METHOD FOR ASSESSING THE CONCENTRATION OF URANIUM IN A SAMPLE BY GAMMA SPECTROMETRY, AND ASSOCIATED DEVICE

Abstract

A method for assessing the mass concentration of uranium in a sample of uranium-bearing material by gamma spectrometry, includes a) acquiring (200) an energy spectrum of gamma radiation from the sample using a scintillator detector, the energy spectrum (100) comprising at least a first energy band (110) between 87 keV and 110 keV, and a second energy band (120) between 560 keV and 660 keV, the second energy band comprising at least one energy line (130) at 609 keV from .sup.214Bi, b) calculating (210) an initial mass concentration of uranium (Cm.sub.U0) using the energy spectrum, c) measuring (220) a parameter representative of the height of the sample and a parameter representative of the density of the sample, d) calculating (230) a corrective coefficient (K), and e) calculating (240) a corrected mass concentration of uranium (Cm.sub.U) using the initial mass concentration of uranium (Cm.sub.U0) and the corrective coefficient (K).

Claims

1-10. (canceled)

11. A method for assessing a concentration of uranium in a sample of uranium-bearing material by gamma spectrometry, the sample having a density and a height, the method comprising: acquiring an energy spectrum of gamma radiation from the sample using a scintillator detector, the energy spectrum comprising at least a first energy band between 87 keV and 110 keV, and a second energy band between 560 keV and 660 keV, the second energy band comprising at least one energy line at 609 keV of .sup.214Bi; calculating an initial mass concentration of uranium using an area of the first energy band, an area of the second energy band, and a net area of the 609 keV energy line of .sup.214Bi; measuring a parameter that is representative of the height of the sample and a parameter that is representative of the density of the sample; calculating a corrective coefficient using the parameter that is representative of the height of the sample, the parameter that is representative of the density of the sample, and the initial mass concentration of uranium; and calculating a corrected mass concentration of uranium using the initial mass concentration of uranium and the corrective coefficient.

12. The method according to claim 11, wherein the initial mass concentration of uranium is calculated using a ratio between the area of the first energy band and the area of the second energy band.

13. The method according to claim 11, wherein the sample has a U/Rn radioactive disequilibrium, the initial mass concentration of uranium being calculated using a parameter that is representative of the U/Rn radioactive disequilibrium.

14. The method according to claim 11, wherein the initial mass concentration of uranium is in addition calculated using at least two calibration coefficients.

15. The method according to claim 14, wherein the at least two calibration coefficients are determined experimentally using a plurality of standard samples or by numerical simulation.

16. The method according to claim 14, wherein the initial mass concentration of uranium is calculated using two calibration coefficients and a ratio, said ratio being representative of a U/Rn radioactive disequilibrium of the sample.

17. The method according to claim 16, wherein the initial mass concentration of uranium Cm.sub.U0 is calculated using the following equation: ${\mathrm{Cm}}_{u0}=\frac{r_{U/U\left(238\right)}\times {10}^6\times M\left({\hspace{0.17em}}_{92}^{238}U\right)\times T_{\frac{1}{2}}\left({\hspace{0.17em}}_{92}^{238}U\right)}{\ln \left(2\right)\times N_A\times M_{\mathrm{ech}}}\times \frac{S_n\left(609\mathrm{keV}\right)}{{\mathrm{Eff}}_{609\mathrm{keV}}\times I_{609\mathrm{keV}}\left({\hspace{0.17em}}_{83}^{214}\mathrm{Bi}\right)\times T_C}\times \frac{\frac{C_U}{C_{\mathrm{Rn}}}-\beta }{\alpha }$ where: r.sub.U/U (238): a mass ratio (.sup.235U+.sup.238U)/.sup.238U in natural uranium which is equal to 1.0072; N.sub.A: the Avogadro constant; M(.sup.238.sub.92U): a molar mass of .sup.238U; $T_{\frac{1}{2}}\left({\hspace{0.17em}}_{92}^{238}U\right)$ a half-life of .sup.238U; ln: a natural logarithm; M.sub.ech: a mass of the sample; S.sub.n(609 keV): the net area in the 609 keV line; Eff.sub.609 keV: an efficiency of the scintillator detector at 609 keV; I.sub.609 keV (.sup.214.sub.83Bi): an emission intensity of .sup.214Bi at 609 keV; T.sub.C: a counting “live time” corrected for a dead time of the scintillator detector.

