Systems and Methods for Separating Yttrium and Strontium
20210238051 · 2021-08-05
Assignee
Inventors
Cpc classification
C01G49/0009
CHEMISTRY; METALLURGY
C22B61/00
CHEMISTRY; METALLURGY
Y02P10/20
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C22B26/20
CHEMISTRY; METALLURGY
C01F11/005
CHEMISTRY; METALLURGY
C01G25/003
CHEMISTRY; METALLURGY
International classification
C22B26/20
CHEMISTRY; METALLURGY
Abstract
Systems and methods for separating Y and Sr are provided. The systems and methods provide combinations of solutions, vessels, and/or media that can provide Y solutions of industrially beneficial concentration.
Claims
1. A method for separating Y and Sr, the method comprising: providing a dilute acidic mixture comprising Y and Sr to a first vessel having a first media therein; and while providing the dilute acidic mixture, retaining at least some of the Y from the dilute acidic mixture within the first vessel while eluting at least some of the Sr from the dilute acidic mixture to form a dilute acidic eluent.
2. The method of claim 1 wherein the dilute acidic mixture comprises .sup.90Y and .sup.90Sr.
3. The method of claim 1 wherein the dilute acidic mixture additionally comprises stable Sr, Ca and/or Ba.
4. The method of claim 1 wherein the dilute acidic mixture comprises stockpiled Sr-bearing nuclear material.
5. The method of claim 1 wherein the first media comprises a resin.
6. The method of claim 1 wherein the first media comprises an HDEHP resin.
7. The method of claim 1 wherein the first media comprises alkylphosphorus extractants.
8. The method of claim 1 wherein the dilute acidic eluent comprises at least some Sr from the dilute acidic mixture.
9. The method of claim 1 further comprising: providing the dilute acidic mixture from a reservoir; and providing the dilute acidic eluent to the reservoir.
10. The method of claim 1 wherein the dilute acidic mixture further comprises Zr.
11. The method of claim 10 wherein while providing the dilute acidic mixture, further comprising retaining at least some of the Zr from the dilute acidic mixture within the first vessel.
12. The method of claim 1 wherein the dilute acidic mixture further comprises Fe.
13. The method of claim 10 wherein while providing the dilute acidic mixture, further comprising retaining at least some of the Fe from the dilute acidic mixture within the first vessel.
14. The method of claim 1 wherein the dilute acidic mixture comprises HCl.
15. A method for separating Y and Sr, the method comprising: providing a first vessel containing a first media and dilute acidic mixture comprising Y; providing a concentrated acid mixture to the first vessel; and while providing the concentrated acid mixture to the first vessel, recovering a concentrated acid eluent comprising at least some of the Y from within the first vessel.
16. The method of claim 15 wherein the first media comprises a resin.
17. The method of claim 15 wherein the first media comprises an HDEHP resin.
18. The method of claim 15 wherein the first media comprises alkylphosphorus extractants.
19. The method of claim 15 wherein the first vessel contains .sup.90Y.
20. The method of claim 15 wherein the first vessel contains one or both of Zr and Fe.
21. The method of claim 20 wherein while providing the concentrated acid mixture to the first vessel, retaining at least some of the one or both of the Zr and Fe.
22. The method of claim 15 wherein the concentrated acid mixture comprises HCl.
23. The method of claim 15 further comprising providing the concentrated acid eluent to a second vessel containing a second media.
24. A method for separating Y and Sr, the method comprising: providing a concentrated acidic mixture comprising Y to a vessel having a media therein; and while providing the concentrated acidic mixture, retaining at least some of the Y from the concentrated acidic mixture within the vessel and forming an eluent.
25. The method of claim 24 wherein the concentrated acidic mixture comprises .sup.90Y.
26. The method of claim 24 wherein the media comprises a resin.
27. The method of claim 24 wherein the media comprises a diglycolamide resin.
28. The method of claim 24 wherein the media comprises N, N, N′, N′-tetra-n-octyldiglycolamide.
29. The method of claim 24 wherein the concentrated acidic mixture comprises at least some Sr.
30. The method of claim 29 wherein while providing the concentrated acidic mixture, retaining at least some of the Y from the concentrated acidic mixture within the vessel and forming an eluent comprising at least some of the Sr.
31. The method of claim 24 wherein the concentrated acidic mixture comprises at least some Zr.
32. The method of claim 31 wherein while providing the concentrated acidic mixture, retaining at least some of the Zr from the concentrated acidic mixture within the vessel.
33. The method of claim 24 wherein the concentrated acidic mixture comprises at least some Fe.
34. The method of claim 33 wherein while providing the concentrated acidic mixture, retaining at least some of the Fe from the concentrated acidic mixture within the vessel.
35. A method for separating Y and Sr, the method comprising: providing a vessel containing a media and a concentrated acidic mixture comprising Y; providing a dilute acid mixture to the vessel; and while providing the dilute acid mixture to the vessel, recovering a dilute acid eluent comprising at least some of the Y from within the vessel.
36. The method of claim 35 wherein the media comprises a resin.
37. The method of claim 35 wherein the media comprises a diglycolamide resin.
38. The method of claim 35 wherein the media comprises N, N, N′, N′-tetra-n-octyldiglycolamide.
39. The method of claim 35 wherein the vessel contains .sup.90Y.
40. The method of claim 35 wherein the vessel contains one or both of Zr and Fe.
41. The method of claim 40 wherein while providing the diluted acid mixture to the vessel, eluting at least some of the one or both of the Zr and/or Fe.
42. The method of claim 35 wherein the diluted acid mixture comprises HCl.
43. The method of claim 35 wherein the vessel contains Sr.
44. The method of claim 40 wherein while providing the diluted acid mixture to the vessel, eluting at least some of the Sr.
45. A method for separating Y and Sr, the method comprising: providing a dilute acidic mixture comprising Y and Sr to a first vessel having a first media therein; separating at least some of the Sr from the Y of the dilute acidic mixture; eluting at least some of the Y from first vessel to form a concentrated acid eluent comprising Y; providing the concentrated acid eluent to a second vessel having a second media therein; and eluting at least some of the Y from the second vessel to form a dilute acid eluant comprising Y.
46. The method of claim 45 wherein the dilute acidic mixture comprises .sup.90Y and .sup.90Sr.
47. The method of claim 45 wherein the dilute acidic mixture additionally comprises stable Sr, Ca and/or Ba.
48. The method of claim 45 wherein the dilute acidic mixture comprises stockpiled Sr-bearing nuclear material.
49. The method of claim 45 wherein the first media comprises a resin.
50. The method of claim 45 wherein the first media comprises an HDEHP resin.
51. The method of claim 45 wherein the first media comprises alkylphosphorus extractants.
52. The method of claim 45 further comprising: providing the dilute acidic mixture from a reservoir; and wherein the separating comprises recovering a dilute acidic eluent comprising Sr, and providing the dilute acidic eluent comprising Sr to the reservoir.
53. The method of claim 45 wherein the dilute acidic mixture further comprises Zr.
54. The method of claim 53 wherein while providing the dilute acidic mixture, further comprising retaining at least some of the Zr from the dilute acidic mixture within the first vessel.
55. The method of claim 45 wherein the dilute acidic mixture further comprises Fe.
56. The method of claim 55 wherein while providing the dilute acidic mixture, further comprises retaining at least some of the Fe from the dilute acidic mixture within the first vessel.
57. The method of claim 45 wherein the dilute acidic mixture comprises HCl.
58. The method of claim 45 wherein the first vessel contains .sup.90Y.
59. The method of claim 45 wherein the first vessel contains one or both of Zr and Fe.
60. The method of claim 59 wherein while providing the concentrated acid mixture to the first vessel, retaining at least some of the one or both of the Zr and Fe.
61. The method of claim 45 wherein the second media comprises a resin.
62. The method of claim 45 wherein the second media comprises a diglycolamide resin.
63. The method of claim 45 wherein the second media comprises N, N, N′, N′-tetra-n-octyldiglycolamide.
64. The method of claim 45 wherein the diluted acid mixture comprises HCl.
65. A method for separating Y and Sr, the method comprising: providing a strong acidic mixture comprising Y and Sr to a first vessel having a first media therein; separating at least some of the Sr from the Y of the strong acidic mixture; eluting at least some of the Y from first vessel to form a dilute acid eluent comprising Y; providing the dilute acid eluent to a second vessel having a second media therein; and eluting at least some of the Y from the second vessel to form a concentrated acid eluant comprising Y.
66. The method of claim 65 wherein the strong acidic mixture comprises .sup.90Y and .sup.90Sr.
67. The method of claim 65 wherein the first media comprises a resin.
68. The method of claim 65 wherein the first media comprises a diglycolamide resin.
69. The method of claim 65 wherein the first media comprises N, N, N′, N′-tetra-n-octyldiglycolamide.
70. The method of claim 65 wherein the dilute acidic eluent comprises HCl.
71. The method of claim 65 wherein the first vessel contains .sup.90Y.
72. The method of claim 65 wherein the second media comprises a resin.
73. The method of claim 65 wherein the second media comprises an HDEHP resin.
74. The method of claim 65 wherein the second media comprises alkylphosphorus extractants.
75. The method of claim 65 wherein the concentrated acid eluent comprises HCl.
76. A method for separating Y and Sr, the method comprising: providing a first mixture of Y and Sr to a first vessel having a first volume; separating at least some of the Y from the first mixture to form a second mixture comprising the separated Y and transferring the second mixture to a second vessel having a second volume, wherein the first volume is greater than or equal to the second volume; and transferring at least some of the separated Y from the second vessel to form a third mixture comprising the transferred Y, wherein the Y concentration of the first mixture is less than the Y concentration of the third mixture.
77. The method of claim 76 wherein the first and third mixtures are dilute acid mixtures.
78. The method of claim 77 wherein the acid mixtures comprise HCl.
79. The method of claim 76 wherein the first vessel houses a first media and the second vessel houses a second media.
80. The method of claim 76 wherein the first media is chemically different than the second media.
81. The method of claim 76 wherein the second mixture is a concentrated acid mixture.
Description
DRAWINGS
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DESCRIPTION
[0029] The systems and methods of the present disclosure will be described with reference to
[0030] General recipes for the preparation of solutions that can simulate Sr-bearing stockpile materials are provided in Table 1.
TABLE-US-00001 TABLE 1 General recipe to prepare a .sup.90Sr-bearing simulant solution containing Group II elements and Y that approximate those found in an example .sup.90Sr product solution. .sup.90Sr simulant Spike conc., Desired conc., Spike vol., sol'n. Element spike mg/mLb μg/mL μL components Ca 99.26 540 33.0 Sr 260.21 50,250 1770 Ba 8.55 20 14.2 Y 3.42 2.30 4.1 Total element spike vol. = 1.22 .sup.90Sr spike vol. = 0 c 0.1M HCl diluent vol. = 4.84 Total vol. = 6.06
[0031] Spiked solutions can also be prepared with reference to Table 2 below as well.
TABLE-US-00002 TABLE 2 .sup.90Sr activities that were spiked into each column load solution prior to .sup.90Y purification. Determined .sup.90Sr Run Run date activity μCi .sup.a, b 1 Feb. 15, 2019 3.96E+2 (2.12E+0) 2 Feb. 20, 2019 7.41E+2 (2.12E+0) 3 Feb. 21, 2019 7.66E+2 (1.56E+0) 4 Feb. 21, 2019 6.82E+2 (8.85E−1) 5 Fab. 27, 2019 7.02E+2 (5.05E−1)
[0032] In accordance with example implementations acidic reagents can be utilized such as solutions of dilute acidic mixtures and concentrated acidic mixtures prepared with the reagents disclosed below for example.
[0033] Concentrated hydrochloric acid (HCl) can be ACS Certified grade or higher (Fisher Scientific, Waltham, Mass.). Dilutions of HCl can be prepared from deionized water (≥18 MΩcm) using a Barnstead E-Pure water purification system (Dubuque, Iowa). Scintillation cocktail was UltimaGold AB (PerkinElmer, Billerica, Mass.).
[0034] A supply of ˜5 mCi .sup.90Sr in ˜2% HNO.sub.3 can be obtained and this solution can be evaporated to nitrate salt, then transformed to formate salt. The .sup.90Sr residue can be evaporated and transformed to chloride salt prior to use. An infrared lamp can be used to evaporate metered volumes of the transformed .sup.90Sr stock solution to Teflon vials (7 mL round-bottom vial, Savillex, Eden Prairie, Minn.).
[0035] Single element solutions containing concentrates of Ca(II), Sr(II), Ba(II), and Y(III) in 0.1 M HCl can be prepared, as briefly described below: [0036] Ca solution can be prepared by dissolving calcium metal chips in concentrated. HCl. After evaporation of excess acid, the CaCl.sub.2 salts can be brought up in 0.1 M HCl. Prepared Ca(II) conc.=99.26 mg/mL. [0037] Sr solution can be prepared from strontium(II) carbonate salt. The salt can be saturated with conc. HCl to destroy carbonate and convert the salts to strontium chloride. The excess acid can be evaporated off overnight, and then the dried salts were brought up in 0.1 M HCl. Prepared Sr(II) conc.=260.21 mg/mL. [0038] Ba solution can be prepared from barium(II) chloride salt. The salt can be dissolved directly in 0.1 M HCl. Prepared Ba(II) conc.=8.55 mg/mL. [0039] Y solution can be prepared from yttrium(III) chloride salt. The salt can be dissolved directly in 0.1 M HCl. Prepared Y(III) conc.=3.42 mg/mL.
[0040] Aliquots of these solutions can be added to .sup.90Sr-spiked solutions in order to simulate the dissolved solids present in .sup.90Sr stocks.
[0041] In accordance with example implementations, and with reference to
[0042] Within vessel 14 can be a first media 20 that includes a resin. This resin can include Bis(2-ethylhexyl) hydrogen phosphate (HDEHP). The first media can also include alkylphosphorus extractants. Alternatively, the first media can also include Si. In accordance with example implementations the media 20 can be considered a first media.
[0043] The Y purification method can employ two columns or vessels in tandem. First vessel 14 can have media 20 that includes a Di-(2-ethylhexyl)phosphoric acid (HDEHP)-based extraction chromatography resin, sold under the trade name Ln Resin (Eichrom Technologies, Ltd, Lisle, Ill.). The particle size distribution used was 100-150 μm, but other size distributions such as 50-100 μm or 20-50 μm are contemplated.
[0044] The Ln Resin can be packed into a column having a ˜0.25 cc internal volume in a 1 cc SPE tube kit (Supelco) that can be cut to the appropriate dimension. The columns can be polypropylene, with 20 μm pore size polyethylene frits. The column can be fitted with a custom-made plastic cap (with female luer fitting) that can be inserted into the top of the trimmed column.
[0045] In accordance with example implementations, while providing the dilute acid mixture comprising Y and Sr the method can provide for retaining at least some of the Y from the dilute acidic mixture within vessel 14 while eluting some of the Sr from the dilute acidic mixture to form a dilute acidic eluent which would be provided to conduit 18. In accordance with example implementations the method can also include providing the dilute acidic mixture from reservoir 12 and then providing the dilute acidic eluent to reservoir 12 via conduit 18 for example.
[0046] In accordance with example implementations, the dilute acidic mixture can further comprise Zr and the method can also include while providing the dilute acidic mixture, retaining at least some of the Zr from the dilute acidic mixture within vessel 14. The method can also include further retaining at least some of the Fe from the dilute acidic mixture within vessel 14. The dilute acidic mixture can include HCl for example, an organic acid for example, such as formic acid for example.
[0047] Referring next to
[0048] In accordance with example implementations, vessel 14 can include one or both of Zr and Fe and while providing the concentrated acid mixture from vessel 24 to vessel 14 at least some or both of the Zr and Fe can be retained. In accordance with example implementations this concentrated acid mixture can include HCl, an organic acid, such as formic acid for example. In further embodiments the method can provide the concentrated acid eluent of 32 from within vessel 30 to another vessel containing another medium. This additional embodiment will be described with more detail herein. Additionally the media 20 remains as the media 20 as described in system 10 for example.
[0049] In accordance with an example embodiment, tandem column-based .sup.90Y purification methods are contemplated and described herein. Referring to
[0050] Further, with reference to
[0051]
TABLE-US-00003 TABLE 3 Example behavior of Y(III) and Sr(II) through the tandem column process. While not exclusively evaluated during the present study, the behavior of Fe(III) and Zr(VI) are also shown. Active Conc. HCl, Retained (↑) or unretained (↓) Step Description column moles/L Y(III) Sr(II) Zr(IV) Fe(III) 3 .sup.90Y load/wash C1 0.1 ↑ ↓ ↑ ↑ 4 .sup.90Y transfer C1 .fwdarw. C2 8 ↓.fwdarw.↑ ↓.fwdarw.↓ ↑.fwdarw.↑ ↑.fwdarw.↑ 5 Wash C2 8 ↑ ↓ ↑ ↑ 6 .sup.90Y elute C2 0.1 ↓ ↓ ↓ ↓
[0052] Referring next to
[0053] In accordance with example implementations media 38 can include a resin such as diglycolimide resin, for example (diglycolamide)-based extraction chromatography resin, sold under the trade name DGA-Normal Resin (Eichrom Technologies, Ltd.). The particle size distribution used can be 20-50 μm, 50-100 μm, and/or 100-150 μm Example extraction media can include N,N,N′,N′-tetra-n-octyldiglycolamide.
[0054] The concentrated acid mixture can include at least some of the Sr for example as radioactive and stable isotopes of Sr such as .sup.90Sr, .sup.89Sr, .sup.88Sr, or .sup.86Sr. The method can include while providing the concentrated acid mixture retaining at least some of the Y from the concentrated acid mixture within vessel 36 and forming an eluent that can include at least some of the Sr in conduit 46. At least some of the concentrated acid mixture can include Zr and the method can include, while providing the concentrated acid mixture to vessel 36, retaining at least some of the Zr from the concentrated acid mixture. Additionally or separately, at least some of the concentrated acid mixture can include Fe and the method can include, while providing in the concentrated acid mixture, retaining at least some of the Fe from the concentrated acid mixture within vessel 36.
[0055] Referring next to
[0056] The vessel 36 can include at least some of the Y for example as radioactive and stable isotopes of Y such as of 90Y, .sup.89Y, .sup.88Y, or .sup.86Y, for example. The vessel can also contain one or more of Zr or Fe and the method can further include for providing dilute acid mixture 56 to vessel 36 eluting at least some of one or both of Zr and/or Fe within vessel 36. As described herein the dilute acidic mixture can include HCl and the mixture can include an organic acid such as formic acid for example. Additionally while providing the dilute acid mixture to vessel 36, the method can include eluting at least some of the Sr within the vessel.
[0057] Referring next and with reference to
[0058] In accordance with example implementations a second mixture 24a can be provided to first vessel 14 and the method can further include recovering a first eluent 28 and providing first eluent 28 that includes Y to a second vessel 36 having a second media 38 therein. The second mixture can be a strong acidic or concentrated acidic solution such as HCl and the second media can be a diglycolamide resin such as N, N, N′, N′-tetra-n-octyldiglycolamide. The method can further include retaining at least some of the Y from first eluent 28 within second vessel 36 utilizing media 38 for example and providing a third mixture 42 to second vessel 36 and, when providing third mixture 42, recovering a second eluent 52 that includes at least some of the Y from the first vessel. This third mixture can be a weak or dilute acid mixture such as HCl.
[0059] In accordance with other example implementations and with reference to
[0060] Continuing with this embodiment, a second mixture 24a can be provided to first vessel 14 and the method can further include recovering a first eluent 28 and providing first eluent 28 that includes Y to a second vessel 36 having a second media 38 therein. This second mixture can be a dilute or weak acidic solution that can include HCl and the first media can be an alkylphosphorus extractant resin such as HDEHP resin.
[0061] The method can further include retaining at least some of the Y from first eluent 28 within second vessel 36 utilizing media 38 for example and providing a third mixture 42 to second vessel 36 and, when providing third mixture 42, recovering a second eluent 52 that includes at least some of the Y from the first vessel. This third mixture can be a strong or concentrated acid mixture such as HCl.
[0062] Additionally the method can provide that vessels 14 and 36 are of substantially different sizes with vessel 14 being at least as large but can be larger than vessel 36. In such a configuration, the Y recovered from the systems and methods of the process can be in a concentrated form and suitable for industrial use. Accordingly, the volume of vessel 14 can be larger than the volume of vessel 36.
[0063] Table 3 above also indicates the behavior of the four selected ions on the second media (DGA Resin) during the .sup.90Y transfer, secondary wash, and .sup.90Y elute steps.
[0064] An example system schematic 60 is shown in
TABLE-US-00004 TABLE 4 Listing of schematic labels presented in FIG. 6. Label ID Label ID SP1-SP2 Syringe pumps 1 & 2 D In-line .sup.90Y product detector (optional) V1 6-port, 2-pos valve FC Fraction collector V2-V3 2-port, 2-pos. valves SR Sample reservoir PP Peristaltic pump .sup.90Sr/Y L Load line for .sup.90Sr/Y C1 Ln Resin column .sup.90Sr R .sup.90Sr return line C2 DGA column OF .sup.90Sr/Y overflow line SL Sample injection loop
[0065] System 60 can be programmed to perform the series of steps outlined in Table 5 below. Delivered reagent volumes and flow rates through the columns may be set, as described below.
[0066] The reagent volumes programmed to be delivered to system 60 can be a function of the fluid delivery systems displacement volume, for example wherein one (or two) syringe volumes were delivered for a particular step. The delivered volumes can be deliberately programmed to be excessive (i.e., many bed volumes of reagent delivered through the columns).
TABLE-US-00005 TABLE 5 Tandem column .sup.90Y purification method steps as tested. Active Conc. HCl, Delivered vol., Flow rate, Step Description column moles/L mL .sup.a mL/min .sup.a Footnotes 1 Condition C1 C1 0.1 3 .sup. 1-2 2 Condition C2 C2 8 2 0.5-1 3 .sup.90Y load/wash C1 0.1 20 .sup. 1-2 b. 4 .sup.90Y transfer C1 .fwdarw. C2 8 10 0.5-1 5 Wash C2 8 2.5 0.5-1 6 .sup.90Y elute C2 0.1 2.5 .sup. 0.2-0.5 c. 7 Clean-up All H.sub.2O 1-3 0.5-2 d. .sup.a As tested; other concentrations, amounts delivered, and/or flow rates are contemplated. b. .sup.90Sr unretained; the .sup.90Y-depleted load/wash solution was returned to a reservoir for eventual reuse. c. The bulk of the .sup.90Y product is in the first ~0.5 to ~0.7 mL elute fraction. d. Water was flushed through all fluid transport lines and then the lines were purged with air. This included a water flush through the SL using thePP.
[0067] The flow rates may be ultimately limited by a number of factors, which may include the following: the back-pressure generated by the fluid pathways (primarily the columns); the amount of back-pressure the columns or fittings or pumps can handle prior to leaking; the amount of back-pressure the extraction chromatography resin can handle prior to bleeding excessive extractant; and the adsorption/desorption rate of the analytes on the column resins. The flow rate range indicated in Table 5 represents the two example rate values assessed. The lower flow rate may be performed for Runs 1-4, and the higher flow rate may be performed for Run 5.
[0068] The elapsed times required to perform the protocol described in Table 5 are shown in Table 6.
TABLE-US-00006 TABLE 6 Approximate, non-optimized elapsed times required to perform the .sup.90Y isolation and purification process. .sup.a Runs 1-4 Run 5 Elapsed Cumulative Elapsed Cumulative time, time, time, time, Step Description min min min min 1 C1 17 17 19 19 2 C2 3 .sup.90Y load/wash 22 39 15 34 4 .sup.90Y transfer 26 65 14 48 5 Wash 9 74 6 54 6 .sup.90Y elute 30 104 7 61 7 Clean-up .sup.b 20 124 20 81 .sup.a Indicated times include line blow-outs at each step and manual fraction collection activities (which introduced some additional time). .sup.b Approximate values; elapsed times not closely tracked.
[0069] An example product solution, which had a .sup.90Sr activity concentration of 1.25 Ci/mL, contained the stable Group II element concentrations listed in the 2nd column of Table 7 for Ca, Sr, and Ba. The Y concentration was based on the approximate mass concentration of .sup.90Y present in a .sup.90Sr solution of this activity concentration. The element and activity concentrations in Table 7 are but one example of a .sup.90Sr product composition, and may not be representative of other .sup.90Sr batches.
TABLE-US-00007 TABLE 7 Stable elements added to .sup.90Sr-spiked simulated working stock, considering a target .sup.90Sr activity concentration of 1.25 Ci/mL. Sum Group II Group Est. Mass Elements, II: Y Ele- conc., in 6 mL, μmoles μmoles mole ment μg/mL μg .sup.b in 6 mL in 6 mL ratio Ca 540 3240 80.84 Sr 50,250 .sup.a 301,500 3441 .sup.a Ba 20 120 0.874 3523 22,980 Y .sup. 2.30 .sup.c 13.80 0.153 .sup.a Sr mass concentration includes contributions from .sup.90Sr. .sup.b Per 7.5 Ci of example .sup.c Based on .sup.90Y specific activity and activity concentration of 1.25 Ci/mL.
[0070] Given the example 1.25 Ci/mL .sup.90Sr activity concentration, it was approximated that 6.4 mL of this solution would be required to obtain a synthetic 8 Ci .sup.90Sr solution. A 6.0 mL sample injection loop can be installed in system 60 (“SL”,
[0071] .sup.90Sr/.sup.90Y-bearing solutions that closely simulated the elemental composition of a stock Sr bearing solution was prepared. The solution stable element compositions are listed in Tables 1 and 7 and the spiked .sup.90Sr activity values are listed in Table 2.
[0072] The isolated .sup.90Y produced by this (or any) purification method for medical purposes oftentimes requires a .sup.90Y: .sup.90Sr activity ratio of ≥1×10.sup.6:1. Accordingly, for every 1 Ci .sup.90Y in an isotope product, a maximum of 1×10.sup.−6 Ci (1 μCi).sup.90Sr may be allowable. Based on the molar specific activities in Table 8, 1 μCi .sup.90Sr is equivalent to 4.7×10.sup.−4 μmoles (0.47 nmoles) of Group II elements (see, for example, simulated .sup.90Sr stock solution that is described in Table 7).
TABLE-US-00008 TABLE 8 Molar specific activity calculations for pure .sup.90Sr and .sup.90Y, as well as .sup.90Sr + Group II elements in simulated aged .sup.90Sr stock. Specific activity Specific activity (pure radionuclide) (w/all Group II elements) Radionuclide μg/Ci μmoles/Ci μmoles/Ci .sup.90Sr 7.28 × 10.sup.3 8.30 × 10.sup.1 4.70 × 10.sup.2 .sup.a .sup.90Y 1.84 × 10.sup.0 2.04 × 10.sup.−2 .sup.a 3523 μmoles/7.5 Ci of .sup.90Sr (per Table 7).
[0073] Using the .sup.90Y isolation and purification processes of the present disclosure, at least a 10.sup.6-fold activity enrichment of .sup.90Y over .sup.90Sr may be attainable. Based on the starting .sup.90Sr activity levels present in the five test runs (1-5), the maximum .sup.90Sr activity levels in the .sup.90Y product fractions are shown in Table 9.
TABLE-US-00009 TABLE 9 .sup.90Sr activities that were spiked into each column load solution prior to .sup.90Y purification (as replicated in Table 2), and the required maximum .sup.90Sr activity levels in the .sup.90Y product fraction to achieve a 10.sup.6-fold .sup.90Y activity enrichment factor. Determined .sup.90Sr Max. .sup.90Sr activity activity, after .sup.90Y purification, Run Run date μCi .sup.a μCi .sup.b 1 Feb. 15, 2019 3.96E+2 3.96E−4 (2.12E+0) 2 Feb. 20, 2019 7.41E+2 7.41E−4 (2.12E+0) 3 Feb. 21, 2019 7.66E+2 7.66E−4 (1.56E+0) 4 Feb. 26, 2019 6.82E+2 6.82E−4 (8.85E−1) 5 Feb. 27, 2019 7.02E+2 7.02E−4 (5.05E−1) .sup.a Mean and (±1 s) values obtained from replicate measurements taken throughout the study interval. .sup.b Maximum .sup.90Sr activity after a 10.sup.6 .sup.90Y product enrichment factor.
[0074] The .sup.90Y isolation and purification method (Table 5) can be performed using the system 60 shown in
[0075] The tandem column process can include a Ln resin and a DGA resin column, respectively. Once the .sup.90Sr/.sup.90Y solution is loaded into the sample injection loop, in semi-automated fashion, for example, with a peristaltic pump, the .sup.90Y isolation and purification process can be fully automated.
[0076] For Run 1, which contained the least .sup.90Sr/.sup.90Y activity of the five runs, a fraction collector can be employed to collect fractions of ˜2 mL volume across the entire process (except for the .sup.90Y elution step, during which <1 mL fractions were collected). The .sup.90Y activity chromatogram is shown immediately after the conclusion of the run, and once the samples achieved secular equilibrium (
[0077] When the .sup.90Sr in the fractions reach equilibrium with .sup.90Y, the profile of the unretained .sup.90Sr, traveling from the sample injection loop and through the load/wash of column 1 can be determined. Example fractions shown can each be 2 mL in volume. The .sup.90Sr can be in the first 6 mL volume; the next 2 mL fraction can contain the bulk of the residual .sup.90Sr. This ˜30 μCi of .sup.90Sr may be carried from the sample injection loop as a segment of wash solution trapped between two air segments, for example. With the passing of the air segments, the .sup.90Sr activity may be at baseline for the remainder of the column wash. Overall, 97% of the .sup.90Sr in the load/wash fraction may be accounted for.
[0078] Runs 2 through 5 can contain approximately double the .sup.90Sr/.sup.90Y activity of Run 1. Some fractions (the .sup.90Sr load effluent and the early .sup.90Y elution), can be split into two. For the .sup.90Sr load, the first and second 10 mL fractions can be collected (except for Run 2, in which the first 18.2 mL and the second 2.35 mL were collected). For the .sup.90Y elution, the first 0.72 to 0.84 mL can be collected in one fraction, and the remainder of the 2.5 mL .sup.90Y elution volume in the second fraction.
[0079] In
[0080] Additionally, a 2 μL aliquot of the Run 5 primary column load/wash fraction effluent can be sampled immediately upon collection. The aliquot can be added to scintillation cocktail and the resulting sample counted by liquid scintillation analyzer (LSA). This sample can be periodically counted until the sample approaches .sup.90Sr/.sup.90Y secular equilibrium. The LSA pulse height spectra at time “near-zero” and beyond are shown in
[0081] Example performance of the tandem purification process is shown in Table 10 for .sup.90Y. The table provides the total injected .sup.90Sr/.sup.90Y into system 60, and the determined .sup.90Y activity across all the collected fractions. Table 11 uses the Table 10 data to calculate the total .sup.90Y recovery across all fractions (% activity balance), and the .sup.90Y recovery in the column 2 elution.
TABLE-US-00010 TABLE 10 Determined .sup.90Y activities (μCi) obtained immediately after completion of the tandem column purification process, including fluidic system rinses and spent columns. Column 2 .sup.90Y elution activities are in bold. Run 1 Run 2 Run 3 Run 4 Run 5 Elapsed days .sup.a 0.087 0.050 0.038 0.073 0.054 Units μCi Injected activity 3.96E+2 7.41E+2 7.66E+2 6.82E+2 7.02E+2 reference .sup.b, c (2.12E+0) (2.12E+0) (1.56E+0) (8.85E−1) (5.05E−1) C1 Load/Wash 2.19E+1 4.28E+1 3.82E+1 4.34E+1 3.80E+1 C1.fwdarw.C2 Transfer 1.01E+1 2.65E+1 1.91E+1 2.41E+1 4.03E+1 C2 Wash 3.25E−3 7.69E−3 7.53E−3 3.33E−3 7.22E−2 C2 .sup.90Y Elute 3.30E+2 7.01E+2 6.57E+2 5.89E+2 6.26E+2 System Rinses 1.76E+0 3.38E−1 2.03E−1 1.68E−1 1.57E+0 Col. 1 5.35E−2 3.94E−1 1.83E−2 3.18E−2 4.46E−2 Col. 2 3.76E−2 3.83E−1 1.10E−1 9.10E−2 9.27E−2 Sum of fractions .sup.d 3.64E+2 7.71E+2 7.15E+2 6.57E+2 7.06E+2 .sup.a Elapsed time at which activity fractions were calculated. .sup.b Small aliquot of the original .sup.90Sr/.sup.90Y column load solution, extrapolated to total load volume. .sup.c Mean and (±1 s) values obtained from replicate measurements taken throughout the study interval. .sup.d Activity sum across all collected/analyzed column effluent fractions, system rinses, and spent columns.
[0082] Across all five runs, 97.2±5.0% of the activity injected into the system can be accounted for. This ±5.0% was assessed as the uncertainty in the measurement approach. Consequently, this same relative uncertainty can be used to assign uncertainties to the individual .sup.90Y elution yields. Across all five runs, it can be determined that the mean .sup.90Y elution fraction was 87.8±4.3% of the total injected .sup.90Y. The .sup.90Y yields for Run 5, which was performed at higher flow rates (for example doubled) than Runs 1-4, can result in .sup.90Y product yields that can be statistically indistinguishable from the other runs.
[0083] The decay of each primary .sup.90Y elution fraction for the five runs can be periodically monitored radiometrically. The activity of the initial .sup.90Y sample can be normalized at time near-zero to “1”, then calculate the activity fraction across the next ˜60 days. The charts in
[0084] Upon approaching ˜60 elapsed days of counting, the .sup.90Y activity in the .sup.90Y product fractions can became too low to accurately measure by the radiometric detector. At that point, some of the volume of the primary .sup.90Y elution fractions may be sacrificed to inject into scintillation cocktail. The samples can then be counted across several more days by LSA. Because of the low activity levels, the samples may be counted for extended periods of time (2 h each) to obtain count rates, which may then converted to net count rates and ultimately decay units (Bq).
[0085] The decay rates from the LSA samples described above can be converted to decay rates for each analysis date; .sup.90Y product fraction activity (Bq) results are displayed in
TABLE-US-00011 TABLE 12 Elapsed time between LSA count results shown in FIG. 17 and initiation of the tandem column purification. Approx. elapsed days to LSA count Run ID Apr. 24, 2019 Apr. 29, 2019 May 2, 2019 1 68 73 76 2 63 68 71 3 62 67 70 4 57 62 65 5 56 61 64
[0086] The LSA data in
[0087] Stocks of .sup.90Sr bearing material can be considered a consumable item in the described process; some losses of .sup.90Sr will be anticipated with each .sup.90Y milking cycle. However, it is desirable to retain as much .sup.90Sr as possible at the conclusion of the .sup.90Y separation process. High .sup.90Sr recoveries can be beneficial for at least two reasons: 1) unrecovered .sup.90Sr will require additional purchases to replace losses in the stockpile, and 2) .sup.90Sr activity levels in process effluents and peripheral components will increase the cost of waste disposal.
[0088] Therefore, in addition to obtaining a high-purity .sup.90Y product with high yields, a method that would result in high recoveries of .sup.90Sr at the conclusion of each purification cycle would be beneficial. Ideally, virtually all of the .sup.90Sr would be recoverable in the effluents of the primary .sup.90Y extraction column.
[0089] Activity results of fractions collected during the tandem column purification process (
[0090] The distribution of .sup.90Sr recovered from all the dual-column effluents and peripheral components involved in the tandem column purification process are listed in Table 13. The top shaded row provides the determined spiked activity of .sup.90Sr injected into each of the five runs; they range between ˜400 and ˜770 μCi. The row in bold reports the .sup.90Sr activity recovered in the column 1 .sup.90Y load/wash effluents. The bottom shaded cell provides the sum of all .sup.90Sr accounted for during the tandem column purification process.
TABLE-US-00012 TABLE 13 Determined .sup.90Sr activities (μCi) in each portion of the tandem column purification process, including fluidic system rinses and spent columns. Recovered .sup.90Sr activity in Col. 1 load/wash is in bold. Run 1 Run 2 Run 3 Run 4 Run 5 Elapsed days .sup.a 59.0 53.9 52.9 48.3 47.4 Units μCi Injected activity 3.96E+2 7.41E+2 7.66E+2 6.82E+2 7.02E+2 reference .sup.b, c (2.12E+0) (2.12E+0) (1.56E+0) (8.85E−1) (5.05E−1) C1 Load/Wash 3.84E+2 7.25E+2 7.45E+2 6.82E+2 7.34E+2 C1.fwdarw.C2 Transfer 3.93E−3 1.70E−2 2.31E−2 3.01E−4 1.73E−2 C2 Wash <MDA <MDA <MDA <MDA <MDA C2 .sup.90Y Elute <MDA 5.76E−4 7.35E−4 2.11E−3 2.78E−3 System Rinses 2.16E−1 7.81E−2 8.33E−2 8.43E−3 1.34E+0 Col. 1 1.90E−3 3.85E−3 3.89E−3 4.42E−3 1.23E−3 Col. 2 <MDA <MDA <MDA 1.08E−5 <MDA Sum of fractions .sup.d 3.85E+2 7.25E+2 7.45E+2 6.82E+2 7.35E+2 .sup.a Elapsed time at which activity values were obtained. .sup.b Small aliquot of the original .sup.90Sr/.sup.90Y column load solution, extrapolated to total load volume. .sup.c Mean and (±1 s) values obtained from replicate measurements taken throughout the study interval. .sup.d Activity sum across all collected and analyzed column effluent fractions, system rinses, and spent columns.
[0091] The data in Table 13 illustrates that virtually all of the .sup.90Sr activity was accounted for in the column 1 load/wash fraction. The fractions with the next-highest .sup.90Sr activities contained levels that were ≤1.8×10.sup.−3 relative to the load/wash fraction (see “system rinses” in Run 5).
[0092] The data in Table 14 summarizes the .sup.90Sr yields across each of the five runs. First, the fraction of .sup.90Sr accounted for in the Table 13 “sum of fractions” vs. the “injected activity reference” values. Overall, it can be possible to account for 99.4±3.2% of the .sup.90Sr relative to the reference aliquots that may be sampled prior to initiating the .sup.90Y purification process. The relative uncertainty of ±3.2% can be employed to assign uncertainties to the .sup.90Sr activities accounted for in the “column 1 load/wash” fraction. Based on this, a mean .sup.90Sr recovery of 99.3±3.1% in the column 1 load/wash effluents across all five runs can be obtained. Virtually all of the .sup.90Sr injected into the .sup.90Y purification process may be recoverable in the fluids emerging from the primary Ln Resin column.
[0093] In compliance with the statute, embodiments of the invention have been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the entire invention is not limited to the specific features and/or embodiments shown and/or described, since the disclosed embodiments comprise forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents.