CN111269761A - Decontamination liquid and application thereof in decontamination of actinide nuclide and transition metal nuclide pollution - Google Patents
Decontamination liquid and application thereof in decontamination of actinide nuclide and transition metal nuclide pollution Download PDFInfo
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- CN111269761A CN111269761A CN202010090235.XA CN202010090235A CN111269761A CN 111269761 A CN111269761 A CN 111269761A CN 202010090235 A CN202010090235 A CN 202010090235A CN 111269761 A CN111269761 A CN 111269761A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/06—Hydroxides
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/10—Salts
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
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Abstract
The invention belongs to the technical field of decontamination solutions, and relates to a decontamination solution and application thereof in decontamination of actinide nuclide and transition metal nuclide pollution. Every 100 weight portions of the decontamination solution contains 0.8 to 1.2 portions of 2-hydroxyphosphonoacetic acid, 6 to 8 portions of nitrilotrimethylene phosphate, 6 to 8 portions of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 0.8 to 1.2 portions of ethylene diamine tetramethylene phosphate and 3 to 5 portions of hydroxyethylidene diphosphonic acid. The decontamination liquid and the application thereof in decontamination of actinide nuclide and transition metal nuclide pollution can be better used for decontamination of skin actinide nuclide and transition metal nuclide pollution.
Description
Technical Field
The invention belongs to the technical field of decontamination solutions, and relates to a decontamination solution and application thereof in decontamination of actinide nuclide and transition metal nuclide pollution.
Background
With the frequent occurrence of nuclear accidents and nuclear terrorist attacks in recent years, nuclear weapons are actively researched and developed and a large number of nuclear tests are carried out in various countries, and the nuclear safety protection is highly emphasized.
In 1986, when the chernobiles accident occurred, up to 8 tons of nuclear waste was ejected into the sky, and contained a large amount of radionuclides, iodine, cobalt, cesium, uranium, plutonium, and the like, which were dispersed into the environment, causing serious nuclear contamination to local residents, mainly body surface contamination, oral cavity, respiratory tract contamination, and nuclides introduced into the body through wound contamination and diet, thereby causing serious in vitro and in vivo irradiation.
In addition, in recent years, the terrorist nuclear attack and frequent nuclear explosion experiments generate a great amount of radioactive dust, the parts most likely to be polluted by the radioactive dust are mainly naked skin, oral cavity, nasal cavity, hair and the like, external irradiation is directly caused, and long-time radioactive nuclide can enter the human body through the parts such as skin absorption, digestive tract and respiratory tract. Once entering blood, these nuclides can be rapidly deposited in viscera to cause internal irradiation, and the chemical toxicity of heavy metals can cause renal failure, liver and kidney insufficiency, lung cancer, bone cancer and the like, which can cause serious death.
In view of the above, it is first required to perform decontamination treatment immediately when the radionuclide is stained on the skin surface, so as to reduce the radionuclide from entering the body as much as possible. The nuclide decontamination solution is a detergent which can be used for cleaning the nuclide, reducing the residue of the nuclide on the surface of skin and avoiding the nuclide from entering the body as much as possible. Aiming at the decontamination of actinides and transition metal nuclides, the essence of improving the decontamination effect of the decontamination solution is that a few low-toxicity actinide chelating agents are added, in the process of washing, the liquid can wash away dust on the surface of the skin, and soluble radionuclide which is difficult to wash and is stuck on the surface of the skin can be complexed by the chelating agents in the decontamination solution and then washed away, so that the effect of efficiently decontaminating is achieved.
Disclosure of Invention
The invention aims at providing a decontamination solution which can be better used for decontaminating skin actinide nuclides and transition metal nuclides.
To achieve this object, in a basic embodiment, the present invention provides a decontamination solution comprising, per 100 parts by weight of the decontamination solution, 0.8 to 1.2 parts of 2-hydroxyphosphonoacetic acid, 6 to 8 parts of nitrilotrimethylene phosphate, 6 to 8 parts of 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 0.8 to 1.2 parts of ethylenediaminetetramethylenephosphoric acid, and 3 to 5 parts of hydroxyethylidene diphosphonic acid.
In a preferred embodiment, the present invention provides a decontamination solution, wherein the decontamination solution comprises, per 100 parts by weight of the decontamination solution, 1 part of 2-hydroxyphosphonoacetic acid, 7 parts of nitrilotrimethylene phosphate, 7 parts of 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 1 part of ethylenediaminetetramethylenephosphoric acid, and 4 parts of hydroxyethylidene diphosphonic acid.
In a preferred embodiment, the invention provides a decontamination solution, wherein the decontamination solution further comprises 0.01-1 part of a humectant selected from one or more of butanediol, glycerol, propylene glycol, dipropylene glycol and hyaluronic acid.
In a preferred embodiment, the invention provides a decontamination solution, wherein the decontamination solution further comprises 0.1-2 parts of an inorganic salt electrolyte selected from one or more of sodium chloride, potassium chloride and calcium chloride.
In a preferred embodiment, the present invention provides a decontamination solution, wherein the decontamination solution further comprises 1-10 parts of an inorganic base selected from sodium hydroxide and/or potassium hydroxide.
The second purpose of the invention is to provide the application of the decontamination liquid for decontaminating skin actinide nuclides and transition metal nuclides, so that the decontamination liquid can be better used for decontaminating skin actinide nuclides and transition metal nuclides.
To achieve this object, in a basic embodiment, the present invention provides the use of the above-described decontamination solution for decontamination of skin actinide and transition metal nuclides.
In a preferred embodiment, the invention provides the use of an above-described decontamination solution for decontamination of skin actinide and transition metal nuclides, wherein said actinide is uranium and/or thorium.
In a preferred embodiment, the present invention provides the use of the above-described decontamination solution for decontamination of skin actinide and transition metal nuclides, wherein said transition metal nuclide is cesium and/or cobalt.
The invention has the beneficial effects that the decontamination liquid and the application thereof in decontamination of actinide nuclide and transition metal nuclide pollution can be better used for decontamination of skin actinide nuclide and transition metal nuclide pollution.
Detailed Description
The following examples further illustrate specific embodiments of the present invention.
Example 1: preparation of decontamination solution
A decontamination solution (each 100g of decontamination solution contains 1g of 2-hydroxyphosphonoacetic acid, 7g of nitrilotrimethylene phosphate, 7g of 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 1g of ethylene diamine tetramethylene phosphate, 4g of hydroxyethylidene diphosphonic acid, 0.1g of a humectant (glycerin), 0.9g of an inorganic salt electrolyte (sodium chloride), 8.8g of potassium hydroxide and the balance of water) is prepared by the following method:
dissolving 2-hydroxyphosphonoacetic acid (produced by Huaweiruike corporation), nitrilotrimethylene phosphoric acid (produced by Saien chemical technology Co., Ltd.), 2-phosphonobutane-1, 2, 4-tricarboxylic acid (produced by Annagi chemical technology Co., Ltd.), ethylene diamine tetramethylene phosphoric acid (produced by Shanghai Tatanke technology Co., Ltd.), and hydroxyethylidene diphosphonic acid (produced by Shanghai Mirui chemical technology Co., Ltd.) in ultrapure water, adding a humectant, an inorganic salt electrolyte and potassium hydroxide, stirring and performing ultrasonic treatment for 10min to obtain the product.
Example 2: decontamination test of skin Actinidia nuclide uranium and thorium contamination with decontamination solution of example 1
84.4mg of UO are weighed out2(NO3)2·6H2Dissolving O into 20mL of aqueous solution to obtain stock solution of nuclide uranium; weighing 101.4mg Th (NO)3)4·6H2O dissolved in 20mL of water to obtain stock solution of nuclide thorium for the following study.
1. Experimental methods
(1) Marking, grouping
12 guinea pigs were divided into 4 groups of 3 replicates each. The control group was designated (S1, S2, S3) and the experimental group was designated (P1, P2, P3), and the guinea pigs were depilated and divided into four regions a, b, c, d, each of which was about 1cm2 (representing different exposure times: 0h, 2h, 6h, 12h, respectively).
(2) Contamination with drugs
20 mul of stock solution of uranium and thorium is taken by a 20 mul of pipette and evenly smeared on the corresponding area of the guinea pig, after the skin surface is dried, the contaminated area is covered by a preservative film, so that the guinea pig is prevented from generating cross contamination in the moving process.
(3) Decontamination
According to different contamination times, decontamination is carried out after 0h, 2h, 6h and 12h of contamination respectively, 5mL of decontamination solution is taken by a 5mL pipette gun to wash contaminated skin for 4 times, and 250mL of beaker is used for receiving the washed decontamination solution to be tested. The control group was rinsed 4 times with 5mL saline using a 5mL pipette, and the rinsed decontaminant was also added to a 250mL beaker.
(4) Measurement of nuclide concentration in a sample
After weighing and recording the samples in each beaker, carrying out aqua regia digestion, adding water for dilution, weighing, filtering and measuring the content of uranium and thorium by using ICP-OES (thermo Fisher company, USA).
