Note: Descriptions are shown in the official language in which they were submitted.
CA 02461872 2011-03-30
TITLE
ENHANCED FORMULATIONS FOR NEUTRALIZATION OF
CHEMICAL, BIOLOGICAL AND INDUSTRIAL TOXANTS
BACKGROUND OF THE INVENTION
Field of the Invention (Technical Field):
The present invention relates to formulations for neutralization of chemical,
biological and industrial toxants.
Background:
The present invention is directed to materials and methods for neutralization
of
toxic chemical, biological and industrial compounds or agents, especially
chemical
and biological weapons agents, and methods of making same. In particular, the
present invention is directed to materials containing solubilizing compounds,
reactive
compounds and bleaching activators that can be delivered as foams, sprays,
liquids,
fogs and aerosols to enhance the rate of reactions leading to neutralization
of chemical
compounds, and other additives which serve to kill or attenuate certain
biological
compounds or agents.
Terrorist threats, potentially involving weapons of mass destruction, are
increasing both in the United States and abroad. The use, and threat of use,
of
chemical and biological agents in the context of weapons of mass destruction
are of
paramount concern both to national defense as well as to state and local law
enforcement.
35
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Certain chemical warfare ("CW") agents known to pose a threat by terrorists
share chemical characteristics that present an opportunity for the development
of
countermeasures. The chemical agents sarin, soman, and tabun (G-agents) are
all
examples of phosphorus-containing compounds which, when altered chemically,
can
lose their toxicity. Mustard, which is an example of the H-agents, and VX,
which is
an example of the V-agents, can also be altered chemically and rendered
harmless. In
addition, certain of the known BW agents include botulinum toxin, anthrax and
other
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3
spore-forming bacteria, vegetative bacteria, including plague and various
viruses can also be
deactivated chemically.
A CW or biological warfare ("BW") attack can involve either local placement or
wide dispersal
of the agent or agents so as to affect a population of human individuals.
Because of the flexibility
with which CW and BW ("CBW") agents can be deployed, respondents might
encounter the agents
in a variety of physical states including bulk, aerosol and vapors.
An effective, rapid, and safe (non-toxic and non-corrosive) decontamination
technology is
required for the restoration of civilian facilities in the event of a domestic
terrorist attack. Ideally, this
technology should be applicable to a variety of scenarios such as the
decontamination of open, semi-
enclosed, and enclosed facilities as well as sensitive equipment. Examples of
types of facilities
where the decontamination formulation may be utilized include a stadium
(open), an underground
subway station (semi-enclosed), and an airport terminal or office building
(enclosed). A foaming
version is useful for extending the contact time of the formulation on
vertical surface.
Decontamination of chemical compounds have focused primarily on chemical
warfare 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 into substitution and oxidation reactions. Decontamination of
biological agents is primarily
focused on bacterial spores (e.g., anthrax), which are considered to be the
most difficult of all
microorganisms to kill. Additional background is discussed in U.S. Patents
6,566,574 and 6,723,890.
A need also exists for rapid, safe, and effective neutralization of toxic
industrial chemicals, such as
Malathion, Hydrogen Cyanide, Sodium Cyanide, Butyl Isocyanate, Carbon
Disulfide, and Phosgene
gas.
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U.S. Patent 6,566,574 is related generally to an aqueous-based decontamination
technology
("DF-100") that rapidly neutralizes chemical and biological warfare ("CBW')
agents. The formulation:
= is effective for neutralizing both chemical and biological agents;
= is environmentally benign (i.e., non-toxic and non-corrosive);
= works on a number of anticipated material surfaces; and
= can be incorporated into a wide variety of carriers (e.g., foams, liquid
sprays, fogs)
that satisfy a wide variety of operational objectives.
A major interest for the use of the technology was from the civilian first
responder (e.g., fire
departments, police departments, and HazMat units who would be the first to
arrive at the scene of
an attack utilizing CBW agents) followed by a secondary interest in use of the
formulation for facility
restoration. Technical issues exist with DF-100 that make use of the
formulation by the civilian first
responder less than optimal. These technical problems include: (1) The pH of
the DF-100 must be
adjusted to optimally decontaminate each specific chemical and biological
agent. In other words, a
different formulation may be required to neutralize each specific agent.
Although it is relatively
simple to adjust the pH of the formulation in the laboratory, this is more
difficult in the field and is
generally unsuitable for the primary users of the technology (i.e., the
civilian first responder). (2) The
reaction rate for one chemical agent, Mustard, is rather slow as compared to
the reaction rates for
other chemical agents.
These technical problems limit the effectiveness of DF-100 in actual use. A
modified
formulation, DF-100A, disclosed in U.S. Patent 6,723,890, addressed the
requirement to adjust the
pH for each specific agent (i.e., the first technical problem described
above). However, while DF-
100A does improve upon the performance of the formulation at a single pH, it
does not completely
solve this problem, and does not even address the second technical problem
(i.e., the relatively slow
reaction rate with Mustard). Additionally, some versions of DF-100/100A can
use short-chain
alcohols (e.g., isobutanol, isopropanol), which can cause flammability
problems if the formulation is
packaged in a concentrated form. Also, some versions of
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OF-100/100A can use diethylene glycol monobutyl ether (DEGMBE), which can
cause false alarms
on some chemical agent sensors and detectors (especially older sensors that
are used in some
military settings).
As a point of comparison, the following is an example of a preferred
formulation for DF-100:
5 DF-100
2.6% Variquat 80MCTm (cationic surfactant)
3.3% Adogen 477TM (cationic hydrotrope)
0.8% 1 -Dodecanol (fatty alcohol)
0.5% Isobutanol (short chain alcohol)
1.6% Isopropanol (short chain alcohol)
0.1% Jaguar 8000 TM (cationic polymer)
1.6% Diethylene Glycol Monobutyl Ether (solvent)
4% Sodium Bicarbonate (buffer and peroxide activator)
4% Hydrogen Peroxide (liquid oxidant)
75% Water
This formulation can be adjusted to a pH value of 8 for optimal
decontamination of Mustard and
Anthrax spores; and can be adjusted to a pH value of 10.5 for optimal
decontamination of VX.
Decontamination of chemical agents is generally effective anywhere between pH
8 and 10.
As a further point of comparison, the following is an example of a preferred
formulation for DF-100A:
DF-100A
5.3% Variquat 80MCTm (cationic surfactant)
2.8% Adogen 477 TM (cationic hydrotrope)
0.65% 1-Dodecanol (fatty alcohol)
0.6% Isobutanol (short chain alcohol)
0.1% Jaguar 8000TM (cationic polymer)
1.35% Diethylene Glycol Monobutyl Ether (solvent)
4% Potassium Bicarbonate (buffer and peroxide activator)
4% Hydrogen Peroxide (oxidant)
81% Water
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This formulation can be adjusted to a pH value of 8 for optimal
decontamination of Mustard and
Anthrax spores; and can be to a pH value of 10 for optimal decontamination of
VX. Decontamination
of chemical agents is generally effective anywhere between pH 8 and 10. Also,
it can be adjusted to
a pH of 9.2 for less than optimal decontamination of all agents.
In both of the examples shown above for DF-100 and DF-100A, the hydrogen
peroxide and
bicarbonate salt react to produce a highly reactive negatively charged
nucleophillic species,
hydroperoxycarbonate (HC04-), which is a strong oxidant. Other negatively-
charged nucleophiles
are formed by the use of hydrogen peroxide, including: hydroxyl ions (OH-) and
hydroperoxide ions
(00H-). The function of the other components in these formulations is
discussed extensively in U.S.
Patents 6,566,574 and 6,773,890.
The present invention presents enhanced decontamination formulations
(generically
designated "DF-200") that include bleaching activators, which leads to faster
reaction kinetics,
improved performance, and the elimination of the need for pH adjustment.
Although bleaching
activators are commonly used in (anionic) laundry detergents, the present
invention can employ them
with cationic surfactants, and where good solubility in water of the activator
is useful for achieving
quick reaction times. A desirable bleaching activator for use in the present
invention is preferably
water-soluble, non-toxic, non-flammable, and low-cost.
Glucose pentaacetate is an 0-acetyl peroxide activator that has been used as
an activation
agent in a sterilizing composition comprising a cationic surface-active agent
and inorganic peroxide
(See Japanese Laid-Open Patent Publication No. 62-155203, entitled
"Sterilizing Composition for
Cattle Shed" (1987)). Glucose pentaacetate is a solid at room temperature
(i.e., melting point 110
degrees C), and is insoluble in water. In an aqueous solution containing
peroxide, it dissolves very
slowly in water as it reacts with the peroxide. At a glucose pentaacetate
concentration of about 2%,
it takes several hours to dissolve. This makes its use less than desirable for
rapid deployment
configurations.
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SUMMARY OF THE INVENTION fDISCLOSURE OF THE INVENTION)
According to one aspect of the invention, there is provided a
combination of ingredients for use in neutralization of at least one toxant,
said combination
of ingredients comprising:
at least two solubilizing compounds, wherein at least one solubilizing
compound is a cationic surfactant and at least one solubilizing compound is a
cationic
hydrotrope;
at least one reactive compound, wherein said at least one reactive
compound is selected from the group consisting of hydrogen peroxide, urea
hydrogen
peroxide, hydroperoxycarbonate, peracetic acid, sodium perborate, sodium
peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and
at least one bleaching activator selected from the group consisting of
methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate,
and propylene
glycol diacetate, and combinations thereof;
wherein said at least two solubilizing compounds, said at least one
reactive compound, and said at least one bleaching activator, when mixed with
water and
exposed to the at least one toxant, neutralizes the at least one toxant.
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- 8 -
According to a further aspect of the invention, there is provided a
combination of ingredients for use in neutralization of at least one toxant,
said formulation
comprising:
at least one cationic surfactant;
at least one reactive compound, wherein said at least one reactive
compound is selected from the group consisting of hydrogen peroxide, urea
hydrogen
peroxide, hydroperoxycarbonate, peracetic acid, sodium perborate, sodium
3.0 peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate;
at least one bleaching activator selected from the group consisting of
methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate,
and propylene
glycol diacetate, and combinations thereof; and
at least one carbonate salt not one of the at least one reactive
compounds;
wherein said at least one surfactant, said at least one reactive
compound, said at least one bleaching activator, and said at least one
carbonate salt, when
mixed with water and exposed to the at least one toxant, neutralizes the at
least one toxant.
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-9-
According to still yet a further aspect of the invention, there is provided a
formulation for use in neutralization of at least one toxant, said formulation
comprising:
at least one cationic surfactant;
at least one reactive compound, wherein said at least one reactive
compound is selected from the group consisting of hydrogen peroxide, urea
hydrogen
peroxide, hydroperoxycarbonate, peracetic acid, sodium peroxypyrophosphate,
sodium
peroxysilicate, and sodium percarbonate;
at least one water-soluble bleaching activator selected from the group
consisting of methyl acetate, dimethyl glutarate, diethylene glycol monoethyl
ether acetate,
propylene glycol diacetate, acetylcholine chloride, monoacetin (glycerol
monoacetate),
4-cyanobenzoic acid, propylene glycol monomethyl ether acetate, methyl
acetate, dimethyl
glutarate, diethylene glycol monoethyl ether acetate, glycerol triacetate,
propylene glycol
diacetate, and combinations thereof; and
wherein said at least one surfactant, said at least one reactive
compound and said at least one water-soluble bleaching activator, when mixed
with water
and exposed to the at least one toxant, neutralizes the at least one toxant.
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According to still yet a further aspect of the invention, there is provided a
formulation for use in neutralization of at least one toxant, said formulation
comprising:
at least one solubilizing compound, selected from the group consisting
of a cationic hydrotrope and a fatty alcohol comprising from 8 to 20 carbon
atoms per
molecule;
at least one reactive compound, wherein said at least one reactive
compound is selected from the group consisting of hydrogen peroxide, urea
hydrogen
peroxide, hydroperoxycarbonate, peracetic acid, sodium perborate, sodium
peroxypyrophosphate, sodium peroxysilicate, and sodium percarbonate; and
at least one bleaching activator selected from the group consisting of
methyl acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate,
propylene
glycol diacetate and combinations thereof;
wherein said at least one solubilizing compound, said at least one
reactive compound, and said at least one bleaching activator, when mixed with
water and
exposed to the at least one toxant, neutralizes the at least one toxant.
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BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying drawings, which are incorporated into and form a part of the
specification,
illustrate one or more embodiments of the present invention and, together with
the description, serve
to explain the principles of the invention. The drawings are only for the
purpose of illustrating one or
more preferred embodiments of the invention and are not to be construed as
limiting the invention.
In the drawings:
Fig. 1 is a graph of the effect of DF-200 components on Bacillus globigii
(anthrax simulant)
spore kill;
Fig. 2 is a schematic diagram of a preferred mixing procedure for a first
rapid deployment
configuration of the present invention ("DF-200HF Rapid Deployment"); and
Fig. 3 is a schematic diagram of a preferred mixing procedure for a second
rapid deployment
configuration of the present invention ("DF-200HF Slurry Rapid Deployment").
DESCRIPTION OF THE PREFERRED EMBODIMENTS
(BEST MODES FOR CARRYING OUT THE INVENTION)
The present invention addresses the need for a general formulation that
neutralizes the
adverse effects of either or both chemical and biological toxants, where a
toxant is defined as any
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chemical or biological compound, constituent, species, or agent that through
its chemical or
biological action on life processes can, if left untreated, cause death,
temporary incapacitation, or
permanent harm to humans or animals. This includes all such chemicals or
biological agents,
regardless of their origin or of their method of production, and regardless of
whether they are
produced in facilities, in munitions or elsewhere. Neutralization is defined
as the mitigation, de-
toxification, decontamination, or otherwise destruction of toxants to the
extent that the toxants no
longer cause acute adverse effects to humans or animals. The formulation and
described variations
of the present invention can neutralize, and does not itself contain or
produce, infection, significant
adverse health effects, or even fatality in animals.
An important subset of chemical and biological compounds that the present
invention
addresses is that of chemical warfare (OW') and biological warfare ("BW")
agents. However, the
present invention also addresses toxants that can cause potential adverse
health effects to animals,
including humans, where such adverse health effects include infections, acute
and chronic health
effects, and fatalities. Such toxants can be found in an agricultural
facility, animal or dairy farm, or
food products processing or packaging facility. Additionally, the present
invention addresses the
need for such a formulation that is itself non-toxic and non-corrosive, and
that can be delivered by a
variety of means and in different phases. Certain embodiments are discussed in
U.S. Patents
6,566,574 and 6,723,890. The present invention presents additional embodiments
that have
substantial differences over both the prior art and the earlier embodiments,
as will be described
below.
The word "formulation" is defined herein as the activated product or solution
(e.g., aqueous
solution) that is applied to a surface or body for the purpose of
neutralization, with or without the
addition of a gas (e.g., air) to create a foam. Unless otherwise specifically
stated, the concentrations,
constituents, or components listed herein are relative to the weight
percentage of the overall
activated solution. The word "water" is defined herein to broadly include:
pure water, tap water,
deionized water, demineralized water, saltwater, or any other liquid
consisting primarily of H20.
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One example of a minimum set of constituents for a DF-200 formulation that can
achieve a
significant rate of spore kill comprises four components:
(1) a solubilizing agent selected from the group consisting of a cationic
surfactant (e.g.,
Variquat 80MCn"), a cationic hydrotrope (e.g., Adogen 4771N), and a fatty
alcohol
(e.g., 1-Dodecanal);
(2) a beaching activator selected from the group consisting of 0-acetyl, N-
acetyl, and nitrile
group peroxide activators (e.g., propylene glycol diacetate);
(3) a reactive compound (e.g., hydrogen peroxide, peracetic acid); and
(4) water.
The solubilizing agent serves to effectively render the toxant susceptible to
attack, while the reactive
compound serves to attack and neutralize the toxant, and the bleaching
activator enhances the
process.
Examples of suitable cationic surfactants include: quaternary ammonium salts
and
polymeric quaternary salts. Examples of suitable quaternary ammonium salts
include: cetyltrimethyl
ammonium bromide, benzalkonium chloride, benzethonium chloride,
cetylpyridinium chloride,
alkyldimethylbenzylammonium salt, and tetrabutyl ammonium bromide. A preferred
cationic
surfactant is WITCO VARIQUAT 80MCTM, which is a mixture of benzyl (C12-C16)
alkyldimethylammonium chlorides. The concentration of quaternary ammonium salt
used in DF-200
formulations is preferably no more than about 10%, because at higher
concentrations the quaternary
ammonium salt becomes significantly toxic to humans and the environment.
Examples of suitable cationic hydrotropes include: tetrapentyl ammonium
bromide, triacetyl
methyl ammonium bromide, and tetrabutyl ammonium bromide. A preferred cationic
hydrotrope is
WITCO ADOGEN 477 TM, which is a pentamethyltallow alkyltrimethylenediammonium
dichloride.
Examples of suitable fatty alcohols include alcohols having 8-20 carbon atoms
per molecule,
such as: 1-dodecanol, pure dodecanol, hexadecanol, and 1-tetradecanol.
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Examples of suitable bleaching activators are discussed subsequently.
Examples of suitable reactive compounds include: peroxide compounds; hydrogen
peroxide;
urea hydrogen peroxide; sodium perborate; sodium percarbonate; sodium
carbonate perhydrate;
sodium peroxypyrophosphate; sodium peroxysilicatehydrogen; peroxide adducts of
pyrophosphates;
citrates; sodium sulfate; urea; and sodium silicate; an activated peroxide
compound (e.g., hydrogen
peroxide + bicarbonate); peracetic acid; oximates (e.g., butane-2,3-dione,
monooximate ion, and
benzohydroxamate); alkoxides (e.g., methoxide and ethoxide); aryloxides (e.g.,
aryl substituted
benzenesulfonates); aldehydes (e.g., glutaraldehyde); peroxymonosulfate;
Fenton's reagent (a
mixture of iron and peroxide); and sodium hypochlorite. Use of these reactive
compounds in DF-200
formulations can produce a variety of negatively-charged nucleophiles, e.g.,
hydroxyl ions (OH-) and
hydroperoxide ions ((00H-) produced when using hydrogen peroxide; and/or
hydroperoxycarbonate
ions (HC04-) produced when hydrogen peroxide is combined with a carbonate
salt.
Hydroperoxycarbonate ions (HC04-) are a much stronger oxidant than hydroxyl
ions (OH-) or
hydroperoxide ions ((DOH), and are especially effective in reacting with
biological toxants. When
using hydrogen peroxide in DF-200 formulations, its concentration is
preferably less than about 10%
because higher concentrations are significantly corrosive, especially in the
range of 30-50%
hydrogen peroxide concentration.
To achieve very high rates of spore kill, a carbonate salt (e.g., sodium
bicarbonate or
potassium bicarbonate) is preferably added to the minimum set of constituents
for DF-200
formulations described above. When using a peroxide compound (e.g., hydrogen
peroxide) as the
reactive compound for DF-200, the added carbonate salt combines with, e.g.,
hydrogen peroxide to
form the highly reactive hydroperoxycarbonate species (HC04-). Addition of
carbonate salts can also
buffer the formulation to optimize the pH.
Hence, a minimum set of constituents for DF-200 formulations that can achieve
a very high
rate of spore kill can comprise five components:
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(1) a solubilizing agent selected from the group consisting of a cationic
surfactant (e.g.,
Variquat 80MCTm), a cationic hydrotrope (e.g., Adogen 477Tm), and a fatty
alcohol
(e.g., 1-Dodecanal);
(2) a beaching activator selected from the group consisting of 0-acetyl, N-
acetyl, and nitrile
5 group peroxide activators (e.g., propylene glycol diacetate);
(3) a reactive component (e.g., hydrogen peroxide, peracetic acid, etc.);
(4) a carbonate salt (e.g., sodium bicarbonate); and
(5) water.
10 Examples of suitable carbonate salts include: potassium bicarbonate,
sodium bicarbonate,
ammonium bicarbonate, ammonium hydrogen bicarbonate, lithium bicarbonate,
ammonium
carbonate, and potassium carbonate.
Figure 1 shows the results of decontamination tests on Bacillus globigii
spores (initial
15 concentration 107 spores/mil). The spores were exposed to four different
sub-combinations of the
various components of DF-200 formulations for 1 hour (the pH of the
formulation was 9.8). The
degree of spore kill was determined by culturing surviving organisms. As shown
in Figure 3,
significant spore kill was achieved by using two different combinations: (1)
an aqueous solution of 2%
Variquat (cationic surfactant), 2% propylene glycol diacetate (bleaching
activator), and 2% hydrogen
peroxide (oxidant) and (2) an aqueous solution of 2% Variquat (a cationic
surfactant), 5% potassium
bicarbonate (buffer and peroxide activator) and 2% hydrogen peroxide
(oxidant). However, very high
spore kill was achieved by using a third combination, comprising (3) an
aqueous solution of 2%
Variquat (a cationic surfactant), 2% propylene glycol diacetate (bleaching
activator), 5% potassium
bicarbonate (buffer and peroxide activator) and 2% hydrogen peroxide
(oxidant).
Next, a variety of alternative embodiments and configurations of DF-200
formulations will be
presented.
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DF-200HF (High Foam)
The present invention provides an enhanced decontamination formulation for
high foam
applications ("DF-200HF"). An example of a formulation for DF-200HF comprises:
DF-200HF (High Foam)
1-4 % (preferably 2%) Variquat 80MCTm (cationic surfactant)
0.5-3% (preferably 1%) Adogen 477TM (cationic hydrotrope)
0.2-0.8% (preferably 0.4%) 1-Dodecanol (fatty alcohol)
0.05-0.1% Jaguar 8000TM (cationic water-soluble polymer)
0.5% Di(propylene glycol) Methyl Ether (solvent)
0.1-10% (preferably 1-4%) Hydrogen Peroxide (oxidant)
0.1-10% (preferably 2-8%) Bicarbonate salt (buffer and peroxide activator)
1-4% Propylene Glycol Diacetate (bleaching activator)
67-97% Water
This formulation is effective at a pH value between 7.5 and 10.5. This
formulation can be adjusted to
a pH value between 9.6 and 9.8 for optimal decontamination of all target
agents. This "high-foam"
formulation includes a cationic water-soluble polymer (e.g., Jaguar 8000Tm),
which increases the bulk
viscosity of the solution and produces a more stable foam.
Examples of suitable non-anionic water-soluble polymers include: polyvinyl
alcohol, guar
gum, (cationic or non-ionic) polydiallyl dimethyl ammonium chloride,
polyacrylamide, polyethylene
glycol 8000 (PEG 8000), and JAGUAR 8000 TM (Guar Gum 2-hydroxypropyl ether). A
cationic
polymer is preferred over a non-ionic polymer; an anionic polymer does not
work well. The fatty
alcohol 1-dodecanol serves to increase the surface viscosity of the foam
lamellae to also increase
foam stability against drainage and bubble collapse.
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DF-200LF (Low Foam)
The present invention provides an enhanced decontamination formulation for low
foam
applications ("DF-200LF"). An example of a formulation for DF-200LF comprises:
DF-200LF (Low Foam)
4% Variquat 80MCTm (cationic surfactant)
0.4% Lauramide DEA [N,N-Bis(2-Hydroxyethyl)-Dodecanamide] (foam booster)
1-4% Propylene Glycol Diacetate (bleaching activator)
0.5% Di(propylene glycol) Methyl Ether (solvent)
0.05-0.1% Jaguar 8000TM Polymer (cationic water-soluble polymer)
0.1-10% (preferably 1-4%) Hydrogen Peroxide (oxidant)
0.1-10% (preferably 2-8%) Bicarbonate salt (buffer and peroxide activator)
71-94% Water
This formulation is generally effective at a pH value between 7.5 and 10.5.
This formulation can be
adjusted to a pH value between about 9.6 and 9.8 for optimal decontamination
of all target agents.
The term 'High Foam' refers to the ability of a formulation to form a highly
stable and
persistent foam, whereas a tow Foam' formulation forms a much less stable
foam. The following
tables show the improved performance of DF-200HF and DF-200LF as compared to
DF-100A. The
notation "ND" refers to a concentration below detectable limits, and "PGD"
refers to propylene glycol
diacetate (a preferred bleaching activator).
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Table 1: Summary of the reaction rates for Mustard simulant (2-Chloroethyl
phenyl sulfide).
Mustard Simulant (% Decontaminated)
Formulation 1 Minute 15 Minutes 60
Minutes
DF-100A(pH 8) 18 42 81
DF-100A (pH 9.2) 16 38 83
DF-200HF (2% PGD / 3% H202/ 4.5% Bicarb) 42 62 ND
DF-200HF (2% PGD / 3.5% H202/4% Bicarb) 94 98 ND
DF-200LF (2.5% PGD / 3% H20214.5% Bicarb) 55 91 ND
Table 2: Summary of the reaction rates for VX simulant (0-Ethyl S-Ethyl
Phenylphosphonothioate).
VX Simulant (% Decontaminated)
Formulation 1 Minute 15 Minutes 60
Minutes
DF-100A (pH 10) 45 99 ND
DF-100A (pH 9.2) 33 71 93
DF-200HF (2% PGD / 3% H202/ 4.5% Bicarb) 63 98 ND
DF-200HF (2% PGD / 3.5% H202/ 4% Bicarb) 66 99 ND
DF-200LF (2.5% PGD / 3% H202/ 4.5 Bicarb) 79 98 ND
Table 3: Summary of the reaction rates for G Agent simulant (Diphenyl
chlorophosphate).
G Agent Simulant (% Decontaminated)
Formulated 1 Minute 15 Minutes 60
Minutes
DF-100A (pH 8) 53 ND ND
DF-100A (pH 9.2) ND ND ND
DF-200 HF (2% PGD /3% H202/4.5 Bicarb) ND ND ND
DF-200HF (2% PGD /3.5% H2024% Bicarb) ND ND ND
DF-200LF (2.5% PGD / 3% H2024.5% Bicarb) ND ND ND
Table 4: Summary of the kill rates for Anthrax simulant (Bacillus globigii
spores)
Anthrax Simulant Anthrax Simulant
Formulation % Kill after 30 Minutes % Kill after
60 Minutes
DF-100A (pH 8) 99.99 99.99999
DF-100A (pH 9.2) 90 99.9
DF-200HF (2% PGD / 3% I-1202/ 4.5 Bicarb) 99.99999 99.99999
DF-200LF (2.5% PGD /3% H202/ 4.5 Bicarb) 99.99999 99.99999
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Differences between formulations of DF-200 and DF-100/100A include:
= DF-200 is active against all agents at a single pH. The formulation is
effective at pH
values between about 7.5 and 10.5; is more effective at pH values between
about 9.2 and 9.8; and is
most effective at pH values between about pH 9.6 and 9.8;
= DF-200 has better performance against Mustard;
= DF-200 has better performance against bacterial spores;
= DF-200 has lower concentrations of both the cationic surfactant and/or
the cationic
hydrotrope, which further lowers the (already low) toxicity and corrosivity
properties of the
formulation;
= DF-200 has a lower concentration of the foam stability component, 1-
Dodecanol;
= DF-200 doesn't use a short-chained alcohol (e.g., isobutanol,
isopropanol), which
causes flammability problems when the formulation is packaged in a
concentrated form;
= DF-200 doesn't use Diethylene Glycol MonoButyl Ether (DEGMBE), which can
cause
false alarms on some chemical agent sensors and detectors (especially older
sensors which are
used in some military settings); and
= DF-200 can contain a lower concentration of hydrogen peroxide, which also
reduces
the (already low) toxicity and corrosivity properties of the formulation.
Additional differences between DF-200 and DF-100A include:
= DF-200 performs optimally at a higher pH (about 9.6 to 9.8) as compared
to OF-
10A. However, note that this is the typical pH value for common household
products such as
laundry detergents, shampoos, and dishwashing detergents; and
= DF-200 has more individual components that should be stored separately
(e.g, the
hydrogen peroxide and the bleaching activator) from the bulk formulation until
use, as compared to
OF-100A (where only one component, hydrogen peroxide, should be stored
separately). This will be
discussed in greater detail below.
One reason for the better performance of DF-200 formulations (e.g., DF-200HF
and
DF-200LF) over OF-100 and OF-100A formulations is the addition of a bleaching
activator (e.g.,
CA 02461872 2010-05-27
propylene glycol diacetate). Bleaching activators can be compounds with 0- or
N- bounded acetyl
groups that react with the strongly nucleophilic hydroperoxy anion (00H-) to
yield peroxygenated
species, which are more efficient oxidizers than hydrogen peroxide alone.
