Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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DECONTAMINATION COMPOSITIONS AND
METHODS OF DECONTAMINATION
Consumers, first responders, and military personnel are often exposed to
potentially undesirable materials, including, but not limited to, phthalate
plasticizers,
formaldehyde, halogenated flame retardants, polycyclic aromatic hydrocarbons
(PAH), and
chemical and biological warfare agents. Examples of PAH include, but are not
limited to,
benzo(a)pyrene, benzo(e)pyrene, benz(a)anthracene, benzo(k)fluoranthene,
fluorene,
anthracene, and fluoranthene. These are compounds with two or more fused
aromatic rings,
containing only carbon and hydrogen. They are potentially endocrine disrupting
as well as
potentially tumorigenic substances. Benzo(a)pyrene (BaP) is a concerning PAH.
PAH present in the soil is typically decontaminated using chemicals,
microbes, and other physical methods, such as adsorption, thermal, ultra-
violet, ultrasonic
and plasma radiations. PAH emitted from automotive fuel exhaust can be
decontaminated
using catalytic oxidation.
When firefighters are exposed to fires, PAHs can be deposited on the surface
of their personal protective clothing. Protective clothing can include, for
example, turnout
clothing, fire proximity suits and hazmat suits, which are worn by
firefighters and first
responders. A firefighter's turnout clothing usually includes a combination of
a uniform
shirt, uniform trousers, a jacket, trousers, gloves, boots, hoods, and
helmets. Protective
clothing may also be worn by personnel in law enforcement, the military,
cleaning or repair
services, and the construction industry.
There is a need to remove these compounds safely from the personal
protective clothing. Currently, the PAHs are removed by washing. However,
while this
works, it can also expose other clothing to the PAHs, which is undesirable.
Decontamination compositions specifically used to decontaminate PAH that
have reported in the literature only remove the contaminant partially from the
surface, and
they are not effective in converting them to less toxic or benign materials at
room
temperature within a brief period time.
Recently, it was reported that using scrubbing and power washing of
firefighters ensemble with soap water removes up to 60 % of the PAH's.
(Reference: Fent et
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al., Contamination of firefighter personal protective equipment and skin and
the effectiveness
of decontamination procedures. J. Occup. Environ. Hyg. 2017, 14, p. 801-814.)
However, there remains a need to remove and/or reduce potentially toxic
material, such as the PAHs, from clothing before laundering to reduce or
eliminate further
exposure to the PAHs.
DETAILED DESCRIPTION
The present invention relates generally to decontaminating clothing having
toxic materials thereon. More particularly, it relates to decontaminating
compositions and
methods useful to decontaminate potentially toxic materials, such as PAH and
others, present
on clothing. Examples of clothing which can be decontaminated using the
decontaminating
composition and method include, but are not limited to, turnout clothing, fire
proximity suits
and hazmat suits, which are worn by firefighters and first responders. A
firefighter's turnout
clothing usually includes a combination of a uniform shirt, uniform trousers,
a jacket,
trousers, gloves, boots, hoods, and helmets. In addition, the normal clothing
of a person who
was exposed to toxic materials, PAH, or both could also decontaminated using
the
decontamination composition.
For effective decontamination of toxic materials, PAH, or both, it is
desirable
that the decontamination composition removes the toxic materials, PAH, or both
from the
surface and/or converts them to corresponding reaction products (e.g.,
oxidized products)
which are typically less toxic or benign materials. It is also desirable that
the
decontamination be effective at temperatures in the range of 4 C to 30 C
within a brief
period of time, e.g., preferably within one hour.
One aspect of the invention is a decontamination composition. In one
embodiment, the decontamination composition comprises an aqueous solution of a
water
soluble cerium salt or a dispersion of cerium oxide in water. The composition
may have a
cerium salt concentration ranging from 0.01 and 80 wt% of the decontamination
composition
(based on total composition), or from 0.01 and 70 wt%, or from 0.01 and 60
wt%, or from
0.01 and 50 wt%, or from 0.01 and 40 wt%, or from 0.01 and 30 wt%, or from
0.01 and 20
wt%, or from 0.01 and 10 wt%, or from 0.01 and 5 wt%, or from 1 and 80 wt%, or
from 1
and 70 wt%, or from 1 and 60 wt%, or from 1 and 50 wt%, or from 1 and 40 wt%,
or from 1
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and 30 wt%, or from 1 and 20 wt%, or from 1 and 10 wt%, or from 1 and 5 wt%,
or from 4
and 80 wt%, or from 4 and 70 wt%, or from 4 and 60 wt%, or from 4 and 50 wt%,
or from 4
and 40 wt%, or from 4 and 30 wt%, or from 4 and 20 wt%, or from 4 and 10 wt%,
or from 10
and 80 wt%, or from 10 and 70 wt%, or from 10 and 60 wt%, or from 10 and 50
wt%, or
from 10 and 40 wt%, or from 10 and 30 wt%, or from 10 and 20 wt%, or from 20
and 80
wt%, or from 20 and 70 wt%, or from 20 and 60 wt%, or from 20 and 50 wt%, or
from 20
and 40 wt%, or from 20 and 30 wt%, or from 25 and 80 wt%, or from 25 and 70
wt%, or
from 25 and 60 wt%, or from 25 and 50 wt%, or from 25 and 40 wt%, or from 25
and 35
wt%. Suitable water soluble cerium salts include, but are not limited to,
ammonium cerium
(IV) nitrate, ammonium cerium(IV) sulfate hydrate, cerium(III) carbonate
hydrate,
cerium(III) chloride heptahydrate, cerium(IV) fluoride, cerium(IV) hydroxide,
cerium(IV)
nitrate hexahydrate, cerium(III) sulfate hydrate, or combinations thereof
The cerium oxide concentration in the dispersion is generally 1 to 50 wt% of
the decontamination composition (based on total composition), or 1 to 45 wt%,
or 1 to 40
wt%, or 1 to 35 wt%, or 1 to 30 wt%, or 1 to 35 wt%, or 1 to 20 wt%, or 1 to
15 wt%, or 1 to
10 wt%, or 1 to 5 wt%, or 5 to 50 wt%, or 10 to 50 wt%, or 15 to 50 wt%, or 20
to 50 wt%,
or 25 to 50 wt%, or 30 to 50 wt%, or 35 to 50 wt%, or 40 to 50 wt%, or 45 to
50 wt%,.
The cerium ion concentration in the decontamination composition is typically
in the range of 1 to 500 parts per million (ppm), or 10 to 500 ppm, or 20 to
500 ppm, or 30 to
500 ppm, or 40 to 500 ppm, or 50 to 500 ppm, or 60 to 500 ppm, or 70 to 500
ppm, or 80 to
500 ppm, or 90 to 500 ppm, or 100 to 500 ppm, or 125 to 500 ppm, or 150 to 500
ppm, or
175 to 500 ppm, or 200 to 500 ppm, or 225 to 500 ppm, or 250 to 500 ppm, or
275 to 500
ppm, or 300 to 500 ppm, or 325 to 500 ppm, or 350 to 500 ppm, or 375 to 500
ppm, or 400 to
500 ppm, or 425 to 500 ppm, or 450 to 500 ppm, or 475 to 500 ppm, or 1 to 475
ppm, or 1 to
.. 450 ppm, or 1 to 425 ppm, or 1 to 400 ppm, or 1 to 375 ppm, or 1 to 350
ppm, or 1 to 325
ppm, or 1 to 300 ppm, or 1 to 275 ppm, or 1 to 250 ppm, or 1 to 225 ppm, or 1
to 200 ppm, or
1 to 175 ppm, or 1 to 150 ppm, or 1 to 125 ppm, or 1 to 100 ppm, or 1 to 75
ppm, or 1 to 50
ppm, or 1 to 25 ppm, or 1 to 10 ppm.
The water used in the solution can be any type of water, including but not
limited to, distilled water, deionized water, tap water, and the like. The
water is generally
present in the decontamination composition in amount ranging from 30 to 99
wt%, or 35 to
99 wt%, or 40 to 99 wt%, or 45 to 99 wt%, or 50 to 99 wt%, or 55 to 99 wt%, or
60 to 99
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wt%, or 65 to 99 wt%, or 70 to 99 wt%, or 75 to 99 wt%, or 80 to 99 wt%, or 85
to 99 wt%,
or 90 to 99 wt%, or 95 to 99 wt%, or 30 to 95 wt%, or 30 to 90 wt%, or 30 to
85 wt%, or 30
to 80 wt%, or 30 to 75 wt%, or 30 to 70 wt%, or 30 to 65 wt%, or 30 to 60 wt%,
or 30 to 55
wt%, or 30 to 50 wt%, or 30 to 45 wt%, or 30 to 40 wt%, or 40 to 95 wt%, or 40
to 90 wt%,
or 40 to 85 wt%, or 40 to 80 wt%, or 40 to 75 wt%, or 40 to 70 wt%, or 40 to
65 wt%, or 40
to 60 wt%, or 40 to 55 wt%, or 40 to 50 wt%, or 40 to 45 wt%.
The decontamination composition may optionally include at least one of an
oxidizer, an activator for the oxidizer, a surfactant, a co-solvent, a
chelating agent, and a
polymer. When any of these components are present, there can be one or more of
that
.. component (i.e., one or more oxidizers, one or more surfactants, one or
more co-solvents, one
or more chelating agents, and/or one or more polymers).
The oxidizer may oxidize and decontaminate phthalate plasticizers,
formaldehyde, halogenated flame retardants, polycyclic aromatic hydrocarbons
(PAH), and
chemical and biological warfare agents. Any suitable oxidizer may be used,
including, but
not limited to, hydrogen peroxide, sodium hypochlorite, sodium percarbonate,
or
combinations thereof. The oxidizer may comprise 1 to 10 wt% of the
decontamination
composition (based on the total composition), or 2 to 10 wt%, or 3 to 10 wt%,
or 4 to 10
wt%, or 5 to 10 wt%, or 6 to 10 wt%, or 7 to 10 wt%, or 8 to 10 wt%, or 9 to
10 wt%, or 1 to
9 wt%, or 1 to 8 wt%, or 1 to 7 wt%, or 1 to 6 wt%, or 1 to 5 wt%, or 1 to 4
wt%, or 1 to 3
wt%, or 1 to 2 wt%.
The activator for the oxidizer activates the oxidizer so that the oxygen
release
takes place at lower temperature. For example, if hydrogen peroxide is used as
an oxidizer to
clean the surface, typically the effectiveness of cleaning is seen above 45 C.
However, if an
activator is used with the hydrogen peroxide, effective cleaning can take
place at
temperatures below 25 C. Suitable activators include, but are not limited to,
tetraacetoxy
ethylene diamine (TAED), sodium nonanoyloxybenzenesulfonate, silver acetate,
silver
nitrate, manganese acetate, copper acetate, iron (II) sulfate, iron (III)
sulfate, or combinations
thereof The activator may comprise 0.01 to 10 wt% of the decontamination
composition
(based on the total composition), or 0.01 to 8 wt%, or 0.01 to 6 wt%, 0.01 to
5 wt%, 0.01 to 4
wt%, or 0.01 to 3 wt%, 0.01 to 2 wt%, or 0.01 to 1 wt%, or 0.01 to 0.8 wt%, or
0.01 to 0.6
wt%, or 0.01 to 0.5 wt%, or 0.01 to 0.4 wt%, or 0.01 to 0.3 wt%, or 0.01 to
0.2 wt%, or 0.01
to 0.1 wt%, or 0.01 to 0.08 wt%, 0.01 to 0.06 wt%, or 0.01 to 0.05 wt%.
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The surfactant may be useful to spread the decontamination composition
evenly on the contaminated surface. Any suitable surfactant may be used. The
surfactant can
be a cationic surfactant, an anionic surfactant, a non-ionic surfactant, or
combinations thereof.
Examples of non-ionic surfactants include, but are not limited to,
poly(ethylene oxide-b-
propylene oxide), poly(ethylene oxide-b-butylene oxide), sorbitol esters of
fatty acids,
ethoxylated fatty alcohols, and combinations thereof Examples of anionic
surfactants
include, but are not limited to, sodium dodecyl sulfate, sodium lauryl benzene
sulfonate, poly
acrylic acid, sulfate based surfactants, and sulfonate based surfactants, and
combinations
thereof Examples of cationic surfactants include, but are not limited to,
benzalkonium salts,
polyquaterniriums, and poly(vinyl pyridine) co-N,N dimethyl ethyl
methacrylate, or
combinations thereof. Polyquaternium is a designation used to emphasize the
presence of
quaternary ammonium centers in the polymer. The numbers are assigned in the
order in
which they are registered rather than because of their chemical structure.
Examples of
polyquaterniums include, but are not limited to, polyquaternium-5 which is a
copolymer of
acrylamide and quaternized dimethylammoniumethyl methacrylate, polyquaternium-
7 which
is copolymer of acrylamide and diallyldimethylammonium chloride, and
polyquaternium-7
which is terpolymer of acrylic acid, methacrylamidopropyl trimethylammonium
chloride, and
methyl acrylate. Some commercial examples of surfactants are: ALGENE , EMPIGEN
B
series, BTC Onixide, and Quaterx 192. The surfactant may comprise 0.5 to 2 wt%
of the
decontamination composition (based on the total composition), or 0.5 to 1.5
wt%, or 0.5 to 1
wt%, or 0.5 to 0.9 wt%, or 0.5 to 0.8 wt%, or 0.5 to 0.7 wt%, or 0.5 to 0.6
wt%, or 0.6 to 2
wt%, or 0.7 to 2 wt%, or 0.8 to 2 wt%, or 0.9 to 2 wt%, or 1.0 to 2 wt%, or
1.1 to 2 wt%, or
1.3 to 2 wt%, or 1.4 to 2 wt%, or 1.5 to 2 wt%, or 1.6 to 2 wt%, or 1.7 to 2
wt%, or 1.8 to 2
wt%, or 1.9 to 2 wt%.
The co-solvent can help to keep the desired solubility of the decontamination
composition. Any suitable co-solvents can be used, including but not limited
to, ethanol,
glycerol, propylene glycol, propylene glycol ethyl ether, ethylene carbonate,
propylene
carbonate, or combinations thereof The co-solvent may comprise 10 to 30 wt% of
the
decontamination composition (based on the total composition), or 10 to 25 wt%,
or 10 to 20
wt%, or 10 to 15 wt%, or 15 to 30 wt%, or 20 to 30 wt%, or 35 to 30 wt%.
The chelating agent can prevent the interference of minerals such as sodium,
potassium, magnesium with cerium during the decontamination reactions. Any
suitable
chelating additives can be used including, but not limited to, citric acid,
ethylene diamine
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tetraacetic acid, or combinations thereof The chelating agent may comprise 0.2
to 1 wt% of
the decontamination composition (based on the total composition), or 0.2 to
0.9 wt%, or 0.2
to 0.8 wt%, or 0.2 to 0.7 wt%, or 0.2 to 0.6 wt%, or 0.2 to 0.5 wt%, or 0.2 to
0.4 wt%, or 0.2
to 0.3 wt%, or 0.3 to 1 wt%, or 0.4 to 1 wt%, or 0.5 to 1 wt%, or 0.6 to 1
wt%, or 0.7 to 1
wt%, or 0.8 to 1 wt%, or 0.9 to 1 wt%.
The polymer can help achieve desirable flow, viscosity, or both of the
decontamination composition during application. Any suitable polymer, can be
used
including, but not limited to, polyacrylic acids, a poly (acrylic acid-co-
methyl vinyl ether),
polyvinyl pyrrolidones, polyvinyl pyridines, polyoxazolidone and
polyoxazolidone
.. copolymers, or combinations thereof The polymer may comprise 0.1 to 5 wt%
of the
decontamination composition (based on the total composition), or 0.1 to 4.5
wt%, or 0.1 to 4
wt%, or 0.1 to 3.5 wt%, or 0.1 to 3 wt%, or 0.1 to 2.5 wt%, or 0.1 to 2 wt%,
or 0.1 to 1.5
wt%, or 0.1 to 1 wt%, or 0.1 to 0.5 wt%, or 0.5 to 5 wt%, or 1 to 5 wt%, or
1.5 to 5 wt%, or 2
to 5 wt%, or 2.5 to 5 wt%, or 3 to 5 wt%, or 3.5 to 5 wt%, or 4 to 5 wt%, or
4.5 to 5 wt%.
In some embodiments, the cerium salt can be reacted with hydroxides to form
a dispersion of cerium oxide in water. However, this is less desirable because
cerium oxide is
more expensive than cerium salts. Suitable hydroxides include, but are not
limited to
tetramethylammonium hydroxide (TMAH), ammonium hydroxide, choline hydroxide,
benzyltrimethylammonium hydroxide, or combinations thereof.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 500 ppm cerium ions.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1-250 ppm cerium ions.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1-100 ppm cerium ions.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 500 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer and wherein the amount of at least one of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
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In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 250 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
wt% polymer and wherein the amount of at least one of the oxidizer, the
activator, the
5 .. surfactant, the co-solvent, the chelating agent, or the polymer is
greater than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 500 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer, and wherein the amount of at least one of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 500 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer and wherein the amount of at least two of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 250 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer and wherein the amount of at least two of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 100 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer, and wherein the amount of at least two of the oxidizer, the
activator, the
.. surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 500 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer and wherein the amount of at least three of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
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In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 250 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
wt% polymer and wherein the amount of at least three of the oxidizer, the
activator, the
5 surfactant, the co-solvent, the chelating agent, or the polymer is
greater than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 100 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer, and wherein the amount of at least three of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 500 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer and wherein the amount of at least four of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 250 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer and wherein the amount of at least four of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 100 ppm cerium ions, 0 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0 to 2 wt% surfactant, 0 to 30 wt% co-solvent, 0 to 1 wt %
chelating agent, and 0 to
5 wt% polymer, and wherein the amount of at least four of the oxidizer, the
activator, the
surfactant, the co-solvent, the chelating agent, or the polymer is greater
than 0.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 500 ppm cerium ions, 1 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0.5 to 2 wt% surfactant, 10 to 30 wt% co-solvent, 0.2 to 1 wt %
chelating agent,
and 0.1 to 5 wt% polymer.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 250 ppm cerium ions, 1 to 10 wt% oxidizer, 0
to 10 wt%
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activator, 0.5 to 2 wt% surfactant, 10 to 30 wt% co-solvent, 0.2 to 1 wt %
chelating agent,
and 0.1 to 5 wt% polymer.
In some embodiments, the decontamination composition comprises an
aqueous solution comprising 1 to 100 ppm cerium salt, 1 to 10 wt% oxidizer, 0
to 10 wt%
activator, 0.5 to 2 wt% surfactant, 10 to 30 wt% co-solvent, 0.2 to 1 wt %
chelating agent,
and 0.1 to 5 wt% polymer.
In an embodiment, the decontamination compositions decontaminate the toxic
materials and/or PAHs by removing at least a portion of the contaminant from
the surface of
the clothing. In some embodiments, the decontamination composition converts
the toxic
materials and/or PAHs to their corresponding oxidized products which are
typically less toxic
or benign materials. In some embodiments, at least some of the toxic materials
and/or PAHs
are removed and converted to less toxic or benign materials. Typically, at
least 50% of the
toxic materials and/or PAHs are removed or converted, or at least 60%, or at
least 70%, or at
least 80%, or at least 90%.