18. The method according to claim 11, wherein the corrected mass concentration of uranium is calculated by multiplying the initial mass concentration of uranium and the corrective coefficient.

19. The method according to claim 11, wherein the corrective coefficient K(d,h,Cm.sub.U0) is calculated using an equation of the following form:
K(d,h,Cm.sub.U0)=a.sub.0+a.sub.1×Cm.sub.U0+a.sub.2×d+a.sub.3×h+a.sub.4×d×h+a.sub.5×d×h×Cm.sub.U0+a.sub.6×Cm.sub.U0.sup.3+a.sub.7×h.sup.3 where d is the parameter that is representative of the density, h the parameter that is representative of the height, and a.sub.0 to a.sub.7 are coefficients.

20. A device for assessing a concentration of uranium in a sample of a uranium-bearing material, the sample having a density and a height, the device comprising: an acquisition module configured for acquiring an energy spectrum of gamma radiation of the sample by a detector, the energy spectrum comprising at least a first energy band between 87 keV and 110 keV, and a second energy band between 560 keV and 660 keV, the second energy band comprising a 609 keV energy line of .sup.214Bi; a calculation module configured for calculating an initial mass concentration of uranium by using an area of the first energy band, an area of the second energy band, and a net area of the 609 keV energy line of .sup.214Bi; a measurement module configured for obtaining a measurement of a parameter that is representative of the height of the sample and a parameter that is representative of the density of the sample; a calculation module configured for calculating a corrective coefficient, by using a parameter that is representative of the height of the sample, a parameter that is representative of the density of the sample, and the initial mass concentration of uranium calculated by the calculation module; and a calculation module configured for calculating a corrected mass concentration of uranium that is corrected by using the initial mass concentration of uranium and the corrective coefficient, each respectively calculated by the corresponding calculation module and the calculation module.

Description

BRIEF SUMMARY OF THE DRAWINGS

[0049] The present disclosure will be better understood upon reading the description that follows, provided solely by way of example, and made with reference to the drawings in which:

[0050] FIG. 1 is a schematic representation of a mass concentration assessment device for assessing the mass concentration of uranium in an ore sample according to the present disclosure;

[0051] FIG. 2 is a schematic representation of a sample used in the device shown in FIG. 1;

[0052] FIG. 3 is an example of the gamma energy spectrum acquired by the device shown in FIG. 1; and

[0053] FIG. 4 is a schematic representation of a method according to the present disclosure.

DETAILED DESCRIPTION

[0054] In the remainder of the description, the terms “mass concentration” and “content” are considered to be synonymous. The terms “line”, “energy line”, “peak” or “energy peak” are also considered to be synonymous.

[0055] A mass concentration assessment device 10 for assessing the mass concentration of uranium in a sample 12 of a uranium-bearing material is shown schematically in FIG. 1.

[0056] The device 10 comprises a scintillator detector 14. The scintillator detector 14 comprises for example a crystal 16 of sodium iodide (NaI).

[0057] The crystal 16 is for example a 3″×3″ crystal, that is to say that the crystal 16 has a diameter of 3″ and a length of 3″.

[0058] The sample 12 of uranium-bearing material is for example obtained from a drill core or crushed ore that is derived from the exploration or operation of a mine. The sample of uranium-bearing material is placed in a container 18 providing a bed of material of height h. The container 18 is for example made of PVC.

[0059] FIG. 2 shows the geometry of the container 18 and of the sample 12.

[0060] The container 18, in this instance having frustoconical shaped form, comprises a lateral wall 20 and a bottom 22 that defines a receiving volume 24 for receiving the crushed sample 12.

[0061] The wall 20 of the container 18 is for example one millimetre thick.

[0062] As shown in FIG. 1, the bottom 22 of the container 18 is intended to be brought into contact with the scintillator detector 14 during the acquisition of the gamma energy spectrum.

[0063] The sample 12 is preferably finely crushed so as to obtain a grain size of less than one millimetre in order to limit the measurement uncertainties linked to the presence of heterogeneities.

