 b) anhydrous sodium carbonate used at a concentration 9 in the decontamination solution so as to produce a molar concentration of 0.0333 mol/L after dilution with the surfactant 11 solution.
12 2) An oxidizing/decontaminating agent, sodium dichloro-s- 13 triazinetrione (more commonly known as sodium 14 dichloroisocyanuric acid), with a chlorine content of 62% w/w.
This material was used at a concentration so as to produce a 16 concentration of 3% w/w in the final solution. It must be 17 pointed out that the oxidizing agent displays signs of 18 precipitation on standing at concentrations above 2%.
19. It was surprising to see that the simultaneous use of the decontamination and foaming solutions had no adverse effect on the foaming 21 characteristics of the blast foam formula there was no change in foam expansion 22 and drainage rate.
23 Furthermore, the foaming solution and the buffer/oxidizing agent 24 solution were directly mixed and foam characteristics were measured as a function WO 00/51687 PCT/CA00/00199 1 of time. It was found that there was no drop in expansion ratio nor increase in 2 drainage rate after the mixture had been standing for'over 30 minutes.
3 4 Example 2 and 3 Two test series were conducted to determine the mitigation capacities 6 of foam formulations to contain CB agents.
7 The first series of tests, Example 2, were performed using non- 8 fragmenting explosive dissemination models designed to project CB simulants.
9 SILVEX foam formulation was used and the results extrapolated to other foam formulations based on blast tests conducted using the formulation of this invention.
11 The second series, example 3, studied the performance of the 12 preferred foam formulation, when challenged by non-explosive dispersal models as 13 well as by high energy devices. The high energy explosive dispersal models 14 provided an indication of the upper device limits that were containable.
During the development stage the nylon tent, used in Example 2, was 16 reinforced by adding a layer of ballistic material over the foamed enclosure. Two 17 ballistic materials were tested; DYNEEMA and KEVLAR. Each fabric was tested 18 alone and in combinations with the other. DYNEEMA was selected as the fabric to 19 be used in the containment structure because it demonstrated superior qualities in capturing high velocity bomb fragments. The dome tent shaped design evolved to 21 a base unit being fabricated from 3 layers of DYNEEMA and an outer and inner 22 layer of rip stop nylon. Two containment structure sizes were produced, one 23 approximately 2.75 meters in diameter and the second approximately 2 meters in 24 diameter (used in Example The contaminant system is the subject of co-pending WO 00/51687 PCT/CA00/00199 1 US application serial no. 60/069,533, filed December 12, 1997, and replaced by a 2 regular application, both of which are incorporated herein in their entirety.
3 4 Example 2 The Chemical Agent Device Model used was a simple device that 6 included a 1 liter high density polyethylene laboratory bottle and a center burster 7 of approximately 125 grams of C-4 explosive, initiated by an electric blasting cap.
8 The bottle was filled with approximately 950 milliliters (mL) of methyl salicylate, a 9 chemical agent simulant for mustard agent.
The Biological Agent Device Model used was essentially the same 11 design as was used in the chemical simulant test, except that the methyl salicylate 12 was replaced by a biological agent simulant, calcium hydroxide.
13 The tests were conducted in a cylindrical shaped blast test chamber, 14 32 feet in diameter and 20 feet high.
A four person, dome shaped nylon tent, 2 meters in diameter was 16 used to contain the foam formulation. The foam formulation used was SILVEX foam 17 concentrate diluted to 1.7 in water. It will be appreciated by those skilled in 18 the art that these results can be extrapolated to other foam formulations according 19 to the invention based on the evaluation of various physical properties of the foam produced with these formulations as compared to SILVEX foams, and a blast test 21 with a preferred formulations against an actual improvised chemical dispersant 22 device containing weapons grade material. Similar blast mitigation properties were 23 observed.
WO 00/51687 PCT/CA00/00199 1 Effectiveness of chemical containment was measured using a miniature 2 infra-red gas analyzer (MIRANTM). Biological containment was determined using an 3 airborne aerosol mass concentration determination wherein simulant is collected on 4 a filter pad in a Gillian Personnel Sampler pump and airborne aerosol mass concentration is extrapolated given known flow rates and chamber volume. Blast 6 overpressures were determined using ENDEVCOTM piezoresistive pressure 7 transducer and Anderson blast gauges.
8 Two baseline tests were performed without an enclosure or foam 9 formulation to determine the dispersal of the methyl salicylate, mustard simulant.
Three tests were performed using the containment tent and the foam formulation.
11 The results, as shown in Fig. 1, show that compared to the baseline test, the tent 12 and foam formulation were able to contain the mustard simulant in excess of 13 Fig. 2 illustrates the concentration gradient of simulant in the test 14 chamber, over 30 minutes, for the three tests performed in Example 1.
Fig. 3 illustrates the comparison between unmitigated baseline tests and 16 biological tests. The biological simulant formed a fine aerosol that behaved like that 17 of a biological agent. The biological simulant was contained in the order of 18 Fig. 4 illustrates the readings obtained by the pressure transducer, 19 placed at 1.5 meters. The foam suppressed simulant tests showed negligible pressure in PSI compared to that observed for the baseline tests.
21 22 Example 3 23 In contrast. to the dispersal device used in Example 1, a more 24 energetic fragmenting device was used to disperse agent as well as a selection of less energetic dispersal systems such as high pressure aerosol formation.
Tests were performed using mustard agent simulant, methyl salicylate only. It was felt that chemical contamination represented the worst case scenario and that biological testing would be an unnecessary duplication.
