Formulations for the Decontamination and Mitigation of CB ... · The SNL Decon Formulation has...

TECHNICAL REPORTMOD2003-1012-GIssued February 2003

Formulations for the Decontaminationand Mitigation of CB Warfare Agents,Toxic Hazardous Materials, Viruses,Bacteria and Bacterial Spores

Prepared by:Modec, Inc.4725 Oakland Street Denver, Coloradowww.deconsolutions.com

Pursuant to its License No. 00-C00872 with Sandia National LaboratoriesAlbuquerque, New Mexico 87185. Approved for General Release 2/23/01.Sandia is a multiprogram laboratory operated by Sandia Corporation,A Lockheed Martin Company, for the United States Department ofEnergy under Contract DE-AC04-94AL85000.

.

www.deconsolutions.com

Formulations for the Decontamination and Mitigation ofCB Warfare Agents, Toxic Hazardous Materials, Viruses

Bacteria and Bacterial Spores

AbstractA non-toxic, non-corrosive aqueous foam with enhanced physical stability for the rapid mitigationand decontamination of chemical and biological warfare (CBW) agents and toxic hazardousmaterials has been developed at Sandia National Laboratories. The foam formulation is basedon a surfactant system to solubolize sparingly soluble agents and increase rates of reaction withnucleophilic reagents and mild oxidizing agents. The formulation also includes water-solublepolymers to enhance the physical stability of the foam.

Experimental results have shown effective decontamination of both chemical warfare (CW) andbiological warfare (BW) agent simulants and live agents on contaminated surfaces and insolution. Testing has also shown that the foam decontaminates thickened agent simulants aswell. Other experimental work has demonstrated that the foam effectively decontaminates CWagent simulants on a variety of surfaces. The foam also kills anthrax spores. In biological tests,7-log kill of the spores has been achieved after exposure to the foam solution. Additional testinghas demonstrated that the foam is also effective in killing vegetative cells of Erwinia herbicola (asimulant for plague) and the MS-2 virus (a simulant for smallpox).

Additional tests indicate that the formulation may be effective as a universal decontaminant on avariety of toxic industrial materials and other hazardous bacteria, viruses and materials such ashydrocarbon based compounds as well.

Modec, Inc. of Denver, Colorado was selected by the Department of Energy to commercialize theinvention pursuant to License No. 00-C00872. Modec has compiled this report for potential end-users for evaluation and analysis. The data herein is based upon previously issued documents inofficial reports including patent disclosures and Department of Energy documents (PatentApplication No. 60/146,432 dated July 29, 2000 and Sandia Report SAND2000-1419 dated June2000) and internally generated information which is proprietary to Modec, Inc.

NOTICE: Information contained in this report was prepared from an account of worksponsored by an agency of the United States Government. Neither the United StatesGovernment, nor any agency thereof, nor any of their employees, nor any of theircontractors, subcontractors, or their employees, make any warranty, express or implied,or assume any legal liability or responsibility for the accuracy, completeness, orusefulness of any information, apparatus, product, or process disclosed, or representedthat its use would not infringe privately owned rights. Reference herein to any specificcommercial product, process, or service by trade name, trademark, manufacturer, orotherwise, does not necessarily constitute or imply its endorsement, recommendation, orfavoring by the United States Government, any agency thereof, or any of their contractorsor subcontractors. The views and opinions expressed herein do not necessarily state orreflect those of the United States Government, any agency thereof, or any of theircontractors.

TABLE OF CONTENTS

Page

Introduction…………………………………………………………. 1

Technology DevelopmentA. Background……………………………………………. 2B. Reaction Mechanisms……………………………….. 3C. Past Decontamination Formulations……….………. 7D. Effect on Toxic Hazardous Materials………………. 8

SNL Decon FormulationA. Objectives…………………………………………….. 9B. SNL Formulation………………..……………………. 9C. Decontamination Effectiveness ..…………………… 10D. Independent Test Results………………….………… 10E. Deployment Methods.………………………………… 15F. Additional CBW Toxants Covered….………………. 17G. Logistical Considerations..…………………………... 18

Operational Characteristics and Adherence toMilitary Standards and Requirements ………………………….… 19

Conclusions…………………………………………………………. 21

Modec, Inc. Technical Report MOD2003-1012-G Page 1 06/03/03

INTRODUCTION

A revolutionary technology that is non-toxic, non-corrosive aqueous foam withenhanced physical stability for the rapid mitigation and decontamination ofchemical (CW) and biological (BW) warfare agents has been developed atSandia National Laboratories. The formulation is based on a surfactant system tosolubolize sparingly soluble CW agents and to increase rates of reaction withnucleophilic reagents. The formulation is the first known to be effective on abroad spectrum of chemical agents as well as biological agents, bacteria,viruses, and bacterial spores. This decontamination technology is attractive for civilian and military applicationsfor several reasons: 1) a single decon solution can be used for both CW and BWagents; 2) it can be rapidly deployed; 3) mitigation of agents can beaccomplished in bulk, aerosol, and vapor phases; 4) it exhibits minimal healthand collateral damage; 5) it requires minimal logistics support; 6) it has minimalrun-off of fluids and no lasting environmental impact; 7) it has a high expansionrate making it logistically desirable; and, 8) contact times can reasonably bedetermined.

The SNL Decon Formulation has decontaminated both CW and BW agents andsimulants. For CW work, live agent testing has been conducted with GD(Soman), VX, and HD (Mustard) at governmental facilities. The half-lives for thedecontamination of these agents in the foam system is on the order of twominutes to twenty minutes. The majority of the work with BW agents has focusedon anthrax where we have achieved 7-log kill (99.99999%) of anthrax sporesafter a ten minute exposure to the foam. Other BW work has demonstrated rapidkill of the simulants for plague (a vegetative bacterial cell) and for the smallpoxvirus.

The technology has been licensed to Modec, Inc., Denver, Colorado, for thepurpose of unrestricted commercialization pursuant to License No. 00-C00872.Modec, Inc. has prepared the following information for the benefit of end-userslooking to utilize the technology. Modec is involved with optimizing theformulation for use by virtue of advanced chemical compounding as part of itscommitment to maximize the technology's performance in detoxification andneutralization of toxic materials. Modec commercially offers its products in avariety of forms under the trade name of MDF (Modec Decon Formulation).


TECHNOLOGY DEVELOPMENT

A. BackgroundThe original objective of the research project at Sandia was to develop aneffective, rapid, and safe (non-toxic and non-corrosive) decontaminationtechnology. Ideally, the technology is applicable to a variety of scenarios such asthe decontamination of open, semi-enclosed, and enclosed facilities, vehicles,personnel and sensitive equipment.

The initial research effort has been directed to materials for neutralization ofchemical and biological compounds or agents, and especially chemical andbiological weapons agents and their method of making. This Program wasfunded by the United States Government under contract DE-AC04-94AL85000awarded by the U.S. Department of Energy's DOE-NN-20 CBNP Program'sDecontamination and Restoration Thrust Area.

In particular, the research was directed to materials containing solubilizingcompounds and reactive compounds that can be delivered as foams, sprays,liquids, fogs and aerosols to enhance the rate of reactions leading toneutralization of chemical compounds, and other additives which serve to kill orattenuate certain biological compounds or agents.

THE NATURE OF CBW AGENTS

Certain CW agents share chemical characteristics that present an opportunity forthe development of countermeasures. The chemical agents sarin, soman, andtabun (G-agents) are all examples of phosphorus-containing compounds which,when altered chemically, can lose their toxicity. Mustard, which is an example ofthe H-agents, and which is an example of the V-agents, can also be alteredchemically and rendered harmless. In addition, certain of the known BW agents,i.e., botulinum toxin, anthrax and other spore-forming bacteria, vegetativebacteria, including plague and various viruses can also be deactivatedchemically.

A CW or BW attack can involve either local placement or wide dispersal of theagent or agents so as to affect a population of human individuals. Because ofthe flexibility with which CW and BW (CBW) agents can be deployed,respondents might encounter the agents in a variety of physical states includingbulk, aerosol and vapors.


Decontamination of chemical compounds have focused primarily on chemicalwarfare agents, particularly on the nerve agents (such as G-agents and V-agents) and on the blistering agents (such as mustard gas, or simply, mustard).Reactions involved in detoxification of chemical agents can be divided intosubstitution and oxidation reactions. Decontamination of biological agents isprimarily focused on bacterial spores (e.g. anthrax) which are considered to bethe most difficult of all microorganisms to kill.

For the first responder, it is critical to decontaminate facilities or equipment to anacceptable level in a very short time so casualties can be located and treated. Inthe restoration scenario, time is of less importance but collateral damage, publicperception, and re-certification (i.e., complete decon) is of greater consequence.Thus, there were numerous research and development challenges associatedwith this effort. One challenge was to develop a common formulation effectiveagainst all chemical and biological agents, while being suitable for use on a widevariety of building materials commonly found in civilian facilities. A secondchallenge was the development of a decontamination formulation that can berapidly deployed in large quantities by first responders to effectively destroy (ordetoxify) chemical or biological agents while remaining relatively harmless toboth people and property. In addition, a formulation is desired that renderschemical and biological agents harmless in a reasonable period of time so thatrelatively rapid restoration of facilities may be achieved

B. Reaction Mechanisms

Decontamination of chemical agents has primarily focused on the nerve agentse.g., Sarin, Soman, (G Agents) and VX (V Agents) and on the blistering agents,e.g., Mustard. Reactions involved in detoxification of chemical agents may bedivided into substitution and oxidation reactions. Decontamination of biologicalagents is primarily focused on bacterial spores (e.g., anthrax), which areconsidered to be the most difficult of all microorganisms to kill. Importantreagents and mechanisms for these reactions are summarized below.

Hydrolysis Substitution Reaction

Hydrolysis of chemical agents can be carried out with water, hydroxyl ions orother nucleophiles. The rate of hydrolysis of mustard and the nature of theproducts formed depends primarily on the solubility of the agent in water and onthe pH of the solution. In the detoxification of Mustard, for example, the moleculefirst forms a cyclic sulfonium cation, which reacts with nucleophilic reagents. Thedominant product is thiodiglycol but this product may react with sulfonium ions togive secondary intermediates HD-TDG and CH-TDG shown below (Figure 1-1).


+ +CH2CH2S(CH2CH2OH)2 CH2CH2S(CH2CH2OH)2

S< S<CH2CH2C1 CH2CH2OH

HD-TDG CH-TDG

Figure 1-1: Secondary intermediate products generated by the hydrolysis ofmustard.

The hydrolysis of Sarin (GB) and Soman (GD) occurs rapidly under alkalineconditions and gives the corresponding O-alkyl methylphosphonic acid. Incontrast, the hydrolysis of VX with OH ions is more complex. In addition todisplacement of the thioalkyl group (i.e., P-S bond breakage), the O-ethyl groupis displaced (i.e., P-O bond breakage) producing a toxic product known as EA-2192. This concept is rationalized by considering that nucleophilic substitution atphosphorous centers involves addition to form a trigonal bipyramidal intermediate(TBP). Nucleophiles enter and depart the intermediate from an apical position.Electronegative groups, such as RO groups, preferentially occupy apicalpositions and groups that are bulky or electron donors, such as RS groups,occupy equatorial positions. If the lifetime of the TBP allows pseudorotation tooccur, the final product will depend on the balance between apicophilicity andleaving group ability. The result is that P-S bond cleavage is favored over P-Obond cleavage by a factor of about 5. Peroxyhydrolysis, on the other hand, usingOOH ions in alkaline medium was shown to involve quantitative P-S cleavage atrates 30-40 times that with OH. This selectivity was related to the relativebasicities of the anionic nucleophile and the leaving anions.

Catalytic species for acceleration of substitution reactions have been reported.An important example is o-iodosobenzoate (IBA). IBA is converted toiodoxybenzoate (IBX) via oxidation that then participates in the reaction with theCW agent.

The compound was also functionalized to introduce surface activity (surfactantcharacter) to the active group. Metal ion-amine complexes, with surface-activemoiety, were also developed and shown to exhibit catalytic effects in substitutionreactions. (Enzymes such as organophosphorous acid anhydrolase have alsobeen shown to accelerate substitution reactions with the G and VX agents.


Oxidation Reaction

Oxidative decontamination methods are especially useful for Mustard and VX.An early oxidant used was potassium permanganate. Recently, Oxone (amixture of KHSO5, KHSO4, and K2SO4) has been developed. Severalperoxygen compounds have also been shown to oxidize chemical agents (e.g.,perborate, peracetic acid, m-chloroperoxybenzoic acid, magnesiummonoperoxyphthalate, and benzoyl peroxide). More recently, hydro-peroxycarbonate anions produced by the reaction of bicarbonate ions withhydrogen peroxide have been shown to effectively oxidize Mustard and VXPolyoxymetalates are being developed as room temperature catalysts foroxidation of chemical agents but the reaction rates are reported to be slow at thisstage of development. Some of these compounds undergo a color change uponinteraction with chemical agents. This phenomenon is being exploited in theformulation of barrier creams and solid sorbents to indicate the presence ofchemical agents.

Kill of Biological Agents

Some consider the BW threat to be more serious than the CW threat. This is inpart because of the high toxicity of BW agents, their ease of acquisition andproduction, and difficulty in detection. There are hundreds of biological warfareagents available for use by terrorists. They may be grouped into the categoriesof spore forming bacterium (e.g., anthrax), vegetative bacterium (e.g., plague,cholera), virus (e.g., smallpox, yellow fever), and bacterial toxins (e.g., plague,cholera), virus (e.g., smallpox, yellow fever), and bacterial toxins (e.g., botulism,ricin). The focus of this work is on the decontamination of spores because theyare recognized to be the most difficult microorganism to kill.

Bacterial spores are highly resistant structures formed by certain gram-positivebacteria usually in response to stresses in their environment. The mostimportant spore-formers are members of the genera, Bacillus and Clostridium.Spores are considerably more complex than vegetative cells. The outer surfaceof a spore consists of the spore coat that is typically made up of a dense layer ofinsoluble proteins usually containing a large number of disulfide bonds. Thecortex consists of peptidoglycan, a polymer primarily made up of highlycrosslinked N-acetylglucosamine and N-acetylmuramic acid. The spore corecontains normal (vegetative) cell structures such as ribosomes and a nucleoid.

Since their discovery, considerable research has been carried out to investigatemethods to kill bacterial spores. Although spores are highly resistant to manycommon physical and chemical agents, a few antibacterial agents are alsosporicidal. However, many powerful bactericides may only be inhibitory to sporegermination or outgrowth (i.e., sporistatic) rather than sporicidal. Examples ofsporicidal reagents, using relatively high concentrations, are: glutaraldehyde,formaldehyde, iodine and chlorine oxyacids compounds, peroxy acids, andethylene oxide. In general, all of these compounds are considered to be toxic.


There are several mechanisms generally recognized for spore kill. Thesemechanisms, which may operate singularly or simultaneously, are describedbelow:

1. The dissolution or chemical disruption of the outer spore coat may allowpenetration of oxidants into the interior of the spore. Several studies (Kingand Gould, 1969; Gould et al., 1970) suggest that the S-S (Disulfide) richspore coat protein forms a structure which successfully masks oxidant-reactive sites. Reagents that disrupt hydrogen and S-S bonds increasethe sensitivity of spores to oxidants. A typical protein with disulfide linkage:

H2N-CH-COOH|

CH2|S|S|

CH2|

H2N-CH-COOH

Figure 1-2: Protein with cysteine linkage.

2. Peptidoglycan, which is loosely cross-linked and electronegative, makesup the cortex of a spore. Interaction between a disinfectant solution andpeptidoglycan may cause collapse of the cortex and loss of resistance.

3. The peptidoglycan of spore-forming bacteria contains teichoic acids (i.e.,polymers of glycerol or ribitol joined by phosphate groups). Disruption ofthe teichoic acid polymers may cause deficiencies in the peptidoglycanstructure making the spore susceptible to attack.

4. Certain surfactants may increase the wetting potential of the spore coat tosuch an extent as to allow greater penetration of oxidants into the interiorof the spore.

With all of these mechanisms, it is generally agreed that actual spore kill is onlyachieved when the SNA of the spore has been sufficiently disrupted ordestroyed.


C. Past Decontamination Formulations

Historically, decontamination solutions have focused strictly on the kill andneutralization of chemical and biological agents. Little emphasis has beenplaced on restoration and re-use of facilities and equipment. Instead, theseitems were considered to be expendable and were expected to be replaced inthe event of a CBW attack. Thus, most decontamination formulations currently inuse are both highly toxic and highly corrosive. A review of many of these currentdecontamination formulations is presented here.

Liquid Decontaminants Against CW Agents

In this section, a number of liquid decontamination formulations that have beendeveloped for the decontamination of chemical agents are documented. Asindicated, each of these formulations is highly toxic and/or highly corrosive.

