WO2015049343A1

WO2015049343A1 - System for the detection and quantification of a uranium ion

Info

Publication number: WO2015049343A1
Application number: PCT/EP2014/071178
Authority: WO
Inventors: Nicolas DROGAT; Julien VERGNAUD; Robert Granet; Vincent CHALEIX; Vincent SOL; Vincent Gloaguen
Original assignee: Universite De Limoges
Priority date: 2013-10-02
Filing date: 2014-10-02
Publication date: 2015-04-09
Also published as: AU2014331103B2; FR3011333A1; AU2014331103A1; FR3011333B1

Abstract

The invention relates to the field associated with the detection or quantification of heavy metals, particularly uranium, present in natural areas, in preparation areas or in ores. The invention relates to a detection or quantification system comprising a coloured indicator selected from among azo-type pigments, combined with a preserving agent and with a coloration homogenisation agent.

Description

SYSTEM FOR DETECTION AND QUANTIFICATION OF A URANIUM ION

Description

The invention relates to the field of the detection or the quantification of heavy metals, in particular uranium, present in natural places, in places of preparation, in particular industrial preparation, or in ores.

The invention relates to a detection or quantification system comprising a color indicator selected from azo-type pigments combined with a preservative and a color homogenizer.

For the invention, the detection or the quantification of a heavy metal is implemented for the detection or the quantification of uranium.

Mineral exploration or mining, including uranium exploration or mining, requires the detection or quantification of uranium and, in particular, the detection or quantification of uranium ion.

The methods of mining and manufacturing uranium derived fuel also require the detection and quantification of heavy metals, especially in liquid media, particularly in liquid and acidic media.

The solutions resulting from the exploitation of heavy metals and in particular uranium often contain very large quantities of heavy metals. These heavy metals are generally very numerous to be present in these solutions.

Concentrations of heavy metals, particularly uranium, can vary widely depending on the exploration or exploitation conditions implemented. These concentrations may also vary from one deposit to another. The concentrations of the different heavy metals can also vary in important proportions.

There are techniques to measure the presence of a heavy metal in a medium. There are also techniques for quantifying a heavy metal in a medium. Thus, there may be mentioned alpha spectrometry, gamma spectrometry, X-ray spectrometry, fluorometry or ICP-MS spectrometry.

However, known techniques generally lead to high times or long periods of measurement.

These techniques are generally expensive and require sophisticated equipment and expensive. They are often difficult to implement quickly and flexibly, especially for measurements in a natural environment or outside a specialized laboratory.

Known techniques do not always allow the analysis of many samples. Known techniques can generate large amounts of waste.

These techniques may also require significant logistics, especially for the preparation, packaging and transport of samples.

Sophisticated and complex techniques of the state of the art present a high risk of manipulation.

The results obtained during the implementation of known techniques are not always reliable nor reproducible.

The invention proposes to provide a solution to all or part of the problems of known technologies of the state of the art.

The invention relates to a system for detecting or quantifying at least one uranium ion comprising a support impregnated with a composition comprising

^■ a colorimetric indicator selected from azo pigments, particularly 2,2 '- (1, 8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonique (arsenazo III) and its derivatives; 2,7-bis (2-hydroxy-3-sulfo-5-chlorophenylazo) acid

1,8-dihydroxynaphthalene-3,6-disulfonic acid (sulfochlorophenol) and its derivatives; their mixtures;

■ a preservative selected from an interpolymer of a d-Ci ₀ -alkylvinyl ether and a CRCI ₀ -alkyl-acid monoester CRCI ₀ alkyl-1, 2-ethylene-dicarboxylic acid, substituted or unsubstituted , in particular an interpolymer of methylvinyl ether and isopropyl monoester of maleic acid, in particular the poly (methyl vinyl ether-allymethyl ester-maleic acid) and its derivatives;

^■ a homogenization of the coloring agent, in particular glycerol, sodium citrate or a mixture of glycerol and sodium citrate.

Advantageously, the system according to the invention can be used for the detection of at least one uranium ion present in a liquid medium in very small quantities. The system according to the invention can in particular make it possible to detect amounts on the order of 1 ppm of a uranium ion in a medium. Also advantageously, the system according to the invention can be used for the quantification of at least one ion of uranium in a liquid medium.

Thus, it is possible to determine the amount of an uranium ion present in a medium.

According to the invention, the quantization also concerns semi-quantization. Semiquantition according to the invention makes it possible to determine the presence of at least one uranium ion in an amount within a range of particular quantities. Semi-quantification ranges accessible by means of the system according to the invention may for example be between 0 and 10 ppm, between 10 and 20 ppm or between 0 and 20 ppm or between 20 and 40 ppm.

Particular range ranges can therefore be determined for semiquantition using the system according to the invention. As examples of such ranges, it is possible to implement a system according to the invention corresponding to ranges of 5 ppm, 10 ppm, 15 ppm, 20 ppm, 25 ppm, 30 ppm, 40 ppm, 50 ppm, 75 ppm, 100 ppm, 120 ppm, 150 ppm, 200 ppm, 400 ppm, 500 ppm, 1000 ppm, etc.

Preferably, the semi-quantification system according to the invention allows measurements of quantities in ranges of 10 ppm. The system according to the invention can be implemented for the detection or for the quantification of at least one ion of uranium, preferably of a uranium ion.

Advantageously, the system according to the invention can be implemented for the detection or for the quantification of at least one uranium ion present in a small quantity.

Preferably, the uranium ion is uranyl (UO ₂ ²⁺ ).

In a preferred manner according to the invention, the support is a porous support or a support chosen from cellulose or a cellulose derivative; tissue ; a polymeric gel; a resin. A mixture of such materials can also be used as a support according to the invention.

The support does not modify the results of the detection or quantification according to the invention. It is absorbent.

As a preferred support, it is possible to use paper, for example 41 grade Whatman paper or strong, stiff, non-veneered paper, particularly Whatman 41 paper. The dimensions of the support according to the invention can vary widely depending on the particular destination of the detection or quantification system. The thickness of the support according to the invention may also vary. Advantageously, the support can be fixed on a means making it easy to handle. This means can take the form of a band, a strip, a sheet, a roll. This means can also have a certain volume. It can then be a rod or a stick.

Preferably, this means is a strip.

This means can be realized in different materials, for example paper, cardboard or a polymeric material, in particular a synthetic polymeric material, for example (poly) ethylene or polypropylene.

Its dimensions can be defined according to the envisaged conditions of use. For the system according to the invention, the impregnated support is fixed on this means for handling it. This attachment is advantageously performed by means of an adhesive or an adhesive.

Preferably, the system according to the invention comprises a colorimetric indicator chosen from pigments comprising an azo function, two azo functions or three azo functions.

Most preferably, the system according to the invention comprises a colorimetric indicator selected from pigments comprising two azo functions.

Preferably, the colorimetric indicator is a derivative of 2,2 '- (1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid. More preferably, the colorimetric indicator is 2,2 '- (1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid (arsenazo III), compound of formula (I):

Also preferably, the colorimetric indicator is a derivative of 2,7-bis (2-hydroxy-3-sulfo-5-chlorophenylazo) -1,8-di-hydroxynaphthalene-3,6-disulfonic acid, 2,7-bis (2-hydroxy-3-sulfo-5-chlorophenylazo) -1,8-dihydroxynaphthalene-3,6-disulfonic acid (sulfochlorophenol), compound of formula (II):

Advantageously, the colorimetric indicator may be a mixture of a 2,2 '- (1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid derivative and a derivative thereof. 2,7-bis (2-hydroxy-3-sulfo-5-chlorophenylazo) -1,8-dihydroxynaphthalene-3,6-disulfonic acid, especially a mixture of arsenazo III and sulfochlorophenol.

Advantageously, the preservative is selected from an interpolymer of a CrCio-alkyl vinyl ether and a d-Cio-alkyl-acid monoester CRCI ₀ alkyl-1, 2-ethylene-dicarboxylic for which the CrCi ₀ -alkyl is independently selected from methyl, ethyl, n-propyl or iso-propyl.

Preferably, the invention provides a system for detecting or quantifying a uranium ion comprising a carrier, made of cellulose or a cellulose derivative, for example paper, impregnated with a composition comprising

2,2 '- (1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid (arsenazo III);

^■ poly (monoethyl ester acid methyl vinyl ether-a / i-maleic);

^■ glycerol and sodium citrate. Advantageously, the invention provides a system whose composition comprises

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^■ 5 to 60% by weight of homogenization of the coloring agent.

Preferably, the invention provides a system whose composition comprises ^■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

^■ 10 to 50% by weight of color homogenizer. In a particularly advantageous manner, the invention provides a system whose composition comprises

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^■ 2 to 35% by weight of glycerol;

■ 2 to 35% by weight of sodium citrate.

In a particularly preferred manner, the invention provides a system whose composition comprises

^■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

■ 5 to 25% by weight of glycerol;

^■ 5 to 25% by weight of sodium citrate.

The system according to the invention allows the detection or the quantification of at least one uranium ion present in a liquid medium in very small quantities.

In particular, the system according to the invention allows the quantification of at least one uranium ion present in amounts ranging from 0 to 100 ppm.

Preferably, the system according to the invention allows the quantification of at least one uranium ion present in amounts ranging from 0 to 100 ppm. Advantageously, the detection or quantification system according to the invention can be implemented for larger quantities of uranium ion, in particular for quantities greater than 100 ppm, for example for quantities ranging from 100 to 500 ppm or from 100 to 1000 ppm or from 500 to 2000 ppm or from 100 to 10,000 ppm.

The system according to the invention then also comprises a retarding agent or a complexing agent competitor of the colorimetric indicator or a mixture of a retarding agent and a complexing agent competitor of the colorimetric indicator.

Advantageously, the retarding agent makes it possible to delay the coloration of the colorimetric indicator. The staining is thus shifted and occurs for larger amounts of uranium ion. Also advantageously, the retarding agent can constitute a partial screen or a partial barrier between the colorimetric indicator and the uranium ion.

Also advantageously, the complexing agent can bind to the uranium ion and form a complex with a fraction of the uranium ion present.

Also advantageously, the complexing agent can bind to the uranium ion because of a complexation constant lower than the complexing constant of the colorimetric indicator with respect to the uranium ion or else because of a complexation constant close to or even greater than the complexing constant of the colorimetric indicator with respect to the uranium ion.

In a preferred manner according to the invention, the retarding agent is chosen from polyvinylpyrrolidone and its derivatives. Polyvinylpyrrolidone is preferred. In a preferred manner according to the invention, the complexing agent is chosen from pyrophosphate or a bisphosphonate. A bis-phosphonate is preferred, in particular alendronate, etidronate, neridronate, risedronate, zoledronate, ibandronate, ethidronate or pamidronate. Also preferably, the system according to the invention combines the presence of polyvinylpyrrolidone as retarding agent and pyrophosphate or bisphosphonate, including alendronate, etidronate, neridronate, risedronate, zoledronate, ibandronate, ethidronate or pamidronate. Advantageously, the invention provides a system whose composition comprises

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^5-60 % by weight of color homogenizer;

^■ 0.5 to 35% by weight of a retarding agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of a preservative;

^■ 2 to 35% by weight of glycerol;

^■ 2 to 35% by weight of sodium citrate;

0.5 to 35% by weight of a retarding agent; or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^5-60 % by weight of a color homogenizer;

^■ 0.5 to 25% by weight of a complexing agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^■ 2 to 35% by weight of glycerol;

^■ 2 to 35% by weight of sodium citrate;

^■ 0.5 to 25% by weight of a complexing agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^5-60 % by weight of color homogenizer;

^■ 0.5 to 35% by weight of a retarding agent;

^■ 0.5 to 25% by weight of a complexing agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^■ 2 to 35% by weight of glycerol;

^■ 2 to 35% by weight of sodium citrate;

^■ 0.5 to 35% by weight of a retarding agent;

^■ 0.5 to 35% by weight of a complexing agent.

Preferably, the invention provides a system whose composition comprises

^■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

^■ 10 to 50% by weight of color homogenizer;

^■ 1 to 20% by weight of a retarding agent;

or

^■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of a preservative;

^■ 5 to 25% by weight of glycerol;

^■ 5 to 25% by weight of sodium citrate; 1 to 20% by weight of a retarding agent;

or

^■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

■ 10 to 50% by weight of a color homogenizer;

^■ 2 to 10% by weight of a complexing agent;

or

^■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

■ 5 to 25% by weight of glycerol;

^■ 5 to 25% by weight of sodium citrate;

^■ 2 to 10% by weight of a complexing agent;

or

^■ 0.9 to 2% by mass of colorimetric indicator;

■ 40 to 70% by weight of preservative;

^■ 10 to 50% by weight of color homogenizer;

^■ 1 to 20% by weight of a retarding agent;

^■ 2 to 10% by weight of a complexing agent;

or

■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

^■ 5 to 25% by weight of glycerol;

^■ 5 to 25% by weight of sodium citrate;

^■ 1 to 20% by weight of a retarding agent;

■ 2 to 10% by weight of a complexing agent.

The invention also provides a method for preparing a detection or quantification system according to the invention.

The preparation method according to the invention comprises

The preparation in a mixture of acetone and ethanol of a solution (S1) comprising

a colorimetric indicator selected from azo-type pigments, in particular 2,2 '- (1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid (arsenazo III) and its derivatives; 2,7-bis (2-hydroxy-3-sulfo-5-chlorophenylazo) -1,8-di-hydroxynaphthalene-3,6- disulfonic (sulfochlorophenol) and its derivatives; their mixtures;

a preserving agent chosen from an interpolymer of a C 10 ₀ -alkylvinyl ether and a substituted or unsubstituted C ₁ -C 12 -alkyl-1,2-ethylene-dicarboxylic acid CrC ₁ _O -alkyl-monoester, in particular an interpolymer of methylvinyl ether and isopropyl monoester of maleic acid, in particular the poly (methyl vinyl ether-ethyl-male-maleate) and its derivatives;

preparing an aqueous solution (S2) of at least one color homogenizer, in particular glycerol, sodium citrate or mixtures thereof;

the preparation of a composition by slow addition or by dropwise addition of the solution (S2) in the solution (S1);

impregnation of a support according to the invention by means of the composition. advantageous, the method of preparation according to the invention comprises

^■ the preparation into a mixture of acetone and ethanol to a solution (S1) comprising

a colorimetric indicator selected from azo-type pigments, in particular 2,2 '- (1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid (arsenazo III) and its derivatives; 2,7-bis (2-hydroxy-3-sulfo-5-chlorophenylazo) -1,8-di-hydroxynaphthalene-3,6-disulfonic acid (sulfochlorophenol) and its derivatives; their mixtures; a preserving agent chosen from an interpolymer of a C 10 ₀ -alkylvinyl ether and a substituted or unsubstituted C ₁ -C 12 -alkyl-1,2-ethylene-dicarboxylic acid CrC ₁ _O -alkyl-monoester, in particular an interpolymer of methylvinyl ether and isopropyl monoester of maleic acid, in particular the poly (methyl vinyl ether-ethyl-male-maleate) and its derivatives;

^■ preparing an aqueous solution (S2) of at least one homogenizing agent staining, especially glycerol, sodium citrate or mixtures thereof;

^■ the preparation of an aqueous solution (S3) comprising

a retarding agent chosen from polyvinylpyrrolidone and its derivatives; or o a complexing agent competitor of the colorimetric indicator and chosen from pyrophosphate or a bisphosphonate, in particular a bis-phosphonate, phosphonate selected from alendronate, etidronate, neridronate, risedronate, zoledronate, ibandronate, ethidronate, pamidronate; or a retarding agent chosen from polyvinylpyrrolidone and its derivatives and a complexing agent competitor of the colorimetric indicator and chosen from pyrophosphate or a bisphosphonate, in particular a bisphosphonate chosen from alendronate, etidronate and neridronate risedronate, zoledronate, ibandronate, ethidronate, pamidronate;

^■ preparing a composition

o by slow addition or by dropwise addition of the solutions (S2) and (S3) in the solution (S1); or

o by slow addition or by dropwise addition of the solution (S2) into the solution (S1) and then addition of the solution (S3) in the solution

(S1) + (S2); or

o by slow addition or by dropwise addition of the solution (S3) into the solution (S1) and addition of the solution (S2) in the solution

(S1) + (S3);

^■ impregnation of a support according to the invention by means of the composition.

Advantageously, during the preparation of the systems according to the invention, the impregnation of the support is carried out in the presence of a wetting agent, in particular a wetting agent chosen from a polyethoxylated fatty alcohol or an anionic surfactant compound such as a dioctyl sodium sulfosuccinate. The wetting agent may also be present within the solution (S1).

As wetting agent, Emulphor ON870 may be mentioned.

As anionic surfactant compound, mention may be made Brij 93 (polyethylene glycol oleyl ether, polyoxyethylene (2) oleyl ether).

The invention also provides a kit comprising at least one system according to the invention and a scale of 2 to 12 colors corresponding to ranges of concentration of the uranium ion in solutions calibrated for amounts of ion of uranium ranging from 0 to 100 ppm.

The system according to the invention then comprises a colorimetric indicator, a preservative and a color homogenizer.

Preferably, the color scale may comprise from 4 to 6 colors. The invention also provides another kit comprising at least one system according to the invention and a scale of 2 to 12 colors corresponding to ranges of concentration of the uranium ion in solutions calibrated for amounts of ion of uranium ranging from 100 to 500 ppm.

The system according to the invention then comprises a colorimetric indicator, a preserving agent, a color homogenizing agent and a retarding agent or a complexing agent. It can also combine a colorimetric indicator, a preservative, a color homogenizer, a retarding agent and a complexing agent.

Preferably, the color scale may comprise from 4 to 6 colors.

The colors may also correspond to ranges of uranium ion concentration in solutions calibrated for uranium ion amounts ranging from 100 to 1000 ppm or from 500 to 2000 ppm or from 100 to 10,000 ppm.

As an example of a color scale, the colors of the Pantone 2385EC, 258EC, 5275EC, 5405C, 3155EC, 322 EC universal color chart can be cited for uranium ion concentrations of 0 ppm, 10 ppm, 25 ppm, 50 ppm, 75 ppm and 100 ppm.

The invention also provides a method for detecting or quantifying at least one uranium ion.

Preferably, the detection or quantification method according to the invention is implemented to detect or quantify a uranium ion.