The dispersal devices used were as follows: Device 1 -100 grams C-4 central burster in 1 liter plastic lab bottle containing approximately 950 mL of MS Device 2 120 grams dispersal charge on bottom of I liter lab bottle containing 1 liter of MS Device 3MX steel tool box with batteries, timer, circuit, 500 mL MS simulant (X denotes grams of C-4 i.e. 115,.230, 345 grams) S Device 4 a commercial garden sprayer containing 1 liter MS The tests were conducted on an open range and in a test chamber measuring 20 ft. x 30 ft. x 10 ft. or 6.10 m x 9.15 m x 3.05 m (170 m 3 A dome shaped DYNEEMA tent was used as the enclosure structure which was subsequently filled with SILVEX foam (approx. 570 cubic ft. or 16 m 3 to :::suppress the blasts of the various dispersal devices.
Effectiveness of chemical containment was measured using a miniature infra-red gas analyzer (MIRANTM). Further, chemical concentration ranges were determined by collecting simulant aerosols on a Depot Area Air Monitoring System (DAAMS) tube followed by thermal desorption into an HP5890 gas chromatography *system equipped with a flame ionization detector. Blast overpressures were determined using ENDEVCO
T
m piezoresistive pressure transducer and Anderson blast 00..oe gauges.
WO 00/51687 PCT/CA00/00199 1 Fig. 5 depicts the concentrations of simulant in the test chamber after 2 an unmitigated baseline test and a contained test. The lethal level of Sarin after a 3 one minute exposure is shown for reference. A high level of simulant capture was 4 observed.
Fig. 6 illustrates the over pressure measurement at the noted 6 distances from the device for both unmitigated and contained tests. Over pressure 7 containment was observed in the order of 90% for contained tests.
8 Fig. 7 illustrates the air concentrations of simulant as measured by 9 DAAMS tube samplers in an outdoor trial, their locations further illustrated in Fig.
8.
11 Fig. 9 illustrates the over pressures recorded on two tests, one 12 unmitigated and the other contained. The readings recorded for the contained test 13 were barely measurable i.e. <1 PSI.
14 Fig. 10 depicts a baseline unmitigated test and three contained tests, each performed using different explosive amounts. Samplers were located as 16 illustrated in Fig. 8. Containment was realized in excess of 17 Fig. 11 illustrates the over pressure readings measured at 1.5 meters 18 from the test device for one unmitigated baseline test and three contained tests, 19 each with different explosive loads, as noted. Over pressure readings were diminished by greater than 90% in the contained tests.
21 Examples 4 and 22 In Examples 4 and 5, staged field tests were conducted to determine 23 the blast suppression decontamination foam formulation's ability to both 24 decontaminate and to suppress a blast.
WO 00/51687 PCT/CA00/00199 1 The presence of G-agent simulant and mustard agent was 2 determined using conventional decontamination monitoring equipment such as 3 Graseby lonics T M Chemical Agent Monitor or CAM and Chemical Agent Detection 4 Systems Mark II (CADS II) stations, each comprising two CAMs. Further, confirmation of the presence or absence of these agents in air samples was 6 determined using Hapsite
T
a portable gas chromatograph/mass spectrometer 7 (GC/MS).
8 Hapsite was adapted for measurement of chemical agents under 9 ambient test conditions by equipping it with an M213 membrane system capable of more rapid permeation of chemical agents, substituting the standard DB-1 GC 11 capillary column by a DB-5 capillary column, adjusting operating temperature to 12 80°C rather than the usual 60 0 C used for volatile organic chemicals, and operating 13 the probe inlet line at 45 0 C rather than the usual 35 0 C. The air samples were 14 subjected to a mass spectral analysis alone, as the agents used in the trials were known. This type of analysis does not require any prior chromatographic separation 16 and allows for longer air sampling times. Typically 5 minute samplings were used for 17 the staged testing. Hapsite was also used for full chromatographic separation and 18 mass spectral analysis in the event that the samples demonstrated unexpected 19 results using mass spectral analysis alone.
21 Example 4 22 In a first stage, the ability of the CAMS and Hapsite to measure 23' dispersion of the agent simulant, diethyl malonate, was determined. In a second 24 stage, the ability of the blast suppressing decontamination foam formulation to WO 00/51687 PCT/CA00/00199 1 decontaminate mustard painted onto a vehicle surface was tested. In a third and 2 last stage, the ability of the blast suppressing decontamination foam formulation to 3 suppress blasts while containing G-agent simulant and mustard vapor and 4 simultaneously decontaminating the mustard agent, were tested.
6 Stage 1 Simulant Dispersion Tests 7 Two dispersal devices, each containing 250 ml of a diethyl malonate 8 (DEM)(propanedioic acid, diethyl ester)/water (50/50 v/v) mixture, were secured to 9 ring stands located in the proximity of target vehicles. One was placed 50 cm above the ground and the other at 75 cm above the ground. Witness cards, containing 11 dyed paper for detecting liquid drops were placed on the ground near the dispersal 12 devices, on the nearby vehicles and on the ground 20 meters downwind of the 13 dispersal devices.
14 The dispersal devices were activated (functioned). As soon as the site was declared safe from explosive hazard, the witness cards were examined and the 16 site monitored by personnel carrying CAMs. Hapsite was brought to the site to 17 acquire and test air samples at locations near the ring stands, vehicle surfaces, open 18 ground and witness cards.
19 All witness cards showed evidence of impact from liquid drops. The CAMs produced G-mode readings in the range of 2 to 6 bars indicating mild to 21 heavy contamination with simulant (DEM registers as a G-agent on a CAM). An 22 MS-only survey method, employed on Hapsite, provided data for a total ion 23 chromatogram as shown in Fig. 1, having a single organic chemical with a 24 predominant mass 115 fragment, consistent with diethyl malonate. Fig. 13 shows 33 WO 00/51687 PCT/CA00/00199 1 the results of the mass spectral data analysis indicating that the chemical is indeed 2 diethyl malonate with a probability of 97.5%.
3 Having determined that the detection equipment was capable of 4 monitoring simulant, the foam formulation was tested to determine its ability to act as a decontaminant in Stage 2.
6 7 Stage 2 Vehicle Decontamination Trial 8 An armored personnel carrier painted with chemical agent resistant 9 coating (CARC) was painted, on one side, with 150mL mustard. Four CADS II monitoring stations were deployed near the vehicle, three placed downwind. A 11 sample of head-space air was taken from the bottle from which the mustard was 12 taken, using Hapsite and CAM readings were taken near the vehicle prior to the 13 application of the foam formulation. Blast suppressant decontaminating foam was 14 applied to the surface of the vehicle using a hose and spray head assembly, followed by manual scrubbing of the surface with long handled brushes. After a 16 minute waiting period, the foam was washed away with water and the vehicle 17 surface re-surveyed with CAMs. Hapsite was used to take air samples around and 18 downwind the vehicle.