Another aspect of the invention involves methods of decontaminating clothing
having toxic materials and/or PAH on it. In one embodiment, the method
involves applying a
decontamination composition to clothing containing toxic materials and/or PAH.
The
decontamination composition comprises an aqueous solution of a water soluble
cerium salt or
dispersion of cerium oxide in water as described above.
The decontamination composition can be applied using any suitable method
including, but not limited to, spraying, dipping, pouring, wiping scrubbing,
and combinations
thereof The decontamination composition can be removed from the clothing after
decontamination by the same methods.
The aqueous solution of the water soluble cerium salt or the dispersion of
cerium oxide in water may be prepared in advance of use or it may be prepared
at the time it
is to be applied.
In some embodiments, the decontamination composition should be maintained
at a temperature in the range of 4 C to 30 C for storage and application, or
10 C to 30 C, or
15 C to 30 C, or 20 C to 30 C, or 22 C to 30 C.
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In some embodiments, the toxic materials, PAH, or both are removed and/or
converted to less toxic or benign materials within 24 hours, or within 12
hours, or within 6
hours, or within 4 hours, or within 2 hours, or within 1 hour.
In some embodiments, the decontamination composition is used to
decontaminate the toxic materials and/or PAHs immediately from the
firefighter's protective
clothing the scene of a fire incident. In other embodiments, the
decontamination composition
is used to decontaminate the toxic materials and/or PAHs from the
firefighter's protective
clothing after the firefighter returns from the scene of a fire incident.
Another aspect of the invention is a kit containing the components for the
decontamination composition. The cerium salt, cerium oxide (or cerium salt and
hydroxide)
could be provided in the appropriate amounts, along with one or more of the
optional
oxidizer, activator, surfactant, co-solvent, chelating agent, and polymer, as
desired. The kit
can be easily stored and transported to the application site where the
components can be
mixed with water and applied. The kit could designed to provide include
sufficient cerium
salt or cerium oxide for a single application, for example for a single fire
fighter, or multiple
applications, for example two or more fire fighters. Instructions can be
included in the kit to
provide directions for the proper mixing and application procedures.
EXAMPLES
The invention is further described with the following examples and should not
be construed as to limit the scope of the invention. All examples were
conducted at room
temperature (approximately 23 C).
Example 1: Preparation of Decontamination Composition A
Ammonium cerium (IV) nitrate, 40 grams (g) (Sigma# C3654) was dissolved
in 100 grams of distilled water. Once the solid was dissolved, a sonicating
horn
(Sonicator=Misonix Sonicator 3000, horn=Misonix Inc. Model#4, ¨1/4 -1/2") was
placed
into the cerium solution. The solution was sonicated, followed by the addition
of 24
milliliters (mL) of tetramethylammonium hydroxide (TMAH, 25% in water, Sigma
#331635). Once all TMAH had been charged, the solution was sonicated for
another 8-10
minutes to produce the decontamination composition A.
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Example la: Preparation of Decontamination Composition lA
4 grams of ammonium cerium (IV) nitrate and 100 mL of distilled water were
weighed in a 250 mL glass jar. The solids were dissolved using a magnetic
stirrer to produce
the decontamination composition lA
Example 2: Preparation of Decontamination Composition B
In a 250 mL glass jar, mix 4 grams of ammonium cerium(IV) sulfate hydrate
and 100 mL of distilled water. The solids are dissolved using a magnetic
stirrer to produce
the decontamination composition B.
Example 3: Preparation of Decontamination Composition C
In a 250 mL glass jar, mix 4 grams of cerium(III) carbonate hydrate and 100
mL of distilled water. The solids are mixed using a magnetic stirrer to
produce the
decontamination composition C.
Example 4: Preparation of Decontamination Composition D
In a 250 mL glass jar, mix 4 grams of cerium(III) chloride heptahydrate and
100 mL of distilled water. The solids are mixed using a magnetic stirrer to
produce the
decontamination composition D.
Example 5: Preparation of decontamination Composition E
In a 250 mL glass jar, mix 4 grams of cerium(IV) fluoride and 100 mL of
distilled water. The solids are mixed using a magnetic stirrer to produce the
decontamination
composition E.
Example 6: Preparation of Decontamination Composition F
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In a 250 mL glass jar, mix 4 grams of cerium(IV) hydroxide and 100 mL of
distilled water. The solids are mixed using a magnetic stirrer to produce the
decontamination
composition F.
Example 7: Preparation of Decontamination Composition G
In a 250 mL glass jar, mix 4 grams of cerium(III) nitrate hexahydrate and 100
mL of distilled water. The solids are mixed using a magnetic stirrer to
produce the
decontamination composition G.
Example 8: Preparation of Decontamination Composition H
In a 250 mL glass jar, mix4 grams of cerium(III) oxalate hydrate hexahydrate
and 100 mL of distilled water. The solids are mixed using a magnetic stirrer
to produce the
decontamination composition H.
Example 9: Preparation of Decontamination Composition I
In a 250 mL glass jar, mix 4 grams of cerium(III) sulfate hydrate and 100 mL
of distilled water. The solids are mixed using a magnetic stirrer to produce
the
decontamination composition I.
Example 10: Decontamination of PAH' s using Decontamination Composition
A
One square inch of poly(benzimidazole) based test fabric was challenged
(applying the contaminant to a substrate) with 315 micrograms of
Benzo(a)pyrene, B(a)P.
B(a)P is one of the concerning PAHs which can be present on the firefighter
ensemble. The
decontamination solution A obtained from example 1 was sprayed onto B(a)p
challenged test
fabrics such that the quantity of cerium added to the fabric was between 7.5
and 10.6 mg/in2
(milligrams per square inch). After 15 minutes, the fabric was extracted with
acetonitrile
solvent. The extracted solution was analyzed for the presence of B(a)P using
High
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Performance Liquid Chromatography (HPLC) with a UV-VIS detector. There was no
B(a)P
left in the extraction solution, suggesting that B(a)P was 100%
decontaminated.
Example 10a (control): Decontamination of PAH' s using water
One square inch of poly(benzimidazole) based test fabric was challenged with
315 micrograms of B(a)P. Water was sprayed onto B(a)p challenged test fabrics,
and, after
minutes, the fabric was extracted with acetonitrile solvent. The extracted
solution was
analyzed for the presence of B(a)P using HPLC with a UV-VIS detector. More
than 250
micrograms of B(a)P remained in the extraction solution, suggesting that less
than 20% of the
10 B(a)P was removed or converted.
Example 11: Decontamination of PAH' s using Decontamination Composition
A
One square inch of poly(benzimidazole) based test fabric was challenged with
15 300 micrograms of B(a)P. The B(a)P challenged test fabric was placed in
a beaker
containing 50 mL of the decontamination solution A obtained from example 1.
After 5
minutes of exposure, the fabric was removed and extracted with acetonitrile
solvent. The
extracted solution was analyzed for the presence of B(a)P using HPLC with a UV-
VIS
detector. There was no B(a)P left in the extraction solution, suggesting that
B(a)P was 100%
decontaminated.
Example 11 a (control): Decontamination of PAH' s using water
One square inch of poly(benzimidazole) based test fabric was challenged with
300 micrograms of B(a)P. The B(a)P challenged test fabric was placed in a
beaker
containing 50 mL water. After 5 minutes of exposure, the fabric was removed
and extracted
with acetonitrile solvent. The extracted solution was analyzed for the
presence of B(a)P
using HPLC with a UV-VIS detector. More than 240 micrograms of B(a)P remained
in the
extraction solution, suggesting that 20% or less of the B(a)P was removed or
converted.
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Example 12: Decontamination of PAH' s using Decontamination Composition
lA
One square inch of poly(benzimidazole) based test fabric was challenged with
500 nanograms each of four major PAH' s: Benzo(a)pyrene (B(a)P),
Benzo(a)anthracene
(B(a)A), Benzo(b)fluoranthene (B(b)F), Dibenz(a,h)anthracene (D(a,h)A). 1 mL
of the
decontamination solution lA obtained from Example la was added in drops to the
test fabrics
which were previously challenged with the combined PAH' s. After specified
exposure times
as shown below, the fabric was extracted with 1:1 (by volume) of
acetone:methylene chloride
solution. The extracted solution was analyzed for the presence of the four
PAH' s using Gas
Chromatography coupled with Mass Spectroscopy (GC/MS). The decontamination
efficiency with respect to time for the PAH' s is shown in the following
table:
PAH type Amount of PAH decontaminated (%) at specified time
(min)
1 5 10 20 30
B(a)P 70 10 100 2 95 5 100 2 100 2
B(a)A 40 10 45 5 50 10 50 2 50 5
B(b)F 38 15 38 10 45 5 35 8 32 10
D(a,h)A 25 15 50 10 35 10 38 10 30 5
Example 13: Example of on-Scene decontamination method at the scene of a
fire incident.
After the rescue operation is complete, proceed for decontamination. Use a
previously made decontamination composition 1A, or prepare a solution
according to the
procedure on the scene by adding packet of concentrate (liquid or powder) into
sprayer and
adding water up to fill line. Mix until dissolved. Pressurize sprayer with
hand pump.
Optional - Connect garden hose (with spray nozzle) to pump with adapter on
engine.
Optional - Spray down firefighter with clean water, removing loose soot from
SCBA, jacket,
trousers, gloves, and boots. Rinse helmet separately. Spray firefighter with
decontamination
solution, making sure to fully cover/saturate all turnout gear, including
hood. Spray helmet
separately, inside and out. After all visible soot has come in contact with
decontamination
solution, firefighter will remove Self-contained Breathing Apparatus (SCBA).
Additional
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solution may be sprayed on areas that were covered with SCBA bottle and
straps. Spray
SCBA completely, including the seal of the mask. Pour out any remaining
decontamination
solution and rinse sprayer with clean water. Return to station, remove turnout
gear, and
shower. Wash turnout gear before wearing again in accordance with NFPA 1851 or
standard
AATCC method.
Example 14: On-Scene decontamination of PAH' s using the decontamination
Composition 1A immediately from the firefighter's ensemble after a rescue
mission on the
scene of a fire incident.
After the rescue operation is complete, the firefighter will proceed to a
mobile
shower unit, wherein the shower unit comprises of shower heads capable of
spraying the
decontamination composition 1A and municipal water in tandem for a specified
amount of
time as soon as the firefighter steps into the shower. The shower booth is
capable of
indicating the firefighter whether the decontamination is complete by flashing
a green light.
.. The shower booth is further capable of collecting the run off solution in
isolated tank for
reuse or safe discharge. Once the decontamination process is complete, the
firefighter can
safely remove the ensemble and return to station.
Example 15: Off-site decontamination of PAH's using the decontamination
solution 1A from the firefighter's ensemble collected and stored after the
rescue mission.
After the rescue operation is complete, remove the ensemble and store in a 55-
gallon (gal) drum liner. Add 2 gal of the decontamination composition 1A
prepared from
Example 1 to the contaminated ensemble and wait for couple of hours. The
ensemble is then
transferred to another 55-gal drum liner containing water, and the ensemble is
thoroughly
rinsed and removed. The decontaminated ensemble is further cleaned in
accordance with
NFPA 1851 or standard AATCC method.
While at least one exemplary embodiment has been presented in the foregoing
detailed description of the invention, it should be appreciated that a vast
number of variations
exist. It should also be appreciated that the exemplary embodiment or
exemplary
.. embodiments are only examples, and are not intended to limit the scope,
applicability, or
configuration of the invention in any way. Rather, the foregoing detailed
description will
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provide those skilled in the art with a convenient road map for implementing
an exemplary
embodiment of the invention. It being understood that various changes may be
made in the
function and arrangement of elements described in an exemplary embodiment
without
departing from the scope of the invention as set forth in the appended claims.
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