[0064] The sample 12 is advantageously homogenised. The term “homogenised” is understood to indicate the absence of any particular graded bedding or granoclassification in the ore sample.

[0065] For example, the sample 12 is crushed by using a ring mill.

[0066] The uranium-bearing material is arranged inside the container 18 without compacting.

[0067] A standard sample is used as a reference sample in the method according to the present disclosure.

[0068] For example the standard sample has a bulk density (or apparent density) d=1.3 and the height of the bed of the standard sample is h=5 cm.

[0069] The term “bulk density” is understood to refer to the density of the sample without compacting.

[0070] The standard sample comprises silicon dioxide (SiO.sub.2).

[0071] The uranium content of the standard sample is for example 1000 ppm.sub.U, that is to say 1000 milligrammes of uranium per kilogramme of sample.

[0072] The device 10 further comprises a shielding enclosure 26, which is for example cylindrical with a circular base.

[0073] The shielding enclosure 26 defines a housing 28, which is for example cylindrical with a circular base, intended to receive the container 18 with the sample 12 and a part of the scintillator detector 14.

[0074] The shielding enclosure 26 is designed to cover the lateral wall 20 of the container 18 and part of the scintillator detector 14, in order to overcome the background noise coming from the measurement chamber.

[0075] The shielding enclosure 26 is preferably made of lead. The thickness of the enclosure 26 is for example 4.5 cm.

[0076] The shielding enclosure 26 is preferably lined with a layer of copper, for example measuring 3 mm, in order to absorb the lead fluorescence X-rays.

[0077] The shielding enclosure 26 is closed by a cap 30, preferably made of lead, arranged on an upper part of the shielding enclosure 26.

[0078] The device 10 includes a computing unit 32 for assessing the mass concentration of uranium in the sample 12, a display unit 34 connected to the computing unit 32 to display the results supplied by the computing unit 32 and a human-machine interface 36.

[0079] The computing unit 32 comprises a database 38.

[0080] The database 38 is intended to record the results supplied by the computing unit 32.

[0081] The computing unit 32 comprises a processor 40 and a memory storage unit 42 that receives software modules. The processor 40 is capable of executing the software modules received in the memory storage unit 42 and of operationally implementing the method according to the present disclosure.

[0082] The memory storage unit 42 comprises an acquisition module 50 for acquiring an energy spectrum of gamma radiation of the sample 12 by means of the scintillator detector 14.

[0083] FIG. 3 shows an example of an energy spectrum 100 acquired by the acquisition module 50.

[0084] The energy spectrum 100 includes at least a first energy band 110 between 87 keV and 110 keV, and a second energy band 120 between 560 keV and 660 keV. The second energy band 120 comprises a 609 keV energy line 130 of .sup.214Bi.

[0085] The memory storage unit 42 further comprises a calculation module 55 for calculating an initial mass concentration of uranium Cm.sub.U0 by using the area C.sub.U of the first energy band 110, the area C.sub.Rn of the second energy band 120, and the net area of the 609 keV energy line 130 of .sup.214Bi.

[0086] The net area at 609 keV derives solely from the gamma emission of .sup.214Bi, after subtraction of the Compton scattering continuum, for example effected in an ad hoc manner by using a software application for processing energy spectra.

[0087] The areas of the first energy band 110 C.sub.U and of the second energy band 120 C.sub.Rn correspond to the raw areas without correction of the Compton scattering continuum.

[0088] The acquisition time depends on the U/Rn (Uranium/Radon) radioactive disequilibrium of the uranium-bearing material sample and on the average uranium content of the sample 12. It is typically between less than one minute and 25 minutes.

[0089] It is recalled that secular equilibrium is a situation in which the quantity (or activity) of a radioactive isotope remains constant because its production rate (due to decay of a parent isotope) is equal to its decay rate. Where such is not the case it is referred to as radioactive disequilibrium. This state of disequilibrium is observed in particular between .sup.222Rn and uranium .sup.238U due to the volatility of radon.

[0090] The memory storage unit 42 comprises a module 60 for obtaining a measurement of a parameter that is representative of the height “h” of the bed of the sample 12 and of a parameter that is representative of the density “d” of the sample 12.

[0091] The parameters representative of the height “h” of the bed of the sample 12 and of the density “d” of the sample 12 are for example measured manually by an operator and entered into the module 60 of the device 10.