19 Initial CADS II readings, during the application of mustard to the vehicle showed significant H-mode readings downwind the vehicle. Fig. 14 shows 21 the Hapsite readings prior to application of the foam formulation and Fig. 15 shows 22 the identification of the sample, containing a predominant mass 109 fragment, as 23 being mustard (bis (2-chloroethyl) sulphide), verifying live agent was used for the 24 trials.
WO 00/51687 PCT/CA00/00199 1 Immediately following application of the foam formulation the CADS 2 II and CAM H-mode readings dropped to a zero response. Hapsite air samples 3 acquired around the vehicle did not show any mustard content as shown in Fig. 16.
4 Clearly the foam formulation was capable of decontaminating the mustard agent, therefore the remaining stage 3 trials were directed towards the 6 foam formulations ability to simultaneously decontaminate and suppress an 7 explosive blast wave.
Stage 3 Blast suppression/decontamination Tent Trials Two separate stage 3 trials were performed, the first using G-agent simulant, diethyl malonate and the second using mustard chemical agent. The ambient temperature during the trials was 6 0
C.
In each trial a dispersal device was loaded with 250 ml of simulant or agent and secured to a ring stand approximately 50 cm off the ground. Four CADS II monitoring stations were deployed near the site, three in the downwind direction.
The stations were activated and allowed to collect and provide data to a remote CPU and computer system. In the case of the simulant trial, the dispersal device was placed inside a commercial tent and then the tent was filled with foamed formulation. In the case of the agent trial, a special tent with an opening in the bottom, but of the same shape and size as the commercial tent, was placed over the dispersal device and then filled with the foamed formulation.
In each case, the device was armed and then functioned. As soon as the area was declared safe from explosive hazard, a survey of the site around the tent was performed by personnel carrying CAMs. Hapsite was used to acquire air IIP_ WO 00/51687 PCT/CA00/00199 1 samples from around the tent and, in the case of the agent trial, was inserted 2 through an opening in the top of the tent to sample the head space above the foam 3 to detect any mustard contamination. CAM readings of the tent head space were 4 also taken.
In both trials, the tent showed no signs of damage or leakage of foam 6 following activation of the dispersal device.
7 Regarding the effectiveness of decontamination in the simulant trial, 8 the CADS II and CAM readings taken in close proximity to the tent found no G- 9 mode readings. No evidence of diethyl malonate was found on in the Hapsite reading over a 5 minute period.
11 Similarly, in the agent trial, CADS II and CAM readings, taken in the 12 proximity of the tent, also showed no H-mode response. No mustard was found in 13 the tent head space air. However, as shown in Fig. 15, the CAM surveys did show 14 a significant H-mode response coupled with a response indicative of a low reference ion peak. This response was exhaustively determined, through both 16 chromatograph and mass spectral analysis (Figs. 16-19b), to have been chlorinated 17 materials, hypothesized to be related to the chlorinated solvents in the original 18 military grade sample of mustard (Figs. 18-19). It may also be possible that 19 dichloroacetic acid may have been produced from chlorinated alkanes as a result of oxidation, either due to the explosion itself or due to the reaction with the strongly 21 oxidizing decontaminant in the foam formulation.
WO 00/51687 PCT/CA00/00199 1 In both stage 3 trials, it is clear that the foam formulation was capable 2 of both suppressing the blast, as evidenced by the intact tent structure following 3 activation, and capable of decontamination, as evidenced by the lack of G-agent 4 simulant and mustard agent following activation.
6 Example 7 A second staged trial was performed. Two formulations of blast 8 suppressing/decontamination foam were used. A first CB-decontaminating blast 9 suppressant foam formulation contained 3% active decontaminating ingredient and a second surface decontaminating foam formulation, contained 6% active 11 decontaminating ingredient.
12 13 Stage 1 Open Dispersion trial 14 A 250mL Nalgene bottle filled with DEM was fastened to a ring stand at approximately 0.3 m above the ground and 4 m from a small metal building.
16 Witness cards were set out near the device and affixed to the facing surfaces of the 17 building to indicate dispersed liquid spray.
18 Following detonation, the witness cards were examined and showed 19 a heavy spray of small droplets for at least 20m downwind of the device location.
The blast produced a loud noise readily heard at least 200m away. CAMs used to 21 survey the area showed strong G-mode responses 10 minutes after dispersal of the 22 simulant. An air sample acquired by Hapsite showed the sample to contain a high 23 concentration of a single component, subsequently identified as DEM, as shown 24 in the total ion chromatogram of Fig. WO 00/51687 PCT/CA00/00199 1 Clearly the dispersal equipment used was capable of dispersing 2 simulant over the test site and the instrumentation used to measure the 3 contamination, capable of measuring the G-simulant, DEM.
4 Stage 2 Vehicle Decontamination 6 A CARC painted armored personnel carrier (APC) was placed within 7 a plastic-lined containment pit and four CADS stations were deployed in a circular 8 pattern around the pit at a standoff distance of approximately 5 m. Hapsite was 9 used to measure a head-space air sample above a bottle of mustard agent producing a total ion and mass 109 reconstructed ion chromatogram as shown in 11 Fig. 21. This was subsequently verified to be that of mustard, with very few 12 impurities. One side of the APC was painted with approximately 75mL mustard. All- 13 CADS II stations, especially those in the downwind direction, showed an immediate, 14 strong response in the H-mode, indicative of mustard vapor. Surface decontaminating foam was applied to the vehicle, the vehicle was then 16 scrubbed with long handled brushes and allowed to sit for 15 minutes.