Also preferably, the detection or quantification method according to the invention is implemented to detect or to quantify at least one uranium ion present in a medium, liquid and acid, in an amount ranging from 0 to 100 ppm. This method includes

^■ bringing the system into contact with the liquid medium for a period ranging from 1 s to 1 hour, preferably from 1 s to 120 s; then

^■ comparing the coloration of the system with a scale of 2 to 12 colors corresponding to the ranges of ion concentration of uranium in the reference solutions calibrated for quantities of uranium ion from 0 to 100 ppm; then

^■ determining the presence of uranium ion and the ion concentration range of the uranium from the liquid medium, by identifying the color of the system with the corresponding color of the color scale. The system according to the invention implemented then comprises a colorimetric indicator, a preservative and a color homogenizer.

Also preferably, the method for detecting or quantifying uranium, present in a medium, liquid and acid, in an amount ranging from 100 to 500 ppm or ranging from 100 to 1000 ppm or from 500 to 2000 ppm or ranging from 100 to 10,000 ppm, of a system according to the invention. This method includes

the comparison of the coloration of the system with a scale of 2 to 12 colors corresponding to ranges of concentration of the uranium ion in calibrated reference solutions for amounts of uranium ion ranging from 100 to 500 ppm or ranging from 100 to 1,000 ppm or from 500 to 2,000 ppm or from 100 to 10,000 ppm; then

determining the presence of uranium ion and the uranium ion concentration range of the liquid medium by identifying the color of the system with the corresponding color of the color scale.

The system according to the invention implemented then comprises a colorimetric indicator, a preserving agent, a homogenizing agent for the coloration and a retarding agent or a complexing agent. It can also combine a colorimetric indicator, a preservative, a color homogenizer, a retarding agent and a complexing agent.

The advantageous, particular or preferred characteristics of the detection or quantification system according to the invention define preferred or preferred methods of preparation, kits or detection or quantification methods incorporating these characteristics.

When implementing the method for detecting or quantifying at least one uranium ion according to the invention, certain chemical elements or species may interfere with one or other of the elements of the system according to the invention. invention and lead to disturbances in the detection or quantification of at least one uranium ion.

In a particularly advantageous manner, the invention also provides a method for detecting or quantifying at least one uranium ion which makes it possible to avoid interference that may be caused by certain chemical elements or species.

Examples of elements or chemical species that can interfere during the implementation of the system according to the invention include: acetate; CN ^" ; Na ⁺ ; As; Co ²⁺ ; NH ₄ ⁺ ; Ag ⁺ ; Cr ³⁺ ; Ni ^2+; Al ³⁺ ; Cr0 ₄ ^2" ; N0 ₂ ^" ; ³⁺ ; Cu ²⁺ ; N0 ₃ ^" ; Ba ²⁺ ; Fe ²⁺ ; Pb ²⁺ ; Ca ²⁺ ; Fe ³⁺ ; P0 ₄ ^{3 "} ; Cd ²⁺ ; Hg ⁺ ; SO ₃ ^2" ; This ³⁺ ; K ⁺ ; S0 ₄ ^{2 "} citrate; Mn ²⁺ ; Zn ²⁺ ; CI ^" ; Mg ²⁺ .

The method according to the invention is particularly advantageous for the following elements or chemical species: CN ^" ; Ce ³⁺ ; Fe ²⁺ ; Fe ³⁺ ; Pb ²⁺ ; Cr0 ₄ ^2" and in particular Fe ²⁺ ; Fe ³⁺ ; Cr0 ₄ ^{2 "} .

For these chemical elements or species, interference may occur depending on the concentration of these chemical elements or species. The following concentrations of chemical elements or species from which these chemical elements or species can lead to interference:

In order to eliminate the interference that may occur with these chemical elements or species, the method for detecting or quantifying at least one uranium ion according to the invention is carried out in the presence of ascorbic acid or in the presence of an ascorbic acid derivative such as an ascorbate. Ascorbic acid is preferred.

Preferably, the method for detecting or quantifying at least one uranium ion according to the invention is then carried out in the presence of ascorbic acid or in the presence of an ascorbic acid derivative in a concentration. ranging from 0.4 to 20 mg for a sample volume of 1 mL. More preferably, this concentration ranges from 1 to

20 mg / mL of sample.

The invention also comprises a kit that can comprise, in addition to a kit for the detection or quantification of at least one uranium ion according to the invention, ascorbic acid or an ascorbic acid derivative such as an ascorbate . Such a kit may also include a tool for measuring the amount of useful ascorbic acid. The various aspects and advantageous properties of the invention can be illustrated by the following examples. These examples do not constitute a limitation of the scope of this invention.

Example 1: Detection and Quantification System for a Range of 0 to 100 ppm Uranium

A first composition comprising:

^■ 25 mg of 2,2 '- (1, 8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonique (arsenazo III);

^■ 1, 0 g of poly (monoethyl ester of methyl vinyl ether-alt-maleic acid) (50 wt% in ethanol);

^■ 550 polyethylene μΙ_ polyoxyethylene (2) oleyl ether (Brij 93 Sigma Aldrich);

■ 15 ml of absolute ethanol;

^■ 3 ml of acetone.