Supertropical Bleach. The neutralization of chemical warfare agents began in1798 when Charles Tennant discovered bleaching powder. In 1917 theGermans used bleaching powder to neutralize mustard agent. Supertropicalbleach was standardized in the 1950's. It is a mixture of 93% calciumhypochlorite and 7% sodium hydroxide and is more stable than bleach in long-term storage and easier to spread. Mustard gas reacts with bleach by oxidationof the sulfide to sulfoxide and sulfone and by dehydrochlorination to formcompounds such as O2S(CHCH2)2. The G agents are converted by hydrolysis tothe corresponding phosphonic acids with the hypochlorite anion acting as acatalyst (Epstein et al., 1956). In acidic solutions, VX is oxidized rapidly bybleach at the sulfur atom and dissolves by protonation at the nitrogen. On theother hand, at high pH the solubility of FX is significantly reduced and thedeprotonated nitrogen is oxidized leading to consumption of greater thanstoichiometric amounts of bleach.

Decontaminant Solution 2 (DS2). Decontamination Solution Number 2 (DS2)was introduced in 1960. This is a non-aqueous liquid composed of 70%diethylenetriamine, 28% ethylene glycol monomethyl ether, and 2% sodiumhydroxide. The reactive component in the conjugate base is CH3OCH2CH2O-1.While DS2 is a highly effective decontaminant for CW agents, ethylene glycolmonomethyl ether has shown tetragonicity in mice and replacement withpropylene glycol monomethyl ether was proposed (DS2P). In addition, DS2attacks paints, plastics, and leather materials. To minimize these problems, thecontact time with DS2 is limited to 30 minutes followed by rinsing with largeamounts of water. Personnel handling DS2 are required to wear respirators witheye shields and chemically protective gloves. The reactions of DS2 with mustardlead to elimination of HC1. The nerve agents react with DS2 to form diesters,which further decompose to the corresponding phosphonic acid. DS2 is not veryeffective in killing spores. Only 1-log kill was observed for Bacillus subtilis after 1hour of treatment (Tucker, 1999).


D. Effect on Toxic Hazardous Materials

Unique Patented Characteristics - The SNL Technology has exhibited similarmitigation and neutralizing effects on a wide variety of toxic industrial materialsand other generally considered hazardous chemicals, compounds and materials.The SNL Decon Formulation contains reactive ingredients that will bothhydrolyze and oxidize organophosphates and mitigate many othertoxic/hazardous materials.

TOXIC INDUSTRIAL MATERIAL TESTING:

Sandia performed testing on a number of Toxic Industrial Chemicals ("TIC's").Analytic tests results are selected materials is shown in the following table:

Toxic IndustrialChemical

% Decontaminated:1 Minute

% Decontaminated:15 Minutes

Malathion (liquid) 89 95Hydrogen Cyanide (gas) >99 >99Sodium Cyanide (solid) 93 98Butyl Isocyanate (liquid) 99 >99Carbon Disulfide (liquid) >99 >99

Phosgene (gas) 98 >99Amhydrous Ammonia (gas) >99 >99

Note: All materials were fully decontaminated after sixty minutes.

Safe - Despite its power, the primary oxidizers within the Sandia Formulation willdecompose into oxygen and water. Consequently, Sandia Formulation has noneof the problems of gaseous release of using chlorine (chlorinated organics) orchemical residues that are associated with other chemical oxidants. And sinceSandia Formulation is totally miscible with water, is perfectly safe to handle andapply to many materials.

Versatile - The Sandia Formulation is very versatile. As a biocide, it can killvegetative biological agents as well as difficult-to-kill spores like anthrax andmolds. Similarly, it can treat both easy-to-oxidize pollutants (iron and sulfides)and difficult-to-oxidize pollutants (solvents, gasolines and pesticides) as well asimmediately reducing the flammability. And there is no residual effect on theenvironment. Further, it can be deployed in a variety of formats (liquid, foam, andvapor) which optimizes contact time and emulsification of target contaminants.


SNL DECON FORMULATION

A. Objectives

The decontamination program at Sandia National Laboratories (SNL) focused onthe development, demonstration, and commercialization of products for effectiveresponse and consequence management in the event of a release of chemicaland/or biological weapons agents on US civilians and facilities. The SNL projectis supported by the DOE NN-20 Chemical and Biological Non-Proliferation(CBNP) Program's Decontamination and Restoration Thrust Area.

It's stated objectives were to develop rapid, effective, and safe (non-toxic andnon-corrosive) decontamination technologies for a range of chemically andbiologically contaminated surfaces in civilian facilities primarily in the urbanenvironment (U.S. Department of Energy, 2000). For the three years, SNLworked on a reagent formulation that has been extremely effective in meetingthese overall objectives.

The SNL foam formulation has the following characteristics:

- it is effective for neutralizing both chemical and biological agents;- it is environmentally benign to both people and property;- it works on all currently anticipated material surfaces;- it can be incorporated into a wide variety of carriers (foams, gels,

and gasses) that satisfy a wide variety of operational objectives.- It can be retrofitted in to many existing decon apparatus.

The initial efforts have been spent on developing a foam formulation that can beused to decontaminate large surface areas such as the interiors of facilities.Progress on this research objective has proceeded to he point wheredevelopmental testing against live agents has been completed and theformulation has been shown to be effective. This section describes the physicaland chemical characteristics of the foam as well as its effectiveness againstchemical and biological agents in both laboratory and field tests.

B. Foam Formulation

The SNL foam is a unique formulation developed exclusively for thedecontamination of chemical and biological warfare agents. The foamformulation is based on a surfactant system to increase solubolization ofchemical agents and reactivity with nucleophilic reagents. A mild oxidizing agent(hydrogen peroxide) is also added to the foam at a low concentration.

The second important physical property of foam is its stability. Foam stability ismeasured by its half-drainage time, which is defined as the time required for afoam to lose half of its original liquid volume. For example, if 1L of solution is


used to generate a foam, the half-drainage time is defined as the amount of timefor 500 ml to drain from the foam. This property is important because a stablefoam allows a greater contact time between the formulation and the chemical orbiological agent. The objective of this program was to develop a formulation thatwill produce foam with half-drainage times of several hours.

C. Decontamination Effectiveness

Certain chemical agents share a similar chemical property in the fact that theycontain phosphorus bonds that can be altered when subjected to nucleophilicattack. These agents (i.e., the nerve agents) include the G agents (e.g., Sarin;Soman, and Tabun) as well as the V agents (e.g., VX). Each of these agentscan be chemically detoxified and neutralized if the phosphorus bond ischemically altered by hydrolysis or by oxidation.

Blistering agents such as mustard (HD) are chemically distinct from the nerveagents in that they do not have a phosphorus-containing group. However, thecarbon-chloride bonds in mustard are also subject to hydrolysis and the centralsulfur can be oxidized to sulfone and sulfoxide, thereby detoxifying the molecule.Mustard does share a similar property with the nerve agents in that they all areonly sparingly soluble in water.

The principle for detoxifying chemical agents in the foam is to provide amechanism to solubolize the sparingly soluble chemical agents and to attract anucleophilic catalyst, dissolved in aqueous media, to a position in close proximityto the agent molecule vulnerable to nucleophilic attack. This is accomplishedthrough the recognition that certain nucleophilic agents are negatively charged.The SNL foam formulation contains positively charged micelles, which solubolizethe CW agents and attract the negatively charged nucleophiles.

In the aqueous environment, the CW agent is located (solubilized) within themicelle comprised of an aggregate of surfactant molecules with hydrophobic tailsforming the interior core of the micelle, and hydrophilic heads concentrating atthe surface of the micelle. These positively charged hydrophilic heads attract thenegatively charged nucleophiles, greatly enhancing the reaction rates with theCW agents within the micelle. This is contrasted within the situation that wouldoccur in typical firefighting foam. Here, the negatively charged micelles repel thenegatively charged nucleophiles.

D. Independent Live Agent Test Results

Live agent tests were conducted at Edgewood Proving Grounds (ECBC),Maryland on the original DF-100 Formulation. Two types of tests wereperformed, kinetic (reaction rate) and contact hazard tests under controlled testprotocol. All tests were conducted with CASARM grade agents (Chemical AgentStandard Analytical Reference Material) at ambient room temperature.


Table 3-1: Percent decontamination in ECBC reaction rate tests for Df-100. Datafor DG and HD collected at pH 9.2. Data for VX collected at pH 10.5.

HD GD VXDecontaminant 10 Min 1 Hour 10 Min 1 Hour 10 Min 1 HourDS2 100 100 100 100 100 100Sandia Foam 47 100 >99 100 100 100

Df-100 was developed through funding provided by the U.S. Department ofEnergy’s and National Nuclear Security Administration’s Chemical and BiologicalNational Security Program (CBNP. During the field testing andcommercialization process, it became apparent that the primary interest for theuse of the decon formulation was from the civilian first responder (e.g., firedepartments, police departments, and HazMat units who would be the first toarrive at the scene of an attack utilizing CBW agents) and from the military (forboth battlefield and fixed site decontamination) followed by a secondary interestin use of the foam for facility restoration. It also became apparent that twoproperties of the original formulation (DF-100) made use of this formulation bythe civilian first responder and the military less than optimal. These propertiesinclude:

Formulation Adjustment for Decon of Each CBW Agent. The pH of the DF-100 has to be adjusted for optimal decontamination of specific chemical andbiological agents;

Relatively Slow Reaction Rate for Mustard. The reaction rate for onechemical agent, Mustard, was slower than the reaction rates for the otherchemical agents.

In July 2000, Sandia issued a non-exclusive, all field-of-use license to Modec,Inc. of Denver, CO for manufacture and sales of the decontamination technology.In October 2000, Sandia received funding from the DOE CBNP program todevelop an enhanced version of the DF-100 product specifically to address theissues described above and to optimize performance for the military and thecivilian first responder. The result of this work is DF-200, an enhanced version ofthe Sandia decon formulation.

The table below summarizes test results from IITRI on live chemical agents.

% Destruction of Chemical Agent Chemical Agent 1 minute 15 minutes 60 minutesGD 99.98 ± 0.01 99.97 ± 0.01 99.98 ± 0.01VX 91.20 ± 8.56 99.80 ± 0.08 99.88 ± 0.04HD 78.13 ± 10.53 98.46 ± 1.43 99.84 ± 0.32

Figure 5: Reaction rates in kinetic testing for DF-200HF against chemical agents.


Detection of very low levels of GD in the 15 and 60-minute samples wasdetermined to be from carryover in the gas chromatography columns and notfrom unreacted agent.

Methylphosphonic acid (MPA) and pinacolyl methylphosphonic acid (PMPA)were identified as byproducts in the decon/GD mixtures. Ethyl methylphosphonicacid (EMPA) and MPA were identified as byproducts in the decon/VX mixtures.This indicated that the destruction of the VX followed the more desirable path tothe phosphonic acids rather than to EA2192 (a toxic byproduct which can also beproduced during VX degradation). The initial degradation products for HD are amixture of the sulfoxide and sulfone byproducts followed by nearly completedisappearance of each of these byproducts after 60 minutes.

Results of tests utilizing DF-200 against anthrax spores is shown in Figures 6and 7 and against Yersinia pestis (i.e., the plague bacterium) are shown in Figure8 (NG refers to ‘no growth’). The detection limit for these tests were 10 CFU/ml.Note that the ‘error bars’ in the ‘% Reduction’ column takes into account thisdetection limit.

B. anthracis AMES-RIID Average CFU/ml Log Reduction % Reduction

Control 1.21E+07 0 0.00

15 min contact NG 7 100±.00004



Figure 6: Kill rates for B. anthracis AMES-RIID spores in a solution of DF-200HF.

B. anthracis ANR-1 Average CFU/ml Log Reduction % Reduction

Control 6.42E+07 0 0.00




Figure 7: Kill rates for B. anthracis ANR-1 spores in a solution of DF-200HF.


Y. pestis (ATCC 11953) Average CFU/ml Log Reduction % Reduction

Control 1.33E+07 0 0.00




Figure 8: Kill rates for Y. pestis cells in a solution of DF-200HF.

Bacillus Subtillus (ATCC19659) Average CFU/ml Log Reduction % Reduction

Control 6.7E+05 0 0.00

1 hr contact NG 7 100±.00004

3 hr contact NG 7 100±.00004

Figure 8: Kill rates for Bacillus Subtillus cells in a solution of DF-200HF in AOAC tests.

The petri dishes used for cell growth on each of these tests were saved for 21 daysfollowing the tests to verify that DF-200 actually killed the spores rather than justinhibited their growth. No growth on any of the petri dishes was observed after the 21-day period.

Modec's Decontamination Formulation MDF200 was independently confirmed by SandiaNational Laboratories in 2002 as effective on G, VX, Mustard and anthrax simulants(Diphenyl chlorophosphate, O-Ethyl S-ethyl Phenylphosphonothioate, 2-Chloroethylphenyl sulfide and Bacillus globigii spores, respectively) by achieving 100%neutralization of all agents. In addition, independent lab tests have shown 100%neutralization of bacillus subtillus spores in a solution of MDF200.


Results with BW Simulants and Agents – Laboratory Tests

Work with biological agents has been focused on what is perceived to be themost difficult of agents to kill, bacterial spores (e.g., Bacillus anthracis oranthrax). Numerous tests have been conducted with the spore-formingbacterium Bacillus globigii (a recognized simulant for anthrax) to determine theeffectiveness of the SNL foam formulation in killing this microorganism. Testshave also been conducted to determine the killing efficiency of the foam on asimulant for plague (Erwinia herbicola – a vegetative bacterial cell) and on asimulant for the smallpox virus (the MS-2 bacteriophage). In addition, live agenttesting has been conducted with Bacillus anthracis ANR-1 at the Illinois Instituteof Technology Research Institute in Chicago, Illinois. The foam has been shownto be effective in killing all of these organisms in a timely manner.

Two basic types of tests have been conducted to test the foam's effectiveness inthe killing of BW simulants and agents. In the first type of test, a solution test, themicroorganisms were dispensed directly into the liquid solution from which thefoam is generated. After specified periods of time, the microorganisms wereextracted from the solution by centrifugation, washed, and then plated on anappropriate biological medium to determine if they had been killed.

Microorganisms used for the spore tests were Bacillus globigii (ATCC 9372) andBacillus anthracis ANR-2. The microorganism used for the vegetative cell testswas Erwinia herbicola (ATCC 39368). The MS-2 bacteriophage (ATCC 15597B)with the bacterial host Escherichia coli (ATCC 15597) was used for the viralinactivation tests.

Photo of Bacillus globigii (anthrax spore simulant) killed during tests.


E. Deployment Methods

The formulation of the present invention can be delivered to the toxants in avariety of manners and phases to provide the necessary detoxification. Oneuseful form of delivery is foam. A non-toxic, non-corrosive aqueous foam withenhanced physical stability for the rapid neutralization of toxants, especially CWand BW agents, was the primary focus of the development work.

This neutralization technology is attractive for civilian and military applications forseveral reasons including: 1) a single neutralization solution can be used forboth chemical and biological toxants; 2) it can be rapidly deployed; 3) mitigationof agents can be accomplished in bulk, aerosol, and vapor phases; 4) it exhibitsminimal health and collateral damage; 5) it requires minimal logistics support; 6)it has minimal run-off of fluids and no lasting environmental impact; and, 7) it isrelatively inexpensive.

The foam formulation of the present invention can be delivered by variousmethods. Foams generated have been shown to have a maximum expansionratio of about 60-100:1 and have been shown to be stable for approximately 1-4hours depending on environmental conditions (temperature, wind, relativehumidity). The foam can also be generated by compressed air foam systemswhere air is directly injected into the liquid foam. Foam generated by this methodgenerally has expansion ratios of about 20-60:1 and is also stable from 1-4hours. The use of foam is desirable as less concentrate can be used (thereforeless weight and logistical burden) for combat or response operations.

Modec, Inc. has designed several highly portable, high volume CAF systems thatcan be easily deployed by a single operator. These systems afford users witheasy to use devices that can rapidly discharge foam to an intended target. Theformulation of the present invention has shown the capability to neutralizetoxants in bulk, aerosol and vapor states, and which can be deployed in a varietyof contexts to protect or clean up targets including equipment, open areas,facilities and buildings. The formulation of the present invention can also beused in disinfection scenarios for both animals and inanimate objects.

Alternative deployment methods for the foam formulation are also available withthe formulation of the present invention. Foam is nothing more than a liquidsolution with a gas phase (in this case, air) blown through it. It is the formulationthat is effective in the destruction/neutralization of the CBW agents, not the foam(in other words, the liquid formulation decontaminates CBW agents, not the air).

Methods such as sprays, mists and fogs can be utilized with the same basicformulation. The objective of these alternative methods will be to minimize thequantity of water that is required to be used in the restoration of controlledenvironments (such as indoor facilities) and to facilitate access of the formulation


to the CBW agents. These alternative deployment methods can have variousadvantages over foam deployment. A fog, for example, can be used to achieveeffective decon in areas where decontamination by a foam would be difficult, ifnot impossible. One example is the interior of air conditioning ducts. Remotelyactivated foggers could be placed inside of a facility and turned on at periodicintervals (from a remote location) to completely decontaminate the facility. Thismethod would greatly decrease the potential for decontamination personnel to beexposed to a CBW agent.

In one embodiment, the formulation of the present invention is an aqueous-basedformulation that is capable of being deployed as a fog (i.e., as an aerosol withparticulate sizes ranging from 1-30 microns) for the rapid neutralization ofchemical and biological warfare (CBW) agents. The formulation exhibits low-corrosivity and low-toxicity properties and can be deployed through commerciallyavailable fog generating devices. Current decontamination formulations utilizetoxic and/or corrosive chemical to achieve destruction of CBW agents that canpotentially damage sensitive equipment in which it comes into contact.

Greater than 99% neutralization of the G agent simulant (diphenyl chlorophosphate) was achieved after one-hour exposure to the fog in a test chamberon all surfaces tested and complete neutralization was achieved after foursuccessive fog treatments (with a one-hour wait between each treatment) for allsurfaces. Between 70% and 99% neutralization was achieved after foursuccessive foggings of the VX simulant (O-ethyl-S-ethyl phenylphosphonothioate) and between 30% and 85% neutralization was achieved withthe mustard simulant (chloroethyl ethylsulfide) after four successive foggings.For the anthrax simulant (B. globigii spores), 7 log kill was achieved after foursuccessive foggings.


F. Additional CBW Toxants Covered

The chemical toxants addressed by the formulation include, but are not limited to:

♦ o-alkyl phosphonofluoridates, such as sarin and soman♦ o-alkyl phophoramidocyanidates, such as tabun,♦ o-alkyl, s-2-dialkyl aminoethyl alkylphosphonothiolates and corresponding

alkylated or protonated salts, such as VX♦ mustard compounds, including 2-chloroethylchloromethylsulfide, bis(2-

chloroethyl)sulfide, bis(2-chloroethylthio)methane, 1,2-bis(2-chloroethylthio)ethane, 1,3-bis(2-chloroethylthio)-n-propane, 1,4-bis(2-chloroethylthio)-n-butane, 1,5-bis(2-chloreothylthio)-n-pentane, bis(2-chloroethylthiomethyl)ether, and bis(2-chloroethylthioethyl)ether

♦ Lewisites, including 2-chlorovinyldichloroarsine, bis(2-chlorovinyl)chloroarsine, tris(2-chlorovinyl)arsine, bis(2-chloroethyl)ethylamine, and bis(2-chloroethyl)methylamine,

♦ Saxitoxin♦ Ricin♦ alkyl phosphonyldifluoride and alkyl phosphorites♦ chlorosarin♦ chlorosoman♦ amiton, 1,1,3,3,3,-pentafluoro-2-(trifluoromethyl)-1-propene, 3-quinuclidinyl

benzilate methylphosphonyl dichloride♦ dimethyl methylphosphonate♦ dialkyl phosphoramidic dihalides♦ dialkyl phosphoramidates♦ arsenic trichloride♦ diphenyl hydroxyacetic acid♦ quinuclidin-3-ol♦ dialkyl aminoethyl-2-chlorides♦ dialkyl aminoethan-2-ols and dialkyl aminoethane-2-thiols♦ thiodigylcols♦ pinacolyl alcohols♦ phosgene♦ cyanogen chloride and thionyl chloride. ♦ hydrogen dyanide and chloropicrin,♦ phosphorous oxychloride♦ phosphorous trichloride, phosphorus pentachloride, and alkyl phosphites♦ sulfur monochloride, sulfur dichloride

These compounds and other chemical compounds that can be neutralized (e.g.detoxified) by nucleophilic and oxidizing reactive agents of the present invention,are neutralized by the formulations of the present invention.


G. Logistical Considerations

The unique formulation is very beneficial to end-users as it can be produced inseveral formats to fulfill operational and logistical requirements such as handling,transportation and dispensing.

The Power of Expansion – The unique expansive properties of the foamaffords end-users tremendous tactical advantageous previously not availablewith DS2. As the foam expands effectively up to 50:1, minimal bulk concentratecan be used to produce large amounts of decontaminant without outside watersources.

Calculation of Desired Coverage – End users can calculate of theamount of decontaminant required for the intended application based upon thetotal meters expected to be mitigated. The guidelines presented herein arebased upon the NATO Standard of 10 grams of CB warfare agent per squaremeter. Based upon application standards developed at Sandia NationalLaboratory .5 liters of decontaminant per square meter is required. On the nextpage are tables of baseline requirements based upon assumed minimalexpansion rates. Users should also be aware that operating conditions canimpact results based upon the type of delivery equipment to be utilized andvariations arising from foam depth, expansion rates, temperatures, wind andcontact surfaces.

Coverage of formulation at 15:1 Expansion Area5 gallons (18.925 liters) 38 sq. meters25 gallons (94.625 liters) 190 sq. meters100 gallons (378.5 liters) 760 sq. meters200 gallons (757 liters) 1,520 sq. meters

Design Considerations – Modec also brings unmatched experience andexpertise from its decade of service to the military and nuclear, chemical andbiological protection and mitigation industry. We understand the logisticalburdens and difficulty that end-users face when combating NBC in MOPP(Mission Oriented Protective Position) Gear and Level A & B PersonnelProtective Equipment (PP&E). Our Concept of Operations for equipment designand use always keep the warfighter and responder in mind as response to aCBW incident is a complex and stressful environment which is generally far fromcontrolled lab conditions.


OPERATIONAL CHARACTERISTICS ANDADHERANCE TO MILITARY STANDARDS ANDREQUIREMENTS

Efficacy Standards – The military has established baseline requirements fordecontaminant performance. The SNL Decon Formulations produced by Modecpresently conform to the following general requirements:

• Reduces the concentration or neutralize the effects of biological warfareagents listed on the Joint Chiefs of Staff’s Threat List (and biologicalpathogens of operational concerns) present on resources to a safeconcentration level for return to unrestricted operational (worldwide) use forintended mission duration.

• Reduces the concentration or neutralizes the effects of Toxic IndustrialMaterials (identified "TIM's") present on resources to a safe level for return ofthe resources to unrestricted operational (worldwide) use for intended missionduration.

• Reduces the concentration or neutralizes the effects of chemical agents to thesafe concentration levels for return of the resources to unrestrictedoperational (worldwide) use for the intended mission duration such that thesingle dose hazard levels are not exceeded.

• Reduces the concentration and/or fully neutralizes contamination within 15minutes (immediately) of application.

• Removes or neutralizes toxic substance absorbed into the surface materials.

• Decontaminates heavily soiled items, including items exposed to petroleum,oils and lubricants.

Material Effects Standards – The SNL formulation adheres to therequirements of minimizing the impact on materials:

• Decontaminant is useable on any surface (e.g. terrain, concrete, asphalt,paint, metal, plastics, composite surfaces, low-observable materials, rubberseals) without causing degradation of the surface to acceptable level.

• There is no adverse effect on systems being decontaminated (to includeindividual protective equipment, collective protective equipment, anddetection devices) to acceptable levels of degradation.


• Does not create residues or vapors during decontamination operations thatare known or potential teratogens or carcinogens, or are acute dermal, oral,or inhalation hazards to levels in accordance with guidelines of the Office ofPrevention, Pesticides and Toxic Substances.

• There are no residues or vapors during decontamination operations that arehazardous waste to the levels in accordance with recommendations of theResource Conservation and Recovery Act.

• There is no hazard to the environment versus current decontaminants (e.g.DS-2, STB, and Hypochlorite). Does not produce toxic by-products as shownin tests.

NOTE: The SNL Decon Formulation has been tested on numerous surfaceswithout causing degradation of any surface material. Formulation is non-toxicand non-corrosive. All systems being decontaminated can be thoroughly deconto reduce contamination to negligible risk levels, and reduce or eliminate theneed for protective clothing. SNL Decon Formulation allows for OperationalDecon and Retrograde Decon without degradation of equipment, collectiveprotective equipment and detection devices. Utilizing the SNL DeconFormulation, end-users do not have to worry about containment of run-offsolutions. No toxic by-products are generated with the SNL Formulation

Operational Environment Standards – Modec decontamination productscan be utilized for worldwide operations and deployment without degradationunder climatic conditions, e.g. rain and/or wind, and heat where agents or TIM’scan be encountered. The formulations perform under climatic conditions basicand hot (-0 C to 49 C) while meeting the functional requirements in thisspecification. When subjected to solar radiation, there is no direct impact on thefunctionality of the product and it will perform in 0 to 100 percent humidity, duringand after exposure to blowing rain. In addition, the formulations meet or exceedthe following operational environment standards:

• Fungus Standard• Salt Fog and/or Spray Standard • Dust and Sand Standard • High Altitude Standard • Shock Standards• Vibration Standards• Explosive Environment Standards• Rapid Decompression Standards• Environmental Standards• Existing Equipment Standards


CONCLUSIONS

The technologies commercialized by Modec, Inc. represent revolutionary newdevelopments for the response to dealing with CB Warfare Agents, ToxicIndustrial Materials, viruses, bacteria and bacteria spores. In addition, theoperational characteristics and unique delivery devices afford end-users withstate-of-the-art means of combating situations.

A non-toxic, non-corrosive aqueous foam with enhanced physical stability for therapid mitigation and decontamination of CBW agents has been developed atSandia National Laboratories. The Formulation is now commercially availablewith advanced delivery devices from Sandia commercial licensee, Modec, Inc.Results have shown effective rapid decontamination of both CW and BW agents.In addition, 99.99999% kill of anthrax spores was achieved after a one-hourexposure to the foam solution. Tests have demonstrated that the foam iseffective in killing vegetative cells of Erwinia herbicola and bacterial viruses(MS2), which are simulants for plague and smallpox.

This formulation is both non-toxic to animals, including humans, generally non-corrosive and can be used for the neutralization of many toxants, both chemicaland biological. The formulation allows decontamination of areas populated withboth people and sensitive equipment; works on all currently anticipated materialsurfaces and can be incorporated into a wide variety of carriers (foams, gels,fogs, aerosols) that satisfy a wide variety of operational objectives. Thisformulation has low toxicity and low corrosivity properties. This allows theformulation to be used where exposure to people, animals, or equipment may benecessary or prudent.

This technology was demonstrated in the Fixed Site Decon Trials at theEdgewood Chemical Biological Center (ECBC) where the foam successfullyneutralized TGD (thickened soman), VX and HD and at the U.S. Army DugwayProving Grounds where the formulation successfully killed Bacillus globigiispores (an anthrax simulant) on common office materials.

This advanced technology represents a significant breakthrough to allow end-users the ability to effectively combat CB warfare agents, viruses, bacteria, toxicindustrial materials and bacterial spores.

Further information is available by contacting Modec, Inc. at 1-800-967-7887, viaour web site at www.deconsolutions.com, email at [email protected] ormail at 4725 Oakland St., Denver, CO 80239.

Formulations for the Decontamination and Mitigation of CB ... · The SNL Decon Formulation has...

Documents

Transcript of Formulations for the Decontamination and Mitigation of CB ... · The SNL Decon Formulation has...