17 Within one minute of application of the foam, the CADS stations 18 responses returned to baseline, indicating the absence of mustard vapor. CAMs 19 were used to survey the air around the vehicle 10 minutes following foam application and showed no H-mode response. An air sample acquired by Hapsite 21 during the scrubbing process did not show the presence of mustard vapor. After 22 minutes, the vehicle was washed down with water and further CAM surveys were 23 conducted, which verified the absence of mustard vapor.
24 Stage 3-Blast SupDressant/Decontamination Tent Trials Two stage 3 trials were performed, one using G-agent simulant (DEM) and one using mustard agent. In both cases, a 250 mL Nalgene bottle equipped with detonation equipment and filled with simulant or agent, was placed on the floor of a steel containment tray, placed inside a 12 ft. x 12 ft. x 10 ft. or 3.66 m x 3.66 m x 3.05 m wood frame enclosure sealed with polyethylene vapor barrier. Two CAMs and components of a CADS station were located within the enclosure. Further, four CADS stations were deployed around the enclosure at a distance of approximately 5 m. All CAMs were set in G-mode for the simulant trial and in H-mode for the mustard trial.
A ballistic tent was placed over the bottle, the tent was filled with CBdecontaminating blast suppressant foam and the bottle was remotely detonated.
In both trials, the tent remained intact and containing all materials. Very little detonation sound was heard outside the test. The head-space air within the tent and the containment shelter were examined using portable CAMs and Hapsite at minutes after detonation. The temperature of the head space was measured. Further CAM surveys were conducted at 30 minutes post-detonation. Foam was then drained from the tent into the containment tray and CAM surveys conducted to determine the presence of residual simulant or agent.
No response for either simulant or agent was recorded by the CADS stations or CAMs deployed within and about the containment. Temperatures measured in the head-space indicated that the explosive event and decontamination process were exothermic.
S. 39 WO 00/51687 PCT/CA00/00199 1 Hapsite GC/MS analysis as shown in Fig. 22 showed a small amount 2 of DEM and dichloroethyl acetate, most likely produced by a reaction between DEM 3 and the chlorinated oxidant in the decontaminant, to be present in the head-space 4 air of the simulant trial. CAM surveys of the released foam materials after minutes showed no evidence of DEM.
6 CAM surveys in the head space air of the agent trial showed a strong 7 H-mode response which was subsequently proven by Hapsite GC/MS analysis, as 8 shown in Fig. 12, not to be mustard, but to be 1,2-dichloroethane instead. It is 9 thought this compound may be a reaction product of the mustard with the chlorinated oxidant in the decontaminant. Again CAM readings taken over the 11 released foam after 30 minutes show no evidence of mustard vapor.
12 Clearly the foam formulation is capable of suppressing a blast and 13 decontaminating the CB agents released as a result.
14 Examples 6-9 16 Examples 6 through 9 are directed solely at various foam 17 formulation's ability to decontaminate various types of contamination. These 18 include, chemical warfare agents of the G and V classes, mustard agent, biological 19 spore-forming warfare agents and radioactive particulates.
Further, in each of Examples 6 8, quantitative analyses for residual 21 agents were performed on a high pressure liquid chromatography (HPLC) system 22 for separation of the reaction components, equipped either with a HPLC-UV 23 detector in series with a commercially available dual flame gas chromatographic 24 flame photometric detector (FPD) from Varian Associates, or, where possible, on WO 00/51687 PCT/CA00/00199 1 a Hewlett-Packard 1100 LC-MS system equipped with a diode-array UV-VIS 2 spectrophotometer and mass selective detector (MSD). The water used in the 3 reactions, prepared solutions, and in the HPLC was distilled and deionized. The 4 formulation for the surfactant/foam was first warmed to 320C to ensure homogeneity. CB agents and simulant DFP were provided by the Canadian Single 6 Small Scale Facility at the Canadian Defence Research Establishment Suffield 7 (DRES) in southern Alberta, Canada and Aldrich Chemical Company, respectively.
8 GB stock calibration solution was prepared by weight in acetonitrile (AcCN) and 9 several dilutions were prepared ranging from 25 to 900 ng/iL for calibration of the FPD, UV, and MSD responses. Stock solutions of the other CW agents were 11 prepared volumetrically in AcCN and similarly diluted for calibration.
12 Unless otherwise specified, in a typical experiment, samples were 13 prepared in 2.0mL autosampler vials. The first addition was a water solution 14 containing the foamer and, if necessary, the co-solvent. This was followed by buffer concentrate, then the decontaminant concentrate which had been separately 16 prepared by adding the active ingredient, anhydrous sodium dichloroisocyanuric 17 acid to water and heating to 290C with stirring for 15-30 minutes. Finally, the 18 CB agent was added defining time zero, and aliquots, at noted elapsed times, were 19 directly injected into the LC. The temperature of the vial holder was maintained at 25.0°C and a mini stirbar in the vial mixed the components. Fresh samples were 21 prepared for each FPD analysis to obtain residual agent concentration profiles over 22 time and these same solutions were subsequently analyzed by LC-MS.
23 WO 00/51687 PCT/CA00/00199 1 Example 6 2 Having reference also to Fig. 24, the effectiveness of several 3 decontaminant formulations against selected G-type nerve gases GB, GA and GD 4 and mustard gas, HD, was determined. The formulations tested consisted of an active ingredient, a foamer, an inorganic buffer mixture and, optionally, co-solvent, 6 in excess of that already present in the foamer mixture. The co-solvent values in 7 Fig. 24 represent added co-solvent and that contained in the foamer.
8 Three decontamination formulations were assessed for effectiveness 9 against typical G-nerve agents; the mildest formulation, using 3% w/w SD, a 2/3 strength buffer, and 1.3% w/w foamer; an intermediate strength formulation with 6% 11 w/w SD, full strength buffer, 4.6% w/w foamer and an additional 6.9% w/w to 7.8% 12 w/w co-solvent, and a full strength formulation with 9% w/w SD, full strength buffer, 13 4.8% w/w foamer and 6.9% w/w additional co-solvent. Although anhydrous SD was 14 used in preparation of the solution, percentages are quoted in terms of the equivalent amount of dihydrate. Percentages quoted for foamer represent 16 undiluted double-strength foamer which has 45.5% surfactant.