2. Results of the experiment
As shown in Table 1, because a certain experimental error may exist in the contamination process, within the experimental error range, the contamination liquid can be immediately decontaminated and decontaminated after 2h of contamination, the decontamination liquid can achieve a one-hundred-percent decontamination effect, the decontamination efficiency of 93.65 +/-5.89% can still be achieved after 6h of contamination, and 77.52 +/-10.48% of uranium on the skin surface can be removed even if 12h of decontamination is delayed. However, the control group has a very limited decontamination effect of washing the uranium on the whole skin surface with normal saline, only 50.22 ± 24.99% of the uranium can be decontaminated immediately, the decontamination efficiency (the decontamination efficiency is equal to the content of the nuclein in the decontamination solution/the content of the nuclide in the stock solution x 100%) is reduced rapidly along with the increase of the contamination time, only 11.72 ± 1.00% of the uranium can be decontaminated after 12h of contamination, and the nuclide remaining on the skin surface can enter the body through the skin along with the increase of the time, thereby causing internal irradiation. The root cause that the washing and disinfecting liquid can efficiently remove nuclide uranium on the surface of the whole skin is that the organic phosphoric acid chelating agent can efficiently chelate the uranium on the surface of the skin, and even if the uranium is combined with the protein on the surface of the skin, the organic phosphoric acid can still compete for chelating the uranium to form a soluble complex.
Table 1 uranium decontaminated efficiency of physiological saline and decontaminant solution to uranium after 0h, 2h, 6h, 12h of intact skin infected with uranium nuclide (n is 3,
) (test for significance of experimental group and control group: p<0.05，**p<0.01，***p<0.001)
Table 2-washing efficiency of thorium by saline and washing liquid after 0h, 2h, 6h and 12h of complete skin contaminated by thorium nuclide (n is 3,
) (test for significance of experimental group and control group: p<0.05，**p<0.01，***p<0.001)
As can be seen from the results in Table 2, within experimental error, 94.43 + -2.92% of the nuclide thorium can be immediately washed and decontaminated by the decontamination solution, and the nuclide thorium on the skin surface can be almost completely removed, while the control group can only remove 32.92 + -11.79% of the thorium on the skin surface. With the prolonged contamination time, the decontamination solution can remove at least about 50% of thorium on the skin surface, the control group has only 2.95 +/-1.91% of decontamination efficiency after 12 hours of washing, and the decontamination efficiency of the thorium by the decontamination solution is at least 20 times higher than that of the control group. Therefore, the organic phosphoric acid chelating agent can effectively chelate the thorium on the surface of the skin, and further improves the decontamination effect of the thorium.
The results show that after 0h, 2h, 6h and 12h of contamination, the decontamination solution can achieve hundred percent decontamination effect within 6h of uranium contamination, 77.52 +/-10.48 percent of uranium can be removed after 12h of decontamination is delayed, and 51.53 +/-6.12 percent of thorium on the surface of skin can be removed after 12h of decontamination is delayed.
Example 3: decontamination test of decontamination solution of example 1 for cesium and cobalt contamination of skin transition metal nuclides
50.7mg of CsCl, a stable isotope salt of cesium, are weighed out2Dissolving into 20mL of aqueous solution to obtain a cesium stock solution; 88.1mg of CoCl, a stable isotope salt of cobalt, was weighed out2The solution was dissolved in 20mL of aqueous solution to obtain a stock solution of cobalt for the following study.
1. Experimental methods
(1) Marking, grouping
12 guinea pigs were divided into 4 groups of 3 replicates each. The control group was designated (S1, S2, S3) and the experimental group was designated (P1, P2, P3), and the guinea pigs were depilated and divided into four regions a, b, c, d, each of which was about 1cm2 (representing different exposure times: 0h, 2h, 6h, 12h, respectively).
(2) Contamination with drugs
20 mul of cesium and cobalt stock solution is uniformly smeared on corresponding areas of guinea pigs by a 20 mul of pipette gun, and after the skin surfaces are dried, the contaminated areas are covered by preservative films to prevent the guinea pigs from generating cross contamination in the moving process.
(3) Decontamination
According to different contamination times, decontamination is carried out after 0h, 2h, 6h and 12h of contamination respectively, 5mL of decontamination solution is taken by a 5mL pipette gun to wash contaminated skin for 4 times, and 250mL of beaker is used for receiving the washed decontamination solution to be tested. The control group was rinsed 4 times with 5mL saline using a 5mL pipette, and the rinsed decontaminant was also added to a 250mL beaker.
(4) Measurement of nuclide concentration in a sample
The samples in each beaker were weighed, recorded, digested with aqua regia, diluted with water, weighed, filtered, and then assayed for cobalt and cesium by ICP-OES (thermo fisher, usa).
2. Results of the experiment
As can be seen from Table 3, within experimental error, both the normal saline and the scrub completely removed the cobalt from the skin surface in the immediate scrub group. Along with the prolonging of the infection time to 2 hours, the decontamination efficiency of the physiological saline is reduced to 38.14 +/-16.14%, and the decontamination solution can still completely remove the cobalt on the surface of the skin. After 6h and 12h of cobalt surface infection, although normal saline has a certain decontamination effect on cobalt, the decontamination liquid obviously improves the decontamination efficiency on cobalt, and can still maintain about 40 percent of decontamination efficiency after 12h of decontamination. The result shows that the organic phosphoric acid chelating agent has good decontamination effect on nuclide cobalt, although the delayed decontamination effect is not as good as the decontamination effect on nuclide uranium and thorium, compared with carboxylic acid chelating agent DTPA or EDTA, the phosphoric acid chelating agent has stronger affinity to cobalt, namely has better decontamination effect.
Table 3 decontamination efficiency of cobalt by physiological saline and decontamination solutions after 0h, 2h, 6h, 12h of intact skin infected with cobalt transition metal (n-3,
) (test for significance of experimental group and control group: p<0.05，**p<0.01，***p<0.001)
Table 4 decontamination efficiency of cesium by saline and decontamination solutions after 0h, 2h, 6h, 12h of intact skin with cesium transition metal (n-3,
) (test for significance of experimental group and control group: p<0.05，**p<0.01，***p<0.001)
As shown in Table 4, within the experimental error range, after 0h and 2h of cesium contamination, the decontamination effect of the stable isotope cesium by the physiological saline and the decontamination solution is basically consistent, which indicates that the action force of cesium ions to the skin surface is weaker in a short time when the cesium ions are contaminated to the skin, and the cesium ions are easier to wash. Along with the prolonging of the contamination time, the adhesion between cesium and the skin or the action of cesium ions and epidermal cell membrane protein is enhanced, the cesium on the surface of the skin is difficult to wash by normal saline, the cesium on the surface of the skin can be effectively chelated by the decontamination solution, and 62.47 +/-8.38% of the cesium on the surface of the skin can be removed even after 12 hours of decontamination, so that the decontamination solution is obviously superior to the normal saline. Therefore, the organic phosphoric acid chelating agent has a good effect of delaying decontamination on the nuclide cesium.
The above results show that the decontamination solution can achieve about 70% decontamination effect on cobalt and cesium after a delay of 6 hours, and can remove about 40% of cobalt and 60% of cesium on the skin surface after a delay of 12 hours.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (8)
1. The decontamination solution is characterized in that: every 100 weight portions of the decontamination solution contains 0.8 to 1.2 portions of 2-hydroxyphosphonoacetic acid, 6 to 8 portions of nitrilotrimethylene phosphate, 6 to 8 portions of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 0.8 to 1.2 portions of ethylene diamine tetramethylene phosphate and 3 to 5 portions of hydroxyethylidene diphosphonic acid.
2. The decontamination solution of claim 1, wherein: every 100 weight portions of the decontamination solution contain 1 portion of 2-hydroxyphosphonoacetic acid, 7 portions of nitrilotrimethylene phosphate, 7 portions of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 1 portion of ethylene diamine tetramethylene phosphate and 4 portions of hydroxyethylidene diphosphonic acid.
3. The decontamination solution of claim 1 or 2, wherein: the decontamination solution also contains 0.01-1 part of humectant selected from one or more of butanediol, glycerol, propylene glycol, dipropylene glycol and hyaluronic acid.
4. The decontamination solution of claim 1 or 2, wherein: the decontamination solution also contains 0.1-2 parts of inorganic salt electrolyte selected from one or more of sodium chloride, potassium chloride and calcium chloride.
5. The decontamination solution of claim 1 or 2, wherein: the decontamination solution also contains 1-10 parts of inorganic alkali selected from sodium hydroxide and/or potassium hydroxide.
6. Use of a decontamination solution according to any one of claims 1-5 for decontamination of skin actinide and transition metal nuclides.
7. Use according to claim 6, characterized in that: the actinide nuclide is uranium and/or thorium.
8. Use according to claim 6, characterized in that: the transition metal species is cesium and/or cobalt.
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Cited By (3)
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| CN112494368A (en) * | 2020-10-12 | 2021-03-16 | 苏州大学 | Composition for radionuclide contamination decontamination and preparation method and application thereof |
| CN113563980A (en) * | 2021-08-27 | 2021-10-29 | 核工业北京化工冶金研究院 | Uranium radioactive decontaminant and uranium removing method of uranium-containing device |
| CN115869212A (en) * | 2022-12-09 | 2023-03-31 | 中国辐射防护研究院 | Transition metal nuclide body surface pollution decontamination agent and preparation method thereof |
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