[0092] The memory storage unit 42 comprises a calculation module 65 for calculating a corrective coefficient K, using the parameter that is representative of the height of the sample 12, the parameter that is representative of the density of the sample 12, and the initial mass concentration of uranium Cm.sub.U0 calculated by the calculation module 50.

[0093] The memory storage unit 42 comprises a calculation module 70 for calculating a corrected mass concentration of uranium Cm.sub.U using the initial mass concentration of uranium Cm.sub.U0 and the corrective coefficient K, each respectively calculated by the corresponding calculation module 55 and the calculation module 65.

[0094] The modules 50, 55, 60, 65 and 70 are programmed to implement the method according to the present disclosure, as described in the following sections.

[0095] FIG. 4 presents the steps of a mass concentration assessment method for assessing the mass concentration of uranium in a sample 12 according to the present disclosure.

[0096] The method comprises an acquisition step 200 for acquiring an energy spectrum 100 of gamma radiation from the sample 12 using a scintillator detector 14. The detector 14 is preferably of the type described above. As previously mentioned above, the scintillator detector 14 comprises, for example, a crystal 16 of sodium iodide (NaI).

[0097] The energy spectrum 100 comprises at least a first energy band 110 between 87 keV and 110 keV, and a second energy band 120 between 560 keV and 660 keV. The second energy band comprises at least one 609 keV energy line 130 of .sup.214Bi (FIG. 3).

[0098] The method thus then includes a calculation step 210 for calculating an initial mass concentration of uranium Cm.sub.U0 by using the area C.sub.U of the first energy band 110, the area C.sub.Rn of the second energy band 120, and the net area of the 609 keV energy line 130 of .sup.214Bi.

[0099] The initial mass concentration of uranium Cm.sub.U0 is calculated by using a ratio (C.sub.U/C.sub.Rn) between the area C.sub.U of the first energy band 110 and the area C.sub.Rn of the second energy band 120, which is a parameter that is representative of the U/Rn radioactive disequilibrium.

[0100] The initial mass concentration Cm.sub.U0 of uranium is in addition calculated using two calibration coefficients β.

[0101] More particularly, the initial mass concentration of uranium Cm.sub.U0, is calculated using the following equation:

[00004]${\mathrm{Cm}}_{u0}=\frac{r_{U/U\left(238\right)}\times {10}^6\times M\left({\hspace{0.17em}}_{92}^{238}U\right)\times T_{\frac{1}{2}}\left({\hspace{0.17em}}_{92}^{238}U\right)}{\ln \left(2\right)\times N_A\times M_{\mathrm{ech}}}\times \frac{S_n\left(609\mathrm{keV}\right)}{{\mathrm{Eff}}_{609\mathrm{keV}}\times I_{609\mathrm{keV}}\left({\hspace{0.17em}}_{83}^{214}\mathrm{Bi}\right)\times T_C}\times \frac{\frac{C_U}{C_{\mathrm{Rn}}}-\beta }{\alpha }$

[0102] where:

[0103] r.sub.U/U (238): the mass ratio (U.sup.235+U.sup.238)/.sup.238U in natural uranium which is equal to 1.0072;

[0104] N.sub.A: Avogadro constant (6.022×10.sup.23 mol.sup.−1);

[0105] M(.sup.238.sub.92U): the molar mass of .sup.238U (238.0507 g.Math.mol.sup.−1);

[0106] T.sub.1/2(.sup.238.sub.92U): the half-life (radioactive period) of .sup.238U (4.468×10.sup.9 years);

[0107] ln: the natural logarithm;

[0108] M.sub.ech: the mass of the sample (in grammes);

[0109] S.sub.n (609 keV): the net area in the 609 keV line (number of counts);

[0110] Eff.sub.609 keV: the efficiency of the detector at 609 keV (dimensionless);

[0111] I.sub.609 keV (.sup.214.sub.83Bi): the emission intensity of .sup.214Bi at 609 keV (number of photons emitted per decay) equal to 46.1% according to the database Evaluated Nuclear Structure Data File of the International Atomic Energy Agency—IAEA);

[0112] T.sub.C: the counting “live time” (in seconds) corrected for the dead time of the detector 14.

[0113] The initial mass concentration of uranium Cm.sub.U0 is expressed here in ppm.sub.U, that is to say, in milligrammes of uranium per kilogramme of sample 12, hence the conversion factor 10.sup.6 in the preceding equation.

[0114] The efficiency Eff.sub.609 keV is calculated for example with the Monte-Carlo N-Particle code (MCNP) which provides the ability to model the transport of X and gamma rays emitted in the sample to the detector and then the interaction thereof (energy deposits) in the germanium crystal (“MCNP6TM, User's manual—Version 1.0—LA-CP-13-00634, Rev. 0, Denise B. Pelowitz”. May-2013).

[0115] The calibration coefficients α, β are experimentally determined using a plurality of standard samples or by means of numerical simulation.

[0116] The calibration coefficients α, β are connected to the area C.sub.U of the first energy band and 110, to the area C.sub.Rn of the second energy band 120, to the U/Rn radioactive disequilibrium of the sample by the equation:

[00005]$\frac{A\left({\hspace{0.17em}}_{92}^{238}U\right)}{A\left({\hspace{0.17em}}_{83}^{214}\mathrm{Bi}\right)}=\frac{\frac{C_U}{C_{\mathrm{Rn}}}-\beta }{\alpha }$

[0117] Experimentally, the coefficients α, β are determined by having available a plurality of standard samples that exhibit different U/Rn disequilibriums. In this case, the standard samples exhibit physical characteristics (mineralogy, height, and density) and a uranium content that is substantially identical to those of the standard sample defined here above.

[0118] The term “substantially identical” is understood to indicate a bed height of 5 cm and a density of 1.3 with a precision of the order of % (a maximum of 3%), as well as identical mineralogy (uranium-bearing material with the same provenance), and a uranium content of 1000 ppm.sub.U, with a tolerance of ±500 ppm.sub.U.

[0119] It is to be noted that for the uranium content, the effect is not significant up to a few thousand ppm.sub.U.

[0120] The measurement of the C.sub.U/C.sub.Rn ratio as a function of the U/Rn disequilibrium of the various standard samples makes it possible to obtain the calibration coefficients α, β for example by linear regression.

[0121] The value of calibration coefficients α, β depends on the measurement geometry, the type of detector 14, and the characteristics of the sample 12 (height, density, and uranium content). In the event of a change of detector 12, or for another measurement geometry, it is then necessary for the calibration coefficients to be determined anew.

[0122] The method comprises a measurement step 220 of measuring a parameter that is representative of the height of the sample 12 and a parameter that is representative of the density of the sample 12.

[0123] According to one particular embodiment, the step 220 is carried out before the acquisition step 200 and/or the calculation step 210.

[0124] The height of the sample 12 is for example measured by using a graduated ruler or an optical method.

[0125] The density of the sample 12 is for example measured using any appropriate protocol known to the person skilled in the art. For example, the mass M.sub.ech of the sample 12 is measured with a balance and the volume V.sub.ech of the sample 12 is determined by immersing it in water in a graduated cylinder. The M/V ratio is used to obtain the density.

[0126] The method then comprises a calculation step 230 of calculating a corrective coefficient K, using the parameter that is representative of the height of the sample 12, the parameter that is representative of the density of the sample 12, and the initial mass concentration of uranium Cm.sub.U0.

[0127] The corrective coefficient K makes it possible to take into account the variation in the density of the sample 12, the height of the sample 12, and the uranium content Cm.sub.U0 of the sample 12, and is a function of these physical parameters.

[0128] The value of the corrective coefficient is preferably obtained by carrying out a multiparametric study by numerical simulation.

[0129] For example, the spectral response of more than 800 configurations of samples that exhibit filling heights h varying from 1 to 9 cm, densities d varying from 1 to 1.6, and uranium contents Cm.sub.U0 comprised between 100 ppm.sub.U and 100,000 ppm.sub.U is simulated.

[0130] It is thus then possible to calculate a corrective factor K(d, h, Cm.sub.U0) that may be used to correct the variations induced by the height of the sample, the density and the uranium content, on the calibration coefficients α, β calculated for the standard sample, using an equation of the following form:

K(d,h,Cm.sub.U0)=a.sub.0+a.sub.1×Cm.sub.U0+a.sub.2×d+a.sub.3×h+a.sub.4×d×h+a.sub.5×d×h×Cm.sub.U0+a.sub.6×Cm.sub.U0.sup.3+a.sub.7×h.sup.3

[0131] The coefficients a.sub.0 to a.sub.7 are determined by multilinear regression.