A second composition is prepared comprising:

^■ 250 mg of trisodium citrate;

^■ 250 mg of glycerol;

■ 15 mL of water.

An impregnating composition is prepared from the second composition which is added to the first drip composition.

A filter paper support (type 8s paper - square size: 1 x 1 cm) is prepared.

The support is immersed in the impregnating composition.

It is dried by drying in an oven (60 ° C. for 120 minutes).

The impregnated support is glued on a PVC strip (1 x 7 cm) using double-sided tape.

The device according to the invention is stable. Indeed, after accelerated aging, the results reveal a stability of at least one year.

A 6-color scale corresponding to increasing concentrations of uranium ion is prepared separately. In 10 ml pill containers, 5 uranium ion solutions (uranyl acetate) in an aqueous solution of HNO ₃ (1.1% M / V) are prepared with respective concentrations of 20, 40, 60, 80. and 100 ppm of uranium ion.

In a sixth pillbox, place 10 mL of aqueous solution HN0 ₃ concentration 1, 1% M / V.

Six devices according to the invention are plunged separately into each of the six pill containers for a period of 60 s and then deposited on a white paper support in order to increase the contrast with the colors corresponding to the different concentrations of uranium. A 6-color scale corresponding to uranium concentrations ranging from 0 to 100 ppm is obtained. The colors (Table 1) correspond to the coloration of the colorimetric indicator of each sample according to the colors coded by the color code scale. corn (http://www.code-couleur.com/index.html).

Table 1: color scale

The color scale then makes it possible to compare the color obtained for a particular sample and to determine the presence and concentration of uranium by visual comparison with the color closest to the scale. Example 2 Quantification of Uranium in a Solution of a Sample and Specificity of the Detection and Quantification Method According to the Invention

An aqueous acidic M composition (from 10 ml of water and at a concentration of 1.1% M / V of HNO ₃ ) comprising 15 metal species (As, Ba, Ca, Cd, Co, Cu, Fe) is prepared. ²⁺ , Fe ³⁺ , Hg, Mg, Mn, Ni, Pb, Zn, UO ₂ ²⁺ ) at 50 ppm of each chemical species.

In an analogous manner, 15 acidic aqueous compositions (from 10 ml of water and at a concentration of 1.1% M / V of HNO ₃ ) are prepared, each comprising one of these 15 metal species (As, Ba, Ca, Cd, Co, Cu, Fe ²⁺ , Fe ³⁺ , Hg, Mg, Mn, Ni, Pb, Zn, UO ₂ ²⁺ ) at 100 ppm.

A device according to the invention (Example 1) is immersed in each of the 16 compositions for 60 seconds.

Then, after drying, the coloration obtained is compared with the color scale according to Example 1.

The device immersed in the composition comprising only uranium has a light marine green color (code: # FF1493). The coloring corresponds to the concentration of 100 ppm uranium.

The device immersed in the composition comprising the composition M has an intermediate color between the dark slate blue color (code: # 483D8B) and the blue cobalt color (code: # FF22427C). The coloration thus corresponds to the concentration of 50 ppm corresponding to the intermediate color between the concentrations of 40 ppm and 60 ppm uranium.

The other 14 compositions lead to dark pink colorations (code: # FF1493). These stains correspond to the concentration of 0 ppm uranium.

The device according to the invention thus allows the quantification of the uranium present in a reference composition but also in a very complex composition comprising 14 other metal chemical species in an identical concentration. The device therefore allows accurate and reliable measurements.

Claims

claims

1. System for the detection or quantification of at least one uranium ion comprising a support impregnated with a composition comprising

A colorimetric indicator selected from azo-type pigments, in particular 2,2 '- (1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid (arsenazo III) and its derivatives; 2,7-bis (2-hydroxy-3-sulfo-5-chlorophenylazo) -1,8-dihydroxynaphthalene-3,6-disulfonic acid (sulfochlorophenol) and its derivatives; their mixtures;

- A preservative selected from an interpolymer of a d-Ci ₀ -alkylvinyl ether and a CrCi ₀ -alkyl-1,2-ethylene-dicarboxylic acid CrCi ₀ -alkyl-monoester, substituted or unsubstituted , in particular an interpolymer of methylvinyl ether and isopropyl monoester of maleic acid, in particular the poly (methyl vinyl ether-allymethyl ester-maleic acid) and its derivatives;

an agent for homogenizing the coloration, in particular glycerol, sodium citrate or a mixture of glycerol and sodium citrate.

2. System according to claim 1 wherein the support is a porous support or a support selected from cellulose or a cellulose derivative, especially paper, for example Whatman paper grade 41; tissue ; a polymeric gel; a resin.

3. System according to claims 1 or 2 for the detection or quantification of a uranium ion comprising a carrier, cellulose or a cellulose derivative, for example paper, impregnated with a composition comprising

^■ poly (monoethyl ester acid methyl vinyl ether-a / maleic-i);

^■ glycerol and sodium citrate.

4. System according to claims 1 to 3, the composition of which comprises

^■ 0.5 to 5% by weight or 0.9 to 2% by mass of colorimetric indicator;

^■ 25 to 80% by mass or 40 to 70% by weight of preservative;

^■ 5 to 60% by weight of agent or 10 to 50% by weight of homogenization of the coloring;

or ^■ 0.5 to 5% by weight or 0.9 to 2% by mass of colorimetric indicator;

^■ 25 to 80% by mass or 40 to 70% by weight of preservative;

^■ 2 to 35% by weight or 5 to 25% by weight of glycerol;

^■ 2 to 35% by weight or 5 to 25% by weight of sodium citrate.

5. System according to claims 1 to 4, the composition of which also comprises

^■ a retarding agent selected from polyvinylpyrrolidone and its derivatives; or

^■ a complexing agent competitor of the colorimetric indicator and selected from pyrophosphate or a bis-phosphonate, especially a bis-phosphonate selected from alendronate, etidronate, neridronate, risedronate, zoledronate, ibandronate, the ethidronate, pamidronate; or

^■ a retarding agent selected from polyvinylpyrrolidone and derivatives thereof and a complexing agent competitor of the colorimetric indicator and selected from pyrophosphate or a bis-phosphonate, especially a bis-phosphonate selected from alendronate, etidronate, neridronate, risedronate, zoledronate, ibandronate, ethidronate, pamidronate.

6. System according to claims 1 to 5, the composition of which comprises

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^5-60 % by weight of color homogenizer;

^■ 0.5 to 35% by weight of a retarding agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of a preservative;

^■ 2 to 35% by weight of glycerol;

^■ 2 to 35% by weight of sodium citrate;

^■ 0.5 to 35% by weight of a retarding agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^5-60 % by weight of a color homogenizer;

^■ 0.5 to 25% by weight of a complexing agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator; ^■ 25 to 80% by weight of preservative;

^■ 2 to 35% by weight of glycerol;

^■ 2 to 35% by weight of sodium citrate;

^■ 0.5 to 25% by weight of a complexing agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^5-60 % by weight of color homogenizer;

^■ 0.5 to 35% by weight of a retarding agent;

0.5 to 25% by weight of a complexing agent;

or

^■ 0.5 to 5% by weight of colorimetric indicator;

^■ 25 to 80% by weight of preservative;

^■ 2 to 35% by weight of glycerol;

■ 2 to 35% by weight of sodium citrate;

^■ 0.5 to 35% by weight of a retarding agent;

^■ 0.5 to 35% by weight of a complexing agent;

or

^■ 0.9 to 2% by mass of colorimetric indicator;

■ 40 to 70% by weight of preservative;

^■ 10 to 50% by weight of color homogenizer;

^■ 1 to 20% by weight of a retarding agent;

or

^■ 0.9 to 2% by mass of colorimetric indicator;

■ 40 to 70% by weight of a preservative;

^■ 5 to 25% by weight of glycerol;

^■ 5 to 25% by weight of sodium citrate;

^■ 1 to 20% by weight of a retarding agent;

or

■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

^■ 10 to 50% by weight of a color homogenizer;

^■ 2 to 10% by weight of a complexing agent;

or

0.9 to 2% by weight of colorimetric indicator; ^■ 40 to 70% by weight of preservative;

^■ 5 to 25% by weight of glycerol;

^■ 5 to 25% by weight of sodium citrate;

^■ 2 to 10% by weight of a complexing agent;

^■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

^■ 10 to 50% by weight of homogenization of the coloring agent

^■ 1 to 20% by weight of a retarding agent;

^■ 2 to 10% by weight of a complexing agent;

^■ 0.9 to 2% by mass of colorimetric indicator;

^■ 40 to 70% by weight of preservative;

^■ 5 to 25% by weight of glycerol;

^■ 5 to 25% by weight of sodium citrate;

^■ 1 to 20% by weight of a retarding agent;

^■ 2 to 10% by weight of a complexing agent.

7. A method of preparing a system defined by claims 1 to 4 comprising the preparation in a mixture of acetone and ethanol of a solution (S1) comprising

a colorimetric indicator selected from azo-type pigments, in particular 2,2 '- (1,8-dihydroxy-3,6-disulfonaphthylene-2,7-bisazo) bisbenzenearsonic acid (arsenazo III) and its derivatives; 2,7-bis (2-hydroxy-3-sulfo-5-chlorophenylazo) -1,8-di-hydroxynaphthalene-3,6-disulfonic acid (sulfochlorophenol) and its derivatives; their mixtures;

The preparation of an aqueous solution (S2) of at least one homogenizing agent for the coloration, in particular glycerol, sodium citrate or their mixtures; ^■ the preparation of a composition according to claims 1 to 4 by slow addition or by dropwise addition of the solution (S2) in the solution (S1);

^■ impregnating a carrier according to claims 1 to 4 by means of the composition, optionally in the presence of a wetting agent, in particular a wetting agent selected from a polyethoxylated fatty alcohol or a surfactant anion such compound dioctyl sodium sulfosuccinate.

8. A method of preparing a system defined by claims 5 or 6 comprising

o a preservative selected from an interpolymer of a C ₁ -C ₁₀ - alkyl vinyl ether and a d-Cio-alkyl-acid monoester CRCI ₀ alkyl-1, 2-ethylene-dicarboxylic acid, substituted or unsubstituted substituted, in particular an interpolymer of methylvinyl ether and isopropyl monoester of maleic acid, in particular poly (methyl vinyl ether-male-methyl-ethyl ester) and its derivatives;

^■ the preparation of an aqueous solution (S3) comprising

a retarding agent chosen from polyvinylpyrrolidone and its derivatives; or o a complexing agent competitor of the colorimetric indicator and chosen from pyrophosphate or a bisphosphonate, in particular a bisphosphonate chosen from alendronate, etidronate, neridronate, risedronate, zoledronate, ibandronate, ethidronate, pamidronate; or a retarding agent chosen from polyvinylpyrrolidone and its derivatives and a complexing agent competitor of the colorimetric indicator and chosen from pyrophosphate or a bisphosphonate, in particular a bisphosphonate chosen from alendronate, etidronate and neridronate risedronate, zoledronate, ibandronate, ethidronate, pamidronate; ^■ the preparation of a composition according to claims 5 or 6 o by slow addition or by dropwise addition of the solutions (S2) and (S3) in the solution (S1); or

(S1) + (S2); or

o by slow addition or by dropwise addition of the solution (S3) into the solution (S1) and addition of the solution (S2) in the solution (S1) + (S3);

■ impregnating a support according to claims 1 to 6 by means of the composition, optionally in the presence of a wetting agent, in particular a wetting agent selected from a polyethoxylated fatty alcohol or an anionic surfactant compound such a dioctyl sodium sulfosuccinate.

9. Kit including

^■ at least one system according to claims 1 to 4 and a scale of 2 to 12 colors or a scale of 4 to 6 or a color scale of 6 colors, corresponding to concentration ranges of the ion of uranium in calibrated solutions for uranium ion quantities ranging from 0 to 100 ppm; or

^■ at least one system according to claims 5 or 6 and a scale of 2 to 12 colors or a scale of 4 to 6 or a color scale of 6 colors, indiscriminately corresponding to concentration ranges of the ion of uranium in Calibrated solutions for uranium ion quantities ranging from 100 to 500 ppm or from 100 to 1000 ppm or from 500 to 2000 ppm or from 100 to 10,000 ppm.

10. A method for detecting or quantifying at least one uranium ion, present in a medium, liquid and acid, in an amount ranging from 0 to 100 ppm by means of a system according to claims 1 to 4; comprising

^■ determining the presence of uranium ion and the ion concentration range of the uranium from the liquid medium, by identifying the color of the system with the corresponding color of the color scale.

1 1. Method for the detection or quantification of at least one uranium ion present in a medium, liquid and acid, in an amount ranging from 100 to 500 ppm or from 100 to 1000 ppm or from 500 to 2,000 ppm or from 100 to 10,000 ppm, by means of a system according to claims 5 or 6; comprising

bringing the system into contact with the liquid medium for a period ranging from 1 s to 1 hour, preferably from 1 s to 120 s; then

^■ comparison of the color of the system with a scale of 2 to 12 colors corresponding to ranges of concentration of the uranium ion in reference solutions calibrated for uranium ion quantities ranging from 100 to 500 ppm or ranging from 100 to 1,000 ppm or from 500 to 2,000 ppm or from 100 to 10,000 ppm; then

^■ determining the presence of uranium ion and the uranium ion concentration range of the liquid medium by identifying the color of the system with the corresponding color of the color scale.

12. A method for the detection or quantification of at least one uranium ion according to one of claims 10 or 11, implemented in the presence of ascorbic acid or in the presence of an ascorbic acid derivative, in a concentration ranging from 0.4 to 20 mg / mL of sample; or a concentration of 1 to 20 mg / mL of sample or a concentration of 1 mg / mL of sample.