17 In order to standardize concentrations between experiments, the 18 effectiveness was calculated as a percentage of residual agent.
19 Using 0.29% w/w GB, there was no evidence of residual agent in any of the LC-FPD or LC-MS analyses for the mildest and intermediate strength 21 formulations w/w and 6% w/w SD). GB was destroyed in each case before the 22 first sample could be taken (0.43 and 1.13 minutes respectively). For the most 23 potent formulation w/w SD), only LC-FPD analysis was performed at 1.78 WO 00/51687 PCT/CA00/00199 1 minutes elapsed time and no agent was detected indicating complete destruction 2 of the agent within 1.78 minutes.
3 Using 0.29% w/w GA, only the mildest and intermediate strength 4 formulations w/w and 6% w/w SD) were evaluated. The mildest formulation was tested in two separate experiments. In the first, containing w/w foamer, 6 LC-FPD analysis indicated that GA was destroyed within 1.33 minutes. In the 7 second, containing w/w foamer, there was no evidence of GA in 1.07 8 minutes elapsed time (LC-FPD) or 3.43 minutes (LC-MS). For the intermediate 9 strength formulation containing an additional 7.5% w/w co-solvent, there was no evidence of GA in 1.07 minutes elapsed time by LC-FPD or 3.35 minutes by LC- 11 MS.
12 Using 0.29% GD, again only the mildest and intermediate strength 13 formulations were each evaluated. The full strength formulation was not tested due 14 to the success with the two milder formulations. The mildest formulation was tested and, in contrast to the other two G-agents examined, small amounts of residual GD 16 appeared to be observed for the shortest reaction time sample. Specifically, as 17 analyzed by LC-FPD, 5.0% residual agent appeared to be present at 1.07 minutes 18 and 0.5% appeared to remain at 4.77 minutes, and the agent was completely gone 19 by 10 minutes, as determined by LC-MS analysis. Similar results were observed using the intermediate solution containing 7.8% additional co-solvent. Complete 21 LC-MS characterization of the peak eluting at GD in a stock solution of GD 22 suggests that a trace of a GD-related impurity, methylpinacolylmethylphosphonate 23 also eluted at this point, possibly contributing to the residual peak observed at short 24 reaction times in HPLC-FP. Thus, although GD appears to be more difficult to
I
WO 00/51687 PCT/CA00/00199 1 destroy than GB or GA, the mildest formulation is still very effective against GD 2 within acceptable time limits.
3 Using 0.27% w/w HD, again due to their success, only the mildest 4 and intermediate strength formulations were evaluated. The mildest formulation was tested for effectiveness against HD in three separate tests. In the first test, 6 there was no evidence of residual HD after 2.67 or 4.92 minutes (reaction solutions 7 had to be mixed more vigorously than the other agents due to limited solubility of 8 HD so earlier sampling was not possible). In the second test, no residual agent 9 was detected after 3.0 or 62.1 minutes, however 6.2% of residual HD appeared to be present after 5.4 minutes assuming that the eluting peak was indeed HD. As a 11 confirmatory test, an third experiment was performed and no HD was detected after 12 3.65 or 4.97 minutes.
13 It is therefore concluded that even the mildest formulation, and least 14 likely to affect a foam's blast suppression capability, is completely effective against this level of HD in less than 2.7 minutes.
16 The intermediate formulation also tested for effectiveness against HD 17 and demonstrated no residual HD after 2.47, 5.27, or 53.3 minutes. Verification by 18 LC-MS could not be performed as HD cannot be detected using positive API-ES 19 under these conditions.
WO 00/51687 PCT/CA00/00199 1 Example 7 2 Having reference also to Fig. 25, the effectiveness of several 3 formulations against the nerve agent VX was determined.
4 Samples were prepared as described in Example 6. Two decontaminant formulations were assessed for effectiveness against VX-nerve 6 agent: the mildest formulation (MILD) with 3% w/w SD, 2/3 strength buffer, and 7 1.3% w/w foamer, and the full strength formulation with 9% w/w SD, full 8 strength buffer, 4.8% w/w foamer and 6.9% w/w additional co-solvent. As with 9 Example 6,.percentages quoted for foamer represent undiluted double-strength foamer.
11 Control formulations were also examined. These included a 12 formulation containing only full strength buffer and foamer (Buffer/Surf) and a 13 formulation containing all ingredients of the full strength decontaminant but without 14 active ingredient (FS*wo/SD).
In order to standardize concentrations between experiments, 16 effectiveness was calculated as percentage of residual agent. In addition, an 17 authentic sample of a known potential toxic product (Toxic Product), of hydrolysis 18 of VX, S-(2-diisopropylaminoethyl) methylphosphonothioic acid was synthesized 19 and characterized by LC-MS to be used as an indicator of unsuccessful detoxification of VX. All reaction mixtures were examined for the presence of this 21 compound; the presence of significant quantities would be sufficient evidence to 22 disallow the formulation as a possible decontaminant candidate. The results are 23 summarized in Fig. WO 00/51687 PCT/CA00/00199 1 In the first evaluation, the control formulation of buffer and foamer 2 (Buffer/Surf) was tested at a low concentration of VX (4 pUml). After six days, 42% 3 of the VX remained and toxic product in significant quantity was detected. The 4 control formulation of full strength formulation without active ingredient (FS*wo/SD) was tested against a concentration of 12 t/ml of VX. Again, significant quantities 6 of VX and toxic product were found at 125 minutes and 6 days. Additionally, there 7 was evidence of VX droplets in the solution at 125 minutes indicating that saturation 8 levels of VX were present in solution and that removal of VX from the system was 9 slow. When full strength formulation with SD was employed in excess (18.2:1 active speciesNX), all VX was destroyed in less than 7 minutes with no evidence 11 of toxic product.