5
0 0
II II
RC¨L + 00H- RC-00H + L-
10 Since the 1950's, a number of different bleaching activators have
been used in commercial
laundry detergents, as well as other commercial products. The most common
activators are
tetraacetyl ethylenediamine (TAED), which is primarily used in Europe and
Asia; and n-
nonanoyloxybenzenesulfonate (NOBS), which is primarily used in the United
States. NOBS is a
proprietary chemical of the Proctor and Gamble company. In a laundry
detergent, hydrogen peroxide
15 is provided in a solid form (usually as sodium perborate, which reacts
in water to form the
hydroperoxy anion). The addition of a bleaching activator greatly enhances the
ability of a laundry
detergent to remove stains from clothing.
It should be noted that TAED and NOBS bleaching activators are extremely
insoluble in water
20 (e.g., TAED is only 0.1% soluble at 25 C). To get around this problem in
a laundry detergent, the
solid TAED or NOBS particles are kept in suspension by the agitating action of
the washing machine,
where they slowly react with the hydrogen peroxide in the detergent. However,
agitation in the field
of DF-200 formulations presents practical problems; hence, a water-soluble
bleaching activator is
preferred.
Useful water-soluble bleaching activators include short-chained organic
compounds that contain an
ester bond, e.g., ethylene glycol diacetate, propylene glycol monomethyl ether
acetate, methyl
acetate, dimethyl glutarate, diethylene glycol monoethyl ether acetate,
glycerol diacetate (Diacetin),
glycerol monoacetate, glycerol triacetate, and propylene glycol diacetate. A
preferred water-soluble
bleaching activator is propylene glycol diacetate (PGD), which is shown below.
CA 02461872 2010-05-27
21
0 CH3 0
II I II
C H3 -C-0 C H2 CHO¨C¨CH 3
This molecule reacts with hydroperoxy anions (001-1), giving up the ester
bonds to form two
peroxygenated molecules.
Propylene glycol diacetate also acts as an organic solvent that is highly
effective in
solubilizing insoluble organic molecules (e.g., chemical warfare agents, as
well as foam
stabilizers/boosters (such as 1-dodecanol and Lauramide DEA)). Therefore, an
added function of
this compound is that it can be used to supplement the diethylene glycol
monobutyl ether (DEGMBE)
solvent that is used in DF-100 and DF-100A, or to supplement the Di(propylene
glycol) methyl ether
solvent used in some DF-200 formulations, thereby allowing the propylene
glycol diacetate to serve a
dual purpose (i.e., solvent and bleaching activator).
Bleaching activators are generally not stable in water for long periods of
time. This is
especially true when the aqueous solution is at a high pH (>10). Therefore,
for long shelf life, the
propylene glycol diacetate (or other bleaching activator) is preferably stored
separate from the
aqueous solution until use. This is not unlike other products that utilize
bleach activators (e.g.,
laundry detergents), where all the components of the formulation are kept dry
and separated until
use (in the case of laundry detergent, the bleaching activator is encapsulated
to prevent it from
reacting with the peroxide component until both components are mixed in
water).
Another example of a water-soluble bleaching activator is ethylene glycol
diacetate, which
works well in DF-200 formulations. However, when ethylene glycol diacetate
reacts with hydrogen
peroxide, it forms ethylene glycol (i.e., anti-freeze), which is a relatively
toxic byproduct. Propylene
glycol diacetate, on the other hand, does not form this relatively toxic
byproduct.
DF-200NF (Non-Foaming)
The present invention is also of a non-foaming embodiment ("DF-200NF") that
may be used
for specific applications, e.g., the kill of biological organisms, batch
processing (such as in chemical
CA 02461872 2010-05-27
22
agent demilitarization neutralization processes, i.e., in a bath of solution),
or spray applications. A
preferred example of this formulation comprises (amounts illustrative):
DF-200NF (Non-Foaming)
1-10% (preferably 2.5%) Benzalkonium Chloride (cationic surfactant)
1-8% Propylene Glycol Diacetate (bleaching activator)
1-16% Hydrogen Peroxide (oxidant)
2-8% Potassium Bicarbonate (buffer and peroxide activator)
65.5-93.5% Water
The formulation can be adjusted to a pH value between about 9.6 and 9.8 for
optimum performance,
and is effective for decontamination of all target agents.
DF-100E
The present invention is also of an enhanced version of DF-100A that utilizes
the propylene
glycol diacetate bleaching activator. A preferred embodiment of this enhanced
formulation, ("DF-
100E") comprises (amounts illustrative):
CA 02461872 2010-05-27
23
DF-100E
5.3% Variquat 80MC TM
2.8% Adogen 477 TM
0.65% 1-Dodecanol
0.5% Isobutanol
0.1% Jaguar 8000TM
1.35% Diethylene Glycol Monobutyl Ether
2-8% Bicarbonate Salt
1-4% Hydrogen Peroxide
1-4% Propylene Glycol Diacetate
73-85% Water
This formulation can be adjusted to a pH value between about 9.6 and 9.8 for
optimal performance
against all agents. The performance of DF-100E (2% PGD /3.00% H202 / 3.75%
Bicarbonate salt)
against chemical simulants is shown below in Table 5:
Table 5: Summary of the reaction rates for the DF-100E formulation in kinetic
testing.
% Decontaminated
Simulant 1 Minute 15 Minutes 60 Minutes
Mustard (HD) 83 92 ND
G Agents ND ND ND
VX 66 96 ND
Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999%
(7-Log) kill after a 30 minute exposure to DF-100E.
Other bleaching activators (such as water-insoluble NOBS or TAED) can be used
in place of
Propylene Glycol Diacetate in DF-100E. However, as noted above, this produces
a slurry mixture
instead of a true liquid solution.
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24
The following table summarizes some differences between DF-100, DF-100A, DF-
100E,
DF-200HF, DF-200LF, DF-200NF, and DF-200HF Slurry:
Table 6: Comparison of Various Decontamination Formulations
Reduction of
Requires pH Improved Flammable Forms
Highly Can Use Saltwater
Formulation Adjustment Kinetics Constituents
Stable Foam for Makeup Water
DF-100
DF-100A
DF-100E
DF-200HF
DF-200LF
DF-20ONF
DF-200HF-
Slurry
Kit Configurations
In the following sections, various examples of 2-part, 3-part, and 4-part
"kit" configurations
are shown for the different embodiments of DF-200 formulations. In general,
the 2-part and 3-part
kits have the bulk of the water already "pre-packaged" in one of the two (or
three) containers (usually
the foam component). This allows for rapid deployment of the decontamination
solution, the use of
small-scale units (e.g., backpacks), and doesn't require any extra water to be
provided in the field.
Conversely, the 4-part kits generally require that the make-up water is added
in the field at,
or near, the site of contamination. This allows the "package" containing the
other three parts to be
much lighter, which makes it easier to ship and store. However, a source of
make-up is required in
the field (which can be saltwater).
CA 02461872 2010-05-27
In general, the DF-200 formulations can be configured either way, with the
bulk of the water
"pre-packaged", or without, depending on the application.
5 DF-200lIF (Kit Configuration)
The DF-2001-IF formulation can be configured as a 4-part kit, and then
prepared for field use
as follows (amounts illustrative):
DF-200 HF (4-part kit)
10 Part A (Foam Concentrate):
20 g Variquat 80MC TM
10 g Adogen 477TM
4 g b-Dodecanol
1 g Jaguar 8000 TM Polymer
15 5 g Di(propylene glycol) methyl ether
7.5 g Potassium Bicarbonate
141 g Water
Part B (Solid Component):
50 g Sodium Percarbonate
20 50 g Urea Hydrogen Peroxide
Part C (Bleaching Activator):
20 g Propylene Glycol Diacetate
Part D (Make-up Water):
800 g Water
In this example of a 4-part configuration, the bulk of the water is not
included in the
"package" (i.e., Parts A, B, and C), which minimizes the weight of the package
for shipping and
storage. Here, the make-up water (Part D) would be supplied in the field at,
or near, the site of
contamination. The pH of the formulation can be adjusted to be between about
9.6 and 9.8 for
CA 02461872 2010-05-27
26
optimal performance. The formulation as described above will produce 1 liter
of "high" foam solution.
In this example, sodium percarbonate supplies a portion of the hydrogen
peroxide, a portion of the
bicarbonate, and a base for buffering the solution. The remainder of the
hydrogen peroxide is
supplied by the urea hydrogen peroxide. The total hydrogen peroxide
concentration is approximately
3% in this example. The viscosity of the formulation can be adjusted to be
between about 4-9 mm2/s.
A variety of different methods can be used in the field to mix the DF-200HF
formulation
configured as a 4-part kit, for example:
Method 1: Supply the make-up water (Part D). Then, mix Part B into Part D.
Then, add Parts C and
A to Part B+D. Use, preferably, within 8 hours.
Method 2: Mix Part C into Part A. Supply the make-up water (Part D). Then, mix
Part B into Part D.
Keep separate until use. When use is required, mix Part A+C into Part B+D.
Use,
preferably, within 8 hours of first mixing Parts A+C into Parts B+D.
In general, activated DF-200 formulations are used preferably within 8 hours
after mixing,
however, they still can be effective for up to 24 hours and longer. DF-200HF
(High Foam) can be
applied to a surface for a long period of time, and then rinsed off. However,
DF-200LF (Low Foam)
can be used in a different manner than the DF-100/100A and DF-200HF
formulations. Instead of
leaving DF-200LF on a surface for long periods of time, it can be applied to a
surface, left for a
relatively short period of time (e.g., 15-60 minutes), and then rinsed off
with a high pressure
freshwater or salt water spray. This will minimize corrosion of the material
to which it is applied,
which will make it especially useful for decontaminating aircraft and other
equipment where corrosion
is a concern. It will also minimize the time required for decontamination,
which is especially
advantageous for military use (on the battlefield or at fixed sites).
CA 02461872 2010-05-27
- 27
Saltwater can also be effectively used as the make-up water (Part D) for DF-
200 formulations. The
table below shows the results of kinetic tests using DF-200HF (2% PGD / 3.50%
H202/ 4.0%
Bicarbonate salt) with saltwater (-35,000 ppm total dissolved solids):
Table 7: Summary of the reaction rates for DF-200HF formulation (2% PGD / 3.5%
H202/ 4.0%
Bicarbonate salt) with saltwater used as the make-up water (Part D).
% Decontaminated
Simulant 1 Minute 15 Minutes 60 Minutes
Mustard 24 42 89
G Agents ND ND ND
VX 62 96 >99
Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999% (7-Log)
kill after a one hour exposure to DF-200HF with saltwater used as the make-up
water.
Surface testing was conducted with DF-200HF against the Mustard and VX
simulant. For this
test, 8 mg of simulant was applied to a 2" diameter test coupon made of CARC
(Chemical Agent
Resistant Coating). CARC is a material commonly used to paint military
vehicles to protect them
against chemical agent attack. After waiting one hour, the test coupon was
placed in a horizontal
position and covered with 1.0 g of DF-200HF (2% PGD / 3.5% H202/ 4.0%
Bicarbonate salt). After
60 minutes, the test coupon was immersed in 25 ml of acetonitrile for 15
minutes to extract unreacted
simulant from the surface. The extraction solvent (acetonitrile) was then
analyzed for the unreacted
simulant. Results (shown in Table 8) demonstrate more effective
decontamination of the test coupon
as compared to DF-100A.
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28
Table 8: Results of Surface Testing of DF-200HF on CARC.
mg VX Simulant Mg Mustard Simulant
Decon Formulation (Unreacted simulant on (Unreacted
simulant on
surface after 60 minutes) surface after 60 minutes)
Control 8.0 0.3 8.0 0.3
DF-100A (pH 9.2) 2.9 4.5
DF-200HF (2% PGD / 3.5% H202/4.0% Bicarb) 1.4 2.5
DF-200HF Slurry (Kit Configuration)
Insoluble bleach activators (such as TAED, NOBS, and N-acetyl glucosamine) can
be
utilized in place of the (water-soluble) propylene glycol diacetate for DF-200
formulations. However,
in this case, the formulation results in a slurry when mixed with water,
instead of a true aqueous
solution.
The present invention also provides a method to utilize a water-insoluble
solid bleach
activator (e.g., TAED) to produce a reactive slurry (wherein a slurry is
defined as a watery mixture
that includes insoluble, undissolved matter). This embodiment, designated "DF-
200HF Slurry", is a
modification of the DF-200HF formulation. An example of a 4-part kit
configuration is shown below
(amounts illustrative):
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29
DF-200HF Slurry (4-part kit)
Part A (Foam Concentrate):
20 g Variquat 80MCTm
g Adogen 477TM
5 4 g 1-Dodecanol
1 g Jaguar 8000Th' Polymer
5 g Di(propylene glycol) methyl ether
7.5 g Potassium Bicarbonate
161 g Water
10 Part B (Solid Component):
50 g Sodium Percarbonate
50 g Urea Hydrogen Peroxide
Part C (Bleaching Activator):
10 g TAED (preferably encapsulated TAED, such as Warwick B637Th')
Part D (Make-up Water):
800 g Water (can be freshwater or saltwater supplied at the site where use is
to
occur)
The formulation as described above will produce 1 liter of foam solution. The
pH of the final
formulation can be adjusted to be between about 9.6 and 9.8 for optimal
performance. The following
mixing procedure can be used: Mix Part B into Part D. Then, add Parts C and A
to Parts B+D. Use,
preferably, within 8 hours.
The performance against each chemical agent simulant for DF-200HF Slurry (1%
TAED / 3%
H202 /4% Bicarbonate salt) is shown below in Table 9:
CA 02461872 2010-05-27
Table 9: Summary of the reaction rates for the DF-200HF Slurry formulation in
kinetic testing.
Note that improved performance can be achieved by using higher concentrations
of TAED (e.g., 2%
TAED, instead of 1% TAED).
5
% Decontaminated
Simulant 1 Minute 15 Minutes 60 Minutes
Mustard (HD) 67 96 ND
G Agents ND ND ND
VX 33 95 ND
The above examples of different embodiments of DF-200 would typically be used
in large-
scale operations where dedicated deployment equipment and a source of make-up
water is readily
available (e.g., for use by the military to decontaminate 'fixed sites' such
as airbases and seaports),
10 or used to minimize the volume of 'pre-packaged' water in order to
minimize the weight of the
formulation that needs to be shipped and stored.
DF-200 Rapid Deployment Configurations
The present invention is also of configurations emphasizing the rapid
deployment of DF-200
15 formulations, and/or its deployment using small-scale deployment
equipment (such as hand-held
units, backpack units, or units mounted on small dollies). For these
applications, all of the water is
'pre-packaged' into the formulation, so that no extra water is required in the
field. A first example of a
3-part kit configuration for a Rapid Deployment version of DF-200HF, "DF-200HF
Rapid Deployment
#1", comprises (amounts illustrative):
CA 02461872 2010-05-27
31
DF-200HF Rapid Deployment #1 (3-part kit)
Part A (Liquid Foam Component):
20 g Variquat 80MCTm
g Adogen 477TM
5 4 g 1-Dodecanol
5 g Poly (Ethylene Oxide)
8 g Diethylene Glycol Monobutyl Ether
5 g lsobutanol
45 g Potassium Bicarbonate
10 app rox. 19 g Potassium Hydroxide (the pH of Part A should be
approximately 10.2)
933 g Water
Part B (Solid Oxidant Component):
97 g Urea Hydrogen Peroxide
Part C (Liquid Bleaching Activator):
20 g Propylene Glycol Diacetate
This configuration will produce 1 liter of foam solution. The pH of the final
formulation can be
adjusted to be between about 9.6 and 9.8 for optimal performance. The
following mixing procedure
can be used: Mix Part B into Part A. After dissolution of the urea hydrogen
peroxide, add Part C to
Part MB. Use, preferably, within 8 hours. The performance of DF-200HF Rapid
Deployment against
chemical agent simulants is shown below in Table 10:
Table 10: Reaction rates from kinetic testing of DF-200HF Rapid Deployment #1
configuration.
% Decontaminated
Simulant 1 Minute 15 Minutes 60
Minutes
Mustard (HD) 48 82 ND
G Agents ND ND ND
VX 71 97 >99
CA 02461872 2010-05-27
32
Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999%
(7-Log) kill after a 30 minute exposure to DF-200HF Rapid Deployment.
A schematic example of a preferred mixing procedure for this first example of
a rapid deployment
configuration of DF-2001-IF is shown in Figure 2. Urea hydrogen peroxide
dissolves rapidly in water.
Therefore, the formulation can be prepared and deployed in a very short time
at the scene of an
incident involving chemical or biological warfare agents, making it ideal for
use by civilian first
responders (firefighters, HazMat units, police officers, and others who would
be the first to arrive at
the location of a CBW attack), and/or the military.
However, the particular bleaching activator (propylene glycol diacetate) used
in this
formulation is not stable in an aqueous solution where the pH is greater than
approximately 9.9.
Therefore, it is important to mix the right components in the correct order.
For example, if Part C is
mixed into Part A before the addition of Part B, there may be some loss of
activity in DF-200HF since
the propylene glycol diacetate is exposed to a solution having a pH value
>9.9. This is not true,
however, if Part B is added to Part A before the addition of Part C, since the
addition of Part B to Part
A brings the pH of the Part A+B mixture to a value below about 9.9.
The solvent, diethylene glycol monobutyl ether, used in Part A (the foam
solution) of the first
example shown above for DF-200HF Rapid Deployment #1 is different than the
solvent that was
used in the previously described DF-200HF formulation (Di(propylene glycol)
methyl ether), because
Di(propylene glycol) methyl ether is not stable in the high pH environment
required for the foam
component (Part A) in the rapid deployment configuration. Also, note that a
short-chained alcohol
(i.e., isobutanol) has been added to the foam component (Part A) in the rapid
deployment
configuration #1 of DF-200lIF. While this low molecular weight alcohol can
cause flammability
problems in highly concentrated configurations of DF-200HF, it is not a
problem in the less
concentrated configurations described herein. The use of isobutanol also helps
solubilize the 1-
dodecanol in Part A, and improves the kinetics (chemical reactivity) of the
formulation. In addition,
CA 02461872 2010-05-27
_ 33
the formulation preferably uses a different polymer, poly (ethylene oxide),
than the polymer used in
the other earlier described DF-200 formulations (i.e., Jaguar 80001TM). This
alternative polymer is
used because Jaguar 8000 TM is also not stable in the high pH environment of
the liquid foam portion
(Part A) of the rapid deployment formulation. Accordingly, a preferred
formulation for DF-2001-IF
Rapid Deployment #1 comprises:
DF-200HF Rapid Deplovment #1
1-4% (preferably 2%) Variquat 80MC TM (cationic surfactant)
0.5-3% (preferably 1%) Adogen 477 TM (cationic hydrotrope)
0.2-0.8% (preferably 0.4%) 1-Dodecanol (fatty alcohol)
0.5-8% (preferably 0.5%) Poly (Ethylene Glycol) (polymer)
0.6-1.2% (preferably 0.8%) Diethylene Glycol Monobutyl Ether (solvent)
0-1% (preferably 0.5%) Isobutanol (short-chained alcohol)
0.1-10% (preferably 2-8%) Bicarbonate salt (buffer and peroxide activator)
0.1-10% (preferably 1-4%) Hydrogen Peroxide (oxidant)
0.1-10% (preferably 1-4%) Propylene Glycol Diacetate (bleaching activator)
52-97% Water
The formulation can be adjusted to a pH value between about 9.6 and 9.8 for
optimal performance,
and is effective for decontamination of all target agents.
A second example of a 3-part kit configuration for a Rapid Deployment version
of DF-200HF,
"DF-200HF Rapid Deployment #2", comprises (amounts illustrative):
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34
DF-200HF Rapid Deployment #2 (3-part kit)
Part A (Liquid Foam Component):
20 g Variguat 80MC TM
g Adogen 477TM
5 4 g 1-Dodecanol
g Polyethylene Glycol 8000 polymer
8 g Diethylene Glycol Monobutyl Ether
5 g lsobutanol
50 g Potassium Bicarbonate
10 approx. 25 g Potassium Hydroxide (the pH of Part A should be
approximately /0.2)
933 g Water
Part B (Solid Oxidant Component):
97 g Urea Hydrogen Peroxide
Part C (Liquid Bleaching Activator):
15 20 g Propylene Glycol Diacetate
In this second example, Polyethylene Glycol 8000 polymer replaced the poly
(Ethylene Oxide)
polymer used in DF-200HF Rapid Deployment #1.
20 A third example of a 3-part kit configuration for a Rapid Deployment
version of DF-200HF,
"DF-200HF Rapid Deployment #3", comprises (amounts illustrative):
CA 02461872 2010-05-27
DF-200HF Rapid Deployment #3 (3-Dart kit)
Part A (Liquid Foam Component):
20 g Variquat 80MC TM
10 g Adogen 477TM
5 4 g 1-Dodecanol
20 g Polyethylene Glycol 8000 polymer
10 g Hexylene Glycol
g Potassium Carbonate
5 g Potassium Bicarbonate
10 700 g Water
Part B (Solid Oxidant Component):
83 g Urea Hydrogen Peroxide
Part C (Liquid Bleaching Activator):
20 g Glycol Diacetate (i.e., Diacetin)
In this third example, Polyethylene Glycol 8000 polymer replaced the poly
(Ethylene Oxide) polymer
used in DF-200HF Rapid Deployment #1 as a water-soluble polymer. Also,
Hexylene Glycol
replaced Diethylene Glycol Monobutyl Ether and Isobutanol used as a solvents.
Finally, Glycol
Diacetate (i.e., Diacetin) replaced Propylene Glycol Diacetate used as the
bleaching activator.
These changes in the third example were made to reduce or eliminate the use of
short-chained
alcohols and/or high vapor-pressure solvents to prevent possible problems with
very long-term
(months to years) shelf life of the liquid foam component (Part A), especially
at high ambient storage
temperatures, due to evaporation of the most-volatile components. Note that
the combination of 45
grams of potassium carbonate and the 5 grams of potassium bicarbonate were
chosen to supply
both the right amount of carbonate/bicarbonate, and to adjust the pH
appropriately. Alternatively, 50
grams of potassium bicarbonate could have been used (with no potassium
carbonate), and then the
right amount of potassium hydroxide (base) could have been added to increase
the pH to the desired
value, as is well-known in the art.
CA 02461872 2010-05-27
36
DF-2001-IF Slurry Rapid Deployment
The present invention is also of a 2-part kit configuration of a rapid
deployment embodiment
of the DF-200lIF Slurry embodiment ("DF-200HF Slurry Rapid Deployment), in
which TAED (or
other solid peroxide activator) is utilized as the bleaching activator. This
example of a rapid
deployment configuration also requires no additional water to be added in the
field (amounts
illustrative):
DF-200HF-Slurry Rapid Deployment (2-part kit)
Part A (Liquid Foam Component):
g Variquat 80MC TM
10 g Adogen 477TM
4 g 1-Dodecanol
15 5 g Poly (Ethylene Glycol)
8 g Diethylene Glycol Monobutyl Ether
5 g Isobutanol
50 g Potassium Bicarbonate
28 g Potassium Hydroxide (the pH of Part A should be approximately 10.4)
20 953 g Water
Part B (Solid Oxidant and Bleaching Activator):
97 g Urea Hydrogen Peroxide
g TAED (preferably in encapsulated form, such as Warwick International B637)
25 This formulation will produce 1 liter of foam solution. The pH of the
final formulation can be adjusted
to be between 9.6 and 9.8 for optimal performance. The following procedure can
be used to mix the
formulation: Mix Part B into Part A. Then, wait for at least one minute before
use to allow time for
the TAED to react with the hydrogen peroxide. Use, preferably, within 8 hours.
It is useful to note
that TAED will not immediately dissolve in water, but will remain as solid
particles for at least 15-20
CA 02461872 2010-05-27
37
minutes. Therefore, a filter or screen may be required so that the undissolved
TAED particles will not
damage or clog any pumps or other components of the deployment device.
However, the
formulation is ready for use approximately 1 minute after addition of the TAED
particles in Part B to
Part A.
It is useful to employ an encapsulated form of TAED in this configuration for
two reasons.
First, the protective coating (which slowly dissolves in water) will protect
the TAED so that it will not
react with the urea hydrogen peroxide during storage. Second, the coating will
protect the TAED
from the high pH conditions in Part A until the urea hydrogen peroxide
dissolves and lowers the pH of
the formulation to a value below approximately 9.9. TAED should be used in a
similar manner as
propylene glycol diacetate with respect to protecting the activator against
exposure to high pH
solutions. TAED will lose much of its effectiveness as a bleaching activator
if it is exposed to
solutions with a pH greater than 9.9. Therefore, the use of an encapsulated
form of TAED will
minimize its exposure to the high pH conditions immediately after Part B is
mixed into Part A. The
performance of DF-200HF Slurry Rapid Deployment against chemical agent
simulants is given in
Table 11 below.
Table 11: Reaction rates in kinetic testing for the DF-200HF Slurry Rapid
Deployment
formulation.
% Decontaminated
Simulant 1 Minute 15 Minutes 60 Minutes
Mustard (HD) 76 97 ND
G Agents ND ND ND
VX 57 97 ND
Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999%
(7-Log) kill after a 30 minute exposure to DF-200HF Slurry Rapid Deployment.
A schematic illustrating an example of a process for field mixing DF-200HF
Slurry Rapid
Deployment is shown in Figure 3.
CA 02461872 2010-05-27
38
_
The above are only a few examples of rapid deployment configurations for DF-
200
formulations. As understood by one of ordinary skill in the art, other rapid
deployment configurations
are possible by utilizing the fundamental considerations presented in this
application.
The present invention is also of a method for preparing the foam component
(Part A) of the
rapid deployment configurations. The following is an example of such a method:
1. Place the appropriate mass of water in a mixing vessel.
2. While stirring the water in the mixing vessel, add the
bicarbonate salt. Stir until
completely dissolved.
3. Slowly add the Poly (Ethylene Glycol) polymer to the mixing vessel while
rapidly
stirring. Be careful to avoid lumps. Stir for approximately 30 minutes, at a
minimum.
4. While stirring the foam solution in the mixing vessel, add the Variquat
80MCTm. Stir
until completely mixed.
5. While stirring the foam solution in the mixing vessel, add the Adogen
477. Stir until
completely mixed.
6. Mix the diethylene glycol monobutyl ether, isobutanol, and 1-dodecanol
in a separate
vessel. Slowly add this mixture to the foam solution while stirring.
7. While stirring the foam solution in the mixing vessel, slowly add solid
KOH until the
pH reaches the appropriate value.
Alternative DF-200 Formulations
The invention is also of the following alternative DF-200 formulations:
1. An alternative formulation that includes propylene glycol to
lower the freezing point of
the solution;
2. An alternative formulation that utilizes sodium percarbonate as a solid
source of
hydrogen peroxide;
3. An alternative formulation that includes a corrosion inhibitor,
CA 02461872 2010-05-27
39
4. An alternative formulation that includes glycerol as a viscosity builder
for operations
such as skin decontamination;
5. An alternative formulation that utilizes 0-acetyl bleaching activators,
including one
which is available in solid form; and
6. An alternative formulation that utilizes a bleaching activator
containing a nitrile group.
DF-200 with Proplvene Glycol
The following is a first example of a 2-part kit configuration for DF-200HF
that includes
propylene glycol as a freezing point depressant, and where all of the water is
'pre-packaged' in Part
A, comprising (amounts illustrative):
DF-200HF Rapid Deployment with Propylene Glycol. first example (2-part kit)
Part A (Liquid Foam Component):
g Variquat 80MCTm
15 10 g Adogen 477TM
20 g Poly (Ethylene Glycol) (MW 8000)
8 g Diethylene Glycol Monobutyl Ether
5 g lsobutanol
4 g 1-Dodecanol
20 20 g Propylene Glycol Diacetate
150 g Propylene Glycol (freeze-point depressant)
approx. 6 g of 10% HCI Solution (sufficient to give a final pH of 2.5 in Part
A)
777 g Water
Part B (Solid Additive):
97 g Urea Hydrogen Peroxide
12 g Potassium Bicarbonate
38 g Potassium Carbonate (buffer, to adjust final pH)
CA 02461872 2010-05-27
This formulation will produce 1 liter of foam solution. The pH of the final
formulation can be adjusted
to be between about 9.6 and 9.8 for optimal performance. A person of ordinary
skill in the art will
understand that the ratio of potassium carbonate to potassium bicarbonate used
in Part B can be
adjusted to achieve the desired final pH of the formulation (preferably about
9.6 to about 9.8). Hence,
5 in this example, the potassium carbonate serves as both a base and a
source of
carbonate/bicarbonate. To prepare this formulation, mix Part B into Part A.
Use, preferably, within 8
hours. The performance of this first example of DF-200HF with propylene glycol
against chemical
agent simulants is shown in Table 12.
10 Table 12: Reaction rates from kinetic testing for DF-200HF with
propylene glycol (first
example).
% Decontaminated
Simulant 1 Minute 15 Minutes 60 Minutes
Mustard (HD) 16 80 ND
G Agents ND ND ND
VX 66 90 >99
Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999%
15 (7-Log) kill after a 30 minute exposure to DF-200HF with propylene
glycol (first example).
When all of the water is "pre-packaged" in Part A, the mixing of the
formulation for use can be
accomplished in a very short time since it only consists of two parts.
Therefore, it could be deployed
very rapidly at the scene of an incident involving chemical and biological
warfare agents. This
20 configuration is ideal for use the civilian first responder
(firefighter, HazMat units, police officers, and
others who would be the first to arrive at the location of a CBW attack).
However, it is heavier to
carry than other configurations that add water in the field.
This configuration also incorporates the bleaching activator, propylene glycol
diacetate, into
25 the foam component Part A (rather than storing it as a separate, third
component). This is possible
because the pH of the foam component is less than 3. Propylene glycol
diacetate will hydrolyze in
CA 02461872 2010-05-27
- 41
solutions of pH greater than 3, but is hydrolytically stable in solutions of
pH less than 3. This
configuration also uses the polyethylene glycol polymer (PEG 8000) for
viscosity enhancement. This
polymer is used in many cosmetics and is extremely soluble and stable in
water. In addition, it is
easier to mix into solution than Jaguar 8000TM or a high molecular weight
poly(ethylene oxide), since
it does not have the tendency to clump.
This configuration includes propylene glycol as a freeze-point depressant.
Propylene glycol is
considered to be an environmentally friendly antifreeze. In this case, the
concentration is
approximately 15% by weight, which lowers the freezing point of Part A to
approximately ¨20 C. This
configuration has also been tested with good results with propylene glycol
concentrations as high as
40% by weight.
An alternative to the first example of DF-200HF with Proplyene Glycol shown
above is to use
sodium percarbonate as the source of the bicarbonate and as a portion of the
peroxide in Part B,
instead of using urea hydrogen peroxide. This substitution is useful because
sodium percarbonate is
much less expensive than urea hydrogen peroxide. This second example of DF-
200HF with
Proplyene Glycol is shown below (amounts illustrative):
CA 02461872 2010-05-27
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DF-200HF Raoid Deployment with Proolyene Glycol. second example (2-Dart kit)
Part A (Liouid Foam Component):
20 g Variquat 80MCT"
g Adogen 477TM
g Poly (Ethylene Glycol) (MW 8000)
8 g Diethylene Glycol Monobutyl Ether
5 g lsobutanol
10 4 g 1-Dodecanol
20 g Propylene Glycol Diacetate
150 g Propylene Glycol (freeze-point depressant)
approx. 6 g of 10% HCI Solution (sufficient to give a final pH of 2.5 in Part
A)
777 g Water
15 Part B (Solid Additive):
90 g Sodium Percarbonate
15 g Citric Acid (buffer, to adjust final pH)
This formulation will produce 1 liter of foam solution. The pH of the final
formulation can be
20 adjusted
to be between about 9.6 and 9.8 for optimal performance. The following mixing
procedure
can be used: Mix Part B into Part A. Use, preferably, within 8 hours.
Alternatively, sodium bisulfate
(a common pool conditioning chemical), or other acid, can be used in place of
citric acid to adjust the
pH. The performance of this second example of DF-200HF with Proplyene Glycol
(utilizing sodium
percarbonate) against chemical agent simulants is shown in Table 13.
Table 13: Reaction rates from kinetic testing for the second example of DF-
200HF with
proplyene glycol (utilizing sodium percarbonate).
% Decontaminated
Simulant 1 Minute 15 Minutes 60
Minutes
Mustard (HD) 80 ND ND
VX 76 96 >99
CA 02461872 2010-05-27
43
In general, sodium percarbonate dissolves much more slowly than urea hydrogen
peroxide
after it has been added to Part A. However, to increase the dissolution
velocity, sodium
percarbonate can be milled to approximately a 100 mesh size for use in this
configuration. The time
to dissolve the sodium percarbonate was decreased from approximately 30
minutes to about 2
minutes when milled sodium percarbonate was used.
DF-200 with Corrosion Inhibitor
Corrosion inhibitors can be added to DF-200 formulations to reduce their
corrosivity. A
preferred corrosion inhibitor for use in DF-200 formulations is N,N-dimethyl
ethanolamine. However,
other corrosion inhibitors, such as triethanolamine, ethanolamine salts of C9,
C10, and C12 diacid
mixtures, dicyclohexyl amine nitrite, and N,N-dibenzylamine, can be used. The
Corrosion inhibitors
added to DF-200 formulations can serve multiple purposes:
1. a corrosion inhibitor,
2. a pH buffer,
3. a solvent to keep 1-dodecanol in solution, and
4. a co-solvent to solubilize insoluble chemical agents, such as sarin or
mustard.
An example of a 3-part kit configuration of DF-200HF with a corrosion
inhibitor comprises (amounts
illustrative):
CA 02461872 2010-05-27
44 -
DF-200HF Rapid Deployment with Corrosion Inhibitor (3-part kit)
Part A (Liquid Foam Component):
20 g Variquat 80MCTm
g Adogen 477TM
5 4 g 1-Dodecanol
5 g Poly (Ethylene Glycol)
10 g N,N-dimethyl ethanolamine (corrosion inhibitor)
50 g Potassium Bicarbonate
approx. 18 g Potassium Hydroxide (sufficient to give a final pH of 10.2 in
Part A)
10 936 g Water
Part B (Solid Oxidant Component):
97 g Urea Hydrogen Peroxide
Part C (Liquid Bleaching Activator):
g Propylene Glycol Diacetate
This formulation will produce 1 liter of foam solution. The pH of the final
formulation can be adjusted
to be between about 9.6 and 9.8 for optimal performance. The following mixing
procedure can be
used: Mix Part B into Part A. Then, after dissolution of the urea hydrogen
peroxide, add Part C to
Part A+B. Use, preferably, within 8 hours. The performance of DF-200HF with
corrosion inhibitor is
shown below against chemical agent simulants is given in Table 14.
Table 14: Reaction rates in kinetic testing for DF-200HF with a corrosion
inhibitor.
% Decontaminated
Simulant 1 Minute 15 Minutes 60
Minutes
Mustard (HD) 7 41 79
VX 58 94 99
Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999%
(7-Log) kill after a 60 minute exposure to DF-200HF with a corrosion
inhibitor. The addition of the
CA 02461872 2010-05-27
corrosion inhibitor has a detrimental effect on the performance of DF-200
against chemical agents,
but has no measured effect on the performance of DF-200HF against biological
agents. Similar
results were obtained when an alternative corrosion inhibitor, 1%
triethanolamine, was used.
5 DF-200 with Glycerol
In another embodiment of a DF-200 formulation, glycerol may be employed as a
viscosity
builder in place of Jaguar 80001, poly (ethylene oxide), or polyethylene
glycol. Glycerol is a
common ingredient in cosmetics, where it is used a viscosity builder, as well
as a solvent, humectant
and emollient. Thus, the use of glycerol in DF-200 formulations can serve
multiple purposes:
10 1. Viscosity builder,
2. a humectant (i.e., a substance which moisturizes the skin),
3. a solvent to keep 1-dodecanol in solution, and
4. a co-solvent to solubilize insoluble chemical agents, such as sarin or
mustard.
15 An example of a 3-part kit configuration of DF-200HF with glycerol
comprises (amounts
illustrative):
DF-200HF Rapid Deployment with Glycerol (3-part kit)
Part A (Liquid Foam Component):
20 20 g Variquat 80MCT"
10 g Adogen 477T"
4 g 1-Dodecanol
40 g Glycerol (viscosity builder)
40 g Potassium Bicarbonate
25 approx. 17 g Potassium Hydroxide (sufficient to give a final pH of
10.2 in Part A)
906 g Water
CA 02461872 2010-05-27
46
Part B (Solid Oxidant Component):
97 g Urea Hydrogen Peroxide
Part C (Liquid Bleaching Activator):
20 g Propylene Glycol Diacetate
This formulation will produce 1 liter of foam solution. The pH of the final
formulation can be adjusted
to be between about 9.6 and 9.8 for optimal performance. The following mixing
procedure can be
used: Mix Part B into Part A. Then after dissolution of the urea hydrogen
peroxide, add Part C to
Part +/B. Use, preferably, within 8 hours. The performance of DF-200HF with
glycerol against
chemical agent simulants is given in Table 15.
Table 15: Reaction rates in kinetic testing for DF-200HF with glycerol.
% Decontaminated
Simulant 1 Minute 15 Minutes 60 Minutes
Mustard (HD) 63 96 ND
G Agents ND ND ND
VX 76 99 ND
Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999%
(7-Log) kill after a 30 minute exposure to DF-200HF with glycerol.
This formulation can be used for direct application to humans because the
glycerol will act as
a humectant. This formulation could also be utilized, e.g., as a spray or
shower, by removing
foaming constituents (such as 1-dodecanol and Adogen 477n1), and by reducing
the concentration of
peroxide. However, a drawback to the use of glycerol is that it is solid at a
fairly high temperature
(below about 10 C). Therefore, it would preferably be used in controlled
temperature conditions (i.e.,
warm temperature conditions).
CA 02461872 2010-05-27
47
Propylene glycol diacetate, a bleaching activator used in many of the
previously described
DF-200 configurations is not presently available in solid form. However, other
bleaching activators
are available in solid form.
DF-200 with Acetylcholine Chloride
Solid 0-acetyl bleaching activators (e.g., acetylcholine chloride, which is
often used in
eyedrop solutions) can be used in DF-200 formulations in place of (liquid)
propylene glycol diacetate.
The chemical structure of this 0-acetyl bleaching activator is shown below. As
can be seen, the
molecule contains an 0-acetyl group that can activate peroxide, and it is a
quaternary compound,
which is very compatible with DF-200 formulations. Acetylcholine chloride is
also soluble in water
and is very hygroscopic.
0 CH3
I I I
CH3 - C -0 CH2 CH2 ¨ N -CH3 CI
1
CH3
An example of a 2-part kit configuration of DF-200HF using acetylcholine
chloride comprises
(amounts illustrative):
CA 02461872 2010-05-27
48
DF-200HF Rai:Ad Deployment using Acetylcholine Chloride (2-Dart kit)
Part A (Liquid Foam Component):
20 g Variquat 80MCTm
g Adogen 477Tm
5 30 g Poly (Ethylene Glycol) (MW 8000)
8 g Diethylene Glycol Monobutyl Ether
5 g lsobutanol
4 g 1-Dodecanol
150 g Propylene Glycol
10 50 g Potassium Bicarbonate
approx. 17 g Potassium Hydroxide (sufficient to give a final pH of 10.2 in
Part A)
803 g Water
Part B (Solid Additive):
97 g Urea Hydrogen Peroxide
25 g Acetycholine Chloride (solid bleaching activator)
This formulation will produce approximately 1 liter of foam solution. The pH
of the final formulation
can be adjusted to be between about 9.6 and 9.8 for optimal performance. To
use this formulation,
mix Part B into Part A. Use, preferably, within 8 hours. The performance of DF-
200HF using
acetylcholine chloride against chemical agent simulants is shown in Table 16.
Table 16: Reaction rates from kinetic testing for the DF-200HF using
acetylcholine chloride
as an activator.
% Decontaminated
Simulant 1 Minute , 15 Minutes 60 Minutes
Mustard (HD) 60 98 ND
VX 10 85 >99
CA 02461872 2010-05-27
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Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999%
(7-Log) kill after a 30 minute exposure to DF-200HF using acetylcholine
chloride.
Two other 0-acetyl bleaching activators, monoacetin (glycerol monoacetate) and
diacetin
(glycerol diacetate), have also been tested for their effectiveness in DF-200
formulations. Both of
these compounds have also proven to be extremely effective bleaching
activators. These
compounds are water-soluble liquids.
Experiments have also shown that the peroxide in DF-200 formulations is also
effectively
activated by a nitrile-containing compound, such as 4-cyanobenzoic acid (which
is water-soluble), at
a concentration of, for example, 2%, for the neutralization of both chemical
agent and biological
agent simulants.
DF-200 using Peracetic Acid
Tests were conducted using peracetic acid as the oxidant in DF-200, instead of
hydrogen
peroxide. The following formulation was used:
2% Variquat 80MC TM (cationic surfactant)
2% peracetic acid (oxidant)
5% potassium bicarbonate (buffer and activator)
91% water
The pH was adjusted to 9.8 with solid KOH and the formulation was tested
against the simulants for
mustard, VX, and anthrax spores. The performance of this formulation is shown
in Table 17 against
chemical agent simulants.
CA 02461872 2010-05-27
Table 17: Reaction rates in kinetic testing for DF-200 with 2% peracetic acid.
% Decontaminated
Simulant 1 Minute 15 Minutes 60 Minutes
Mustard (HD) 27 58 68
VX 68 76 95
5 Tests against the anthrax spore simulant (Bacillus globigii spores)
demonstrated 99.9999%
(7-Log) kill after a 30 minute exposure to DF-200 with 2% peracetic acid.
Tests were also conducted for DF-200 using a higher concentration of peracetic
acid (3.5%)
in the following formulation:
2% Variquat 80MCTm (cationic surfactant)
3.5% peracetic acid (oxidant)
5% potassium bicarbonate (buffer and activator)
89.5% water
The pH was adjusted to 9.8 with solid KOH and the formulation was tested
against the simulants for
mustard, VX, and anthrax spores. The performance of this formulation is shown
in Table 18 against
chemical agent simulants.
Table 18: Reaction rates in kinetic testing for DF-200 with 3.5% peracetic
acid.
% Decontaminated
Simulant 1 Minute 15 Minutes 60 Minutes
Mustard (HD) 40 94 ND
VX 74 96 98
The results show that use of peracetic acid as an alternative oxidant is
effective against
chemical agent simulants, but is not as effective as DF-200 formulations using
activated hydrogen
CA 02461872 2010-05-27
_ 51
peroxide (i.e., the combination of hydrogen peroxide, bicarbonate, and
propylene glycol diacetate) as
the oxidant. However, the DF-200 formulations with 2-3.5% peracetic acid are
very effective for
spore kill. Nevertheless, use of this oxidant is not as attractive as hydrogen
peroxide because
peracetic acid is not presently available in a safe, convenient solid form,
and the shelf life of the liquid
form is rather short.
Tests were also conducted to determine the minimum constituents required for
spore kill in a
DF-200 formulation which utilizes peracetic acid as an oxidant. These results
indicate that only three
constituents, i.e., peracetic acid, bicarbonate and the cationic surfactant,
are necessary to achieve
high rates of spore kill.
Live Agent Tests Using DF-200HF
Live agent tests on three chemical agents (soman ("GD"), VX, and mustard
("HD")) and two
biological agents (anthrax spores and Yersinia pestis) were conducted. The
results of kinetic testing
of DF-200HF (using a three-part configuration) on the chemical agents is shown
in Table 19.
Table 19: Reaction rates in kinetic testing for DF-200HF against chemical
agents.
% Destruction of Chemical Agent at Time Interval
1 minute 15 minutes 60 minutes
Chemical Agent
GD 99.98 0.01 99.97 0.01 99.98 0.01
VX 91.20 8.56 99.80 0.08 99.88 0.04
HD 78.13 10.53 98.46 1.43 99.84 0.32
After exposure of GD to DF-200HF, methylphosphonic acid (MPA) and pinacolyl
methylphosphonic
acid (PMPA) were identified as byproducts. After exposure of VX to DF-200HF,
ethyl
methylphosphonic acid (EMPA) and MPA were identified as byproducts. This
indicated that the
destruction of the VX followed the more desirable path to the phosphonic
acids, rather than to
EA2192 (a toxic byproduct which can also be produced during VX degradation).
Lastly, after
exposure of HD to DF-2001-IF, the initial degradation products for HD
comprised a mixture of the
CA 02461872 2010-05-27
52
sulfoxide and sulfone byproducts, followed later by nearly complete
disappearance of each of these
byproducts after 60 minutes.
Results of tests against anthrax spores is shown in Tables 20 and 21 and
against Yersinia
pestis (i.e., the plague bacterium) are shown in Table 22 (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 this detection limit.
Table 20: Kill rates for B. anthracis AMES-RIID spores in a solution of DF-
200HF.
B. anthracis AMES-RID Average CFU/ml Log Reduction '% Reduction
Control 1.21E+07 0 0.00
min contact NO 7 100 .00004
30 min contact NG 7 100 .00004
60 min contact NG 7 100 .00004
Table 21: Kill rates for B. anthracis ANR-1 spores in a solution of DF-200HF.
B. anthracis ANR-1 Average CFU/ml Log Reduction %
Reduction
Control 6.42E+07 0 0/00
15 min contact NG 7 100 .00004
30 min contact NG 7 100 .00004
60 min contact NO 7 100 .00004
Table 22: Kill rates for Y. pestis cells in a solution of DF-200HF.
Y. pestis (ATCC 11953) Average CFU/ml Log Reduction %Reduction
Control 1.33E+07 0 0.00
15 min contact NG 7 100 .00004
30 min contact NG 7 100 .00004
60 min contact NG 7 100 .00004
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53
The petri dishes used for cell growth on each of these tests were saved for 21
days following
the tests to verify that DF-200HF had actually killed the spores, rather than
just inhibiting their
growth. No growth on any of the petri dishes was observed after the 21-day
period.
Toxic Industrial Chemicals Tests Usina DF-200HF
Several toxic industrial chemicals (TICs) have also been tested against DF-
200HF. A
summary of the TICs tested to date and the results of those tests is shown in
Table 23. Note that the
results for malathion, butyl isocyanate, sodium cyanide, and carbon disulfide
were obtained by
analyzing for the unreacted chemical in foam solution, while the results for
phosgene was obtained
by analyzing for the chemical in the headspace above a foam solution. These
results demonstrate
very effective neutralization of these toxic industrial chemicals.
Table 23: Summary of Toxic Industrial Chemical (TIC) Neutralization Tests with
DF-200HF.
TIC % Decontaminated
1 minute 15 minutes 60 minutes
Malathion (liquid) 89 95 Below Detection
Hydrogen Cyanide (gas) >99 >99 >99
Sodium Cyanide (solid) 93 98 >99
Butyl lsocyanate (liquid) 99 Below Detection Below Detection
Carbon Disulfide (liquid) >99 >99 Below Detection
Phosgene (gas) 98 >99 >99
The preceding examples can be repeated with similar success by substituting
the generically
or specifically described reactants and/or operating conditions of this
invention for those used in the
preceding examples.
Although the invention has been described in detail with particular reference
to these
preferred embodiments, other embodiments can achieve the same results.
Variations and
modifications of the present invention will be obvious to those skilled in the
art and it is intended to
CA 02461872 2010-05-27
_ 54
cover in the appended claims all such modifications and equivalents.