[0132] The method according to the present disclosure finally comprises a calculation step 240 of calculating a corrected mass concentration of uranium Cm.sub.U using the initial mass concentration of uranium Cm.sub.U0 and the corrective coefficient K.

[0133] More particularly, the corrected mass concentration of uranium Cm.sub.U is obtained by the product of the initial mass concentration of uranium Cm.sub.U0 and the corrective coefficient K:

Cm.sub.U=Cm.sub.U0×K

[0134] The inventors have carried out a study on the uncertainty associated with the value of the corrected uranium mass concentration Cm.sub.U assuming a sample 12 that is finely crushed (grain less than 2 mm), and homogenised, with a U/Rn disequilibrium greater than 0.1, and a counting time that is long enough to obtain a statistical uncertainty of less than 1% on the ratio of counts C.sub.U/C.sub.Rn.

[0135] This assumption is borne out when the acquisition time is greater than a minimum value T.sub.min which is equal to:

[00006]$T_{\min }=\frac{\left(\frac{1}{{\tau }_U}\right)+\left(\frac{1}{{\tau }_{\mathrm{Rn}}}\right)}{{\left(1\%\right)}^2}$ [0136] Where: [0137] τ.sub.U: the count rate in the first energy band 110, measurable starting from the initial minutes of acquisition and which, after any duration T, is equal to

[00007]${\tau }_U\left(T\right)=\frac{C_U\left(T\right)}{T};$ [0138] τ.sub.Rn: the count rate in the second energy band 120, which is equal to

[00008]${\tau }_{\mathrm{Rn}}\left(T\right)=\frac{C_{\mathrm{Rn}}\left(T\right)}{T};$

these count rates remain constant with the exception of statistical counting fluctuations and they hardly vary anymore when T.sub.min is reached.

[0139] The calculation of the uncertainty on the uranium content takes into account separately the uncertainty due to the characteristics of the sample 12, the uncertainty due to the mineralogy of the sample 12, the uncertainty due to a possible heterogeneity of the sample 12, the uncertainty due to the counting statistics, and finally the uncertainty due to the measurement of the specific activity of .sup.214Bi.

[0140] The uncertainty associated with the value of the corrected uranium mass concentration Cm.sub.U, obtained by quadratic sum of the various uncertainties mentioned above, is 20% if the sample 12 is finely crushed (2 mm) and homogenised. For a more coarsely crushed sample 12 (8 mm), this uncertainty amounts to approximately 30%.

[0141] An experimental validation was also performed using 38 samples 12 having a uranium content of between 100 and 100,000 ppm.sub.U. For each content level, different U/Rn disequilibriums were selected.

[0142] For each sample 12, a reference uranium content was measured by inductively coupled plasma mass spectrometry (ICP-MS) with a level of precision of the order of 10%.

[0143] The method according to the present disclosure and the method described in Domingos and Melo (1967) mentioned above were applied to the 38 samples.

[0144] The mean relative deviation from the reference content is about 33% using an energy band ranging from 52 keV to 108 keV in order to measure the contribution of uranium in the spectrum, as in the method of Domingos and Melo (1967).

[0145] The mean relative deviation from the reference content is of the order of 15% using the method according to the present disclosure with an energy band between 87 keV and 110 keV.

[0146] Thus, by advantageously taking into account the corrective factor K, the method according to the present disclosure makes it possible to obtain a value of the mass concentration of uranium that is more precise than the methods of the state of the art. The use of the first energy band between 87 keV and 110 keV is in effect particularly stable with respect to heterogeneities and self-attenuation as compared to the 53 keV-108 keV band used by the method of Domingos and Melo (1967), but it is also less sensitive to variations in the mineralogy of the ore.

[0147] The method according to the present disclosure serves to enable a rapid assessment of the mass concentration of uranium of the sample. The measurements are inexpensive because the method does not require a germanium semiconductor detector. A “simple” sodium iodide scintillation detector provides the ability to obtain reliable and precise measurements.