12 A more extensive examination of the temporal effectiveness of the 13 mildest formulation was undertaken in which the stoichiometric ratios of 14 concentrations of VX to active chlorine present in solution were varied. For the lowest ratio effective decontamination of VX was not achieved although only 16 small traces of toxic product were observed. On the other hand, if the ratio was 17 -16-18:1, complete decontamination without significant production of toxic product 18 was achieved. As shown in Fig. 25, the mildest formulation at a ratio of 18.2:1 is 19 completely effective in less than eleven minutes. A similar formulation reacting at a ratio of 29:1 resulted in similar effectiveness, however this is most likely due to 21 the fact that the trace recorded by the LC-MS is at its detection limit using this 22 procedure.
WO 00/51687 PCT/CA00/00199 1 An analysis of the mild formulation without added VX did not register 2 any response for VX eliminating the possibility of a false positive VX result due to 3 the formulation itself.
4 In conclusion, even the mildest formulation is highly effective against VX provided that the ratio of reactant to agent is maintained over at least 17:1. This 6 finding is in accordance with statements made in Y-C Yang, J.A. Baker, and J.R.
7 Ward, Chem Rev., 1992, 92, p1731, in which the authors state that greater than 8 moles of active chlorine are required to oxidize 1 mole of VX.
9 Example 8 11 The effectiveness of foam phase-detoxification of anthrax spores was 12 determined. A suspension of Bacillus anthracis (Ames strain) was heat shocked 13 to kill the vegetative cells, leaving only the viable spores. Small metal coupons, 14 painted as per in-service military vehicles, were cleaned with ethanol wipes and sterilised by autoclaving. Each coupon to be used was spotted with 200 tL spore 16 suspension, distributed over the surface of the coupon as 60-70 small droplets and 17 allowed to dry overnight in a biosafety cabinet in a Level 3 Biocontainment 18 laboratory.
19 Two trials were performed on two separate days using freshly prepared foam formulations. Each trial used two of these coupons, one to test the 21 decontamination formulation and one to act as a control. Each coupon was placed 22 in a 100 mm petri dish, supported to keep it from coming in contact with the bottom 23 of the dish and covered with either the decontamination foam of the present 24 invention or a control foam not containing the decontaminant active ingredients.
WO 00/51687 PCT/CA00/00199 1 The lid of the petri dish was replaced and twisted to ensure that the foam contacted 2 the entire coupon. After 30 minutes each coupon was removed from the petri dish 3 using forceps, rinsed with sterile PBS, then swabbed twice over its entire surface 4 with a sterile sampling swab. The swab was placed in 5 ml of Heart Infusion broth and vortexed.
6 In both trials, 200 pL of neat broth from the decontamination foam- 7 treated coupon and 200 pl of a 1 x 10- 4 dilution (in PBS) of the broth from the 8 control foam-treated coupon were plated onto each of four Blood Agar plates. The 9 plates were incubated overnight at 370 C and the Colony Forming Units (CFU) observed the following day, are given in Table II. The Control foam results are 11 shown multiplied by 104 to adjust for the 10- 4 dilution.
12 Trial 1 and Trial 2 indicate, respectively, that, on average, only 13 0.0108% and 0.00109% of the original material on the decontamination foam- 14 treated coupons remained viable, translating into a 99.989% and 99.999% kill for simple contact with the decontamination foam for a period of 30 minutes.
16 17 Table II Data from Anthrax Spore Decontamination Trials.
Experiment Colony Counts Plate 1 Plate 2 Plate 3 Plate 4 Trial 1 Decon foam 33 26 28 21 Trial 1 Control foam 22 x10 4 22 x10 4 29 x10 4 28 x10 4 Trial 2 Decon foam 13 10 5 3 Trial 2 Control foam 66 x10 4 72 x10 4 68 x10 4 78 x10 4 18 19 Example 9 Having reference to Fig. 26, the effectiveness of the one variant of 21 the foaming agent by itself to effect decontamination of radioactive dusts from the 22 exterior surface of an armored vehicle was demonstrated. The vehicle, a French 48
I
WO 00/51687 PCT/CA00/00199 1 AMX-10 Armored Personnel Carrier, was contaminated by spraying the exterior 2 with 40 La particles (100-200 pm) to simulate surface contamination as might be 3 caused by driving across contaminated dusty terrain. Decontamination formulation 4 using Silv-Ex foamer was sprayed over the surface of the vehicle using a powered pressure washer fixed with an air induction foam nozzle of the type normally used 6 in applying fire-fighting foams. Subsequent to the application of decontaminant, the 7 vehicle was towed to a sensing frame where radiation measurements on the 8 exterior could be made. In Figure 15, the radiation level measured inside the 9 vehicle in the first trial was observed to be in the order of 30 mRem/hr. After towing to the decontamination site and commencing application, the radiation level was 11 observed to drop significantly (to approximately 11 mRem/hr) presumably due to 12 foam layers dropping off the sides of the vehicle during the application stage. The 13 radiation level flattened off over the course of the decontamination probably due to 14 residual particles remaining on the vehicle in areas where the foam could not drop off (top, crevices) readily. On commencement of rinsing of the vehicle with water, 16 the radiation level dropped even further (to approx. 6 mRem/hr) presumably due to 17 flushing off some of the remaining radioactive particles. A map of the radiation 18 emitted from the exterior surface of the vehicle as sampled by a frame of 80 probes 19 confirmed that the radiation had been significantly reduced by decontamination using Silv-Ex-based decontamination foam.
21 In a subsequent trial, the same vehicle was contaminated to a level 22 of approximately 45 mRem/hr. During movement of the contaminated vehicle to the 23 site of decontamination, significant loss in the level of radioactivity was observed.
24 The loss was such that the trial was terminated. It was apparent that the exterior WO 00/51687 PCT/CA00/00199 1 surface, having been previously cleaned in an earlier trial, did not retain radioactive 2 particles sprayed onto it. In other words the surface had been degreased and dust 3 adherence had been significantly decreased, suggesting an additional benefit to the 4 use of the formulation.
In a related examination in which paint panels were contaminated 6 and subsequently decontaminated by dry scrubbing, the standard approach for 7 decontamination of radioactive particulate matter was observed to attain a low level 8 of 0.55 mRem/hr whereas decontamination with Silv-Ex-based decontamination 9 foam reduced the radiation to a level of 0.33 mRem/hr after one application and 0.22 mRem/hr after a second decontaminant application, both of which surpass the 11 standard approach for addressing this hazard.

Claims (23)

1. A method for dispersal suppression from an explosive CB contamination device comprising the steps of: surrounding the explosive contamination device with a containment structure; and filling the containment structure with an aerated foam comprising both, i) a high expansion foamer; and ii) afoamer-compatible decontamination formulation effective on chemical and biological agents without significantly and adversely affecting the formation of foam, wherein before filling the containment structure, further comprising the steps of: preparing a foamer from a surfactant, a co-solvent selected from the group consisting of polypropylene glycol, polyethylene glycol, and derivatives and mixtures thereof, and a foam stabilizer; preparing the decontamination formulation from a chloroisocyanuric acid salt, and a buffer to maintain said formulation at a pH from about 11 to about preparing a mixture of the foamer and decontamination 20 formulation in water; and S. foaming the mixture. a..
2. The method of claim 1, wherein said chloroisocyanuric acid salt is selected from the group consisting of an alkali metal salt of monochloroisocyanuric acid, 25 dichloroisocyanuric acid, and.a combination thereof with cyanuric acid.
3. The method of claim 2, wherein said alkali metal salt of dichloroisocyanuric acid is sodium dichloroisocyanurate. 51 o
4. The method of any of claims 1 to 3, wherein said buffer fails over time, allowing the pH to fall from an initial pH of about 11 to a pH about The method of claim 4, wherein the buffer maintains the pH of the formulation above 8.5 for at least 30 minutes.
6. The method of any of claims 1 to 5, wherein the co-solvent is polypropylene glycol having the chemical formula R,-(OCH(CH 3 )CH 2 )n-OR 2 where'R, arid R 2 are independently H, an alkyl, or an ester group and n>l.
7. The method of claim 6, wherein said alkyl group representing Ri or R, is a methyl, ethyl, propyl, or butyl group or a mixture thereof.
8. The method of claim 6, wherein at least one of said R, or R 2 is hydrogen.
9. The method of claim 6, wherein both said Ri and R 2 are hydrogen. The method of any of claims 1 to 5, wherein said co-solvent is a 20 partially etherified polypropylene glycol.
11. The method of claim 10, wherein said partially etherified polypropylene glycol has the formula R,-(OCH(CH,)CH),-OR 2 where one of the R, or R 2 is independently H, or an alkyl group and n l.
12. The method of claim 11, wherein. said alkyl representing R, or R 2 is a S. methyl, ethyl, propyl, butyl group or a mixture thereof.
13. The method of claim 11, wherein at least one of said R, or R 2 is hydrogen. *52 52
14. The method of any of claims 1 to 13, wherein lithium hypochlorite is included in the decontamination formulation in amounts in the range of from about to about 10% by weight of the chloroisocyanuric acid salt.
15. A process for neutralizing an explosive CB contamination device comprising: producing an aerated foam formed from. a formulation in water comprising a surfactant, a co-solvent selected from the group consisting of polypropylene glycol, polyethylene glycol, and derivatives and mixtures thereof, a foam stabilizer, a chloroisocyanuric acid salt, and a buffer to maintain, said formulation at a pH from about 11 to about 8.5; and surrounding the explosive CB contamination device with the foam.
16. The process of claim 15 further comprising surrounding the explosive CB contamination device with a containment structure and filling the structure with the aerated foam.
17. In combination, a system for dispersal suppression of an explosive CB contamination device comprising: 20 a containment structure for surrounding the explosive contamination device; and aerated foam contained within the structure being formed from a foam formulation in water comprising a surfactant, a foam stabilizer, a co-solvent selected from the group consisting of polypropylene glycol, polyethylene glycol, and 25 derivatives and mixture thereof, a chloroisocyanuric acid salt, and a buffer to maintain said formulation at a pH from about 11 to about
18. The system of claim 17 wherein the foam formulation comprises: a foamer comprising a surfactant, a co-solvent selected from the 30 group consisting of polypropylene glycol, polyethylene glycol, and derivatives and mixtures thereof, and a foam stabilizer; and 53 nA/l.//nl 12:56 FAX 613 952 6082 INTELLECTUAL PROPERTY ?inno S11-04-2001 CA 00000019. 1 a decontamination formulation comprising a chloroisocyanuric 2 acid salt, and a buffer to maintain said formulation at a pH from about 11 to 3 about 4
19.The system of claim 17, wherein the foam formulation 6 comprises: 7 about 0.4 4 weight of the surfactant; about 0.03 8 weight of the foam stabilizer; and about 0.10 9.5 weight of the co-solvent; 9 about 3 6 of the chloroisocyanuric acid salt; and the balance being water. 11 12 20.The system of claim 19, wherein the foam formulation 13 comprises: 14 about 3% by weight of a chloroisocyanuric acid salt; about 0.6 weight of the surfactant; 16 about 0.03 weight of the foam stabilizer; 17 and about 0.75 of the co-solvent selected from the group 18 consisting of polypropylene glycol, polyethylene glycol, and derivatives and 19 mixtures thereof; a buffer to maintain said formulation at a pH from about 11 to 21 about 8.5; and 22 the balance being water. 23 24 21.A decontaminating and dispersion suppressing foam formulation in water comprising: 26 a surfactant; 27 a foam stabilizer; 28 a co-solvent selected from the group consisting of polypropylene 29 glycol, polyethylene glycol, and derivatives and mixtures thereof; a chloroisocyanuric acid salt; and 31 a buffer to maintain said formulation at a pH from about 11 to about 32 33 54 AMENDED SHEET Fmnfanr ~oit IlI.Anr. 1Q:R7
22. A decontaminating and dispersion suppressing foam formulation in water comprising: a foamer comprising a surfactant, a co-solvent selected from the group consisting of polypropylene glycol, polyethylene glycol, and derivatives and mixtures thereof, and a foam stabilizer; and a decontamination formulation comprising a chloroisocyanuric acid, and a buffer to maintain said formulation at a pH from about 11 to about
23. The decontaminating and dispersion suppressing foam formulation of claim 21, wherein the foam formulation comprises: about 0.4 -4 weight of the surfactant; about 0.03 0.5 weight of the foam stabilizer; and about 0.10 9.5 weight of the co-solvent; about 3-6% of the chloroisocyanuric acid salt;. and the balance being water.
24. The decontaminating and dispersion suppressing foam formulation of claim 21, wherein the foam formulation comprises: about 3% by weight of a chloroisocyanuric acid salt; about 0.6 weight of the surfactant; 0 about 0.03 weight of the foam stabilizer; and about 0.75 of the co-solvent selected from the group consisting of polypropylene glycol, polyethylene glycol, and derivatives and mixtures thereof; a bufferto maintain said formulation at a pH from about 11 to about S 25 8.5; and the balance being water.
25. The decontaminating and dispersion suppressing foam formulation of claim 24, additionally comprising lithium hypochlorite in amounts in the range of from 30 about 5 to about 10% by weight of the chloroisocyanuric acid salt. S. nfli/11 12:57 FAX 613 952 6082 ,11-04-2001 I NTELLECTUAL PROPERTY Ehio0 1 CA 0000001 9E 2 3 4
26. The decontaminating and dispersion suppressing foam formulation of any one of Claims 21-24, wherein the surfactant is of the formula [R(OCH 2 CH 2 )MS 4 2 where R is an alkyl group having fronm eight to fourteen carbon atoms, m is an integer from 1 to 3, and M is Na+ or NK 4 in mixture with CH 3 (CH 2 1 CHCHCH 2 SO 3 Na.
27. The decontaminating and dispersion suppressing foam formulation of any one of Claims 21-26, wherein the foam stabilizer is an aliphatic alcohol of formula CH 3 (CH 2 OH, where n =8 to 16. 56 AMENDED SHEET FmDf~n9R7Ait ii .ADr. 19:57
AU27898/00A 1999-02-26 2000-02-25 Decontaminating and dispersion suppressing foam formulation Ceased AU766865B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US12209199P 1999-02-26 1999-02-26
US60/122091 1999-02-26
PCT/CA2000/000199 WO2000051687A1 (en) 1999-02-26 2000-02-25 Decontaminating and dispersion suppressing foam formulation

Publications (2)

Publication Number Publication Date
AU2789800A AU2789800A (en) 2000-09-21
AU766865B2 true AU766865B2 (en) 2003-10-23

Family

ID=22400549

Family Applications (1)

Application Number Title Priority Date Filing Date
AU27898/00A Ceased AU766865B2 (en) 1999-02-26 2000-02-25 Decontaminating and dispersion suppressing foam formulation

Country Status (7)

Country Link
EP (1) EP1154821B1 (en)
AT (1) ATE267630T1 (en)
AU (1) AU766865B2 (en)
CA (1) CA2299259C (en)
DE (1) DE60011050T2 (en)
IL (2) IL145033A0 (en)
WO (1) WO2000051687A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004052918A2 (en) 2002-12-09 2004-06-24 The Trustees Of Columbia University In The City Of New York Peptides and methods for deactivation of organophosphorus-based nerve agents and insecticides
FR2931687B1 (en) * 2008-05-27 2017-11-24 Commissariat A L'energie Atomique AQUEOUS DECONTAMINANT AND FOAMING SOLUTION.
FR3103549B1 (en) * 2019-11-25 2021-12-03 Arianegroup Sas MOBILE DEVICE FOR NEUTRALIZING CHEMICAL OR BIOLOGICAL WEAPONS

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030861A2 (en) * 1997-01-10 1998-07-16 Loizeaux Group Int'l Ltd. Method and apparatus for the destruction of articles

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5271592A (en) * 1975-12-12 1977-06-15 Mitsubishi Chem Ind Ltd Production of regenerared nylon resin
ZA775615B (en) * 1976-10-26 1978-08-30 Stauffer Chemical Co Hard surface cleaning composition
JPS56143300A (en) * 1980-04-09 1981-11-07 Kao Corp Foamable composition
JPS5953314B2 (en) * 1980-04-09 1984-12-24 花王株式会社 foamable composition
KR930009035B1 (en) * 1990-03-19 1993-09-22 국방과학연구소 Aqueous antidote composition
FR2679458A1 (en) * 1991-07-23 1993-01-29 Commissariat Energie Atomique DECONTAMINATION FOAM WITH CONTROLLED LIFETIME AND DECONTAMINATION INSTALLATION OF OBJECTS USING SUCH FOAM.

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998030861A2 (en) * 1997-01-10 1998-07-16 Loizeaux Group Int'l Ltd. Method and apparatus for the destruction of articles

Also Published As

Publication number Publication date
ATE267630T1 (en) 2004-06-15
WO2000051687B1 (en) 2000-11-23
DE60011050T2 (en) 2005-11-03
IL145033A0 (en) 2002-06-30
IL145033A (en) 2006-07-05
CA2299259C (en) 2007-12-04
EP1154821A1 (en) 2001-11-21
AU2789800A (en) 2000-09-21
DE60011050D1 (en) 2004-07-01
EP1154821B1 (en) 2004-05-26
WO2000051687A1 (en) 2000-09-08
CA2299259A1 (en) 2000-08-26

Similar Documents

Publication Publication Date Title
US6405626B1 (en) Decontaminating and dispersion suppressing foam formulation
CA2300698C (en) Broad spectrum decontamination formulation and method of use
US8241562B1 (en) Enhanced toxic cloud knockdown spray system for decontamination applications
Talmage et al. Chemical warfare agent degradation and decontamination
CA2328016C (en) Formulations for neutralization of chemical and biological toxants
US20030060517A1 (en) Concentrated formulations and methods for neutralizing chemical and biological toxants
US6245957B1 (en) Universal decontaminating solution for chemical warfare agents
WO2005055963A2 (en) Decontamination formulation with sorbent additive
US7390432B2 (en) Enhanced formulations for neutralization of chemical, biological and industrial toxants
EP1155281B1 (en) Foam formulations
CA2461872C (en) Enhanced formulations for neutralization of chemical, biological and industrial toxants
AU766865B2 (en) Decontaminating and dispersion suppressing foam formulation
US20070185002A1 (en) Long lasting decontamination foam
Tucker et al. Decontamination formulation with sorbent additive
Tucker et al. Knockdown and Neutralization of Clouds of Toxic Chemical and Biological Materials.
Ciegler et al. AD-A202 525
Jacobson Particulate aerosols–update on performance and engineering
Maupin MOBILE CHEMICAL MUNITIONS TREATMENT TECHNOLOGY
Tucker Granulated decontamination formulations
Systems et al. Decontamination

Legal Events

Date Code Title Description
MK6 Application lapsed section 142(2)(f)/reg. 8.3(3) - pct applic. not entering national phase
TH Corrigenda

Free format text: IN VOL 14, NO 49, PAGE(S) 8945-8948 UNDER THE HEADING APPLICATIONS LAPSED, REFUSED OR WITHDRAWN PLEASE DELETE ALL REFERENCE TO APPLICATION NO. 17952/00, 26939/00, 27028/00, 27898/00, 28132/00, 29361/00, 31332/00, 33140/00, AND 33180/00

FGA Letters patent sealed or granted (